DE1811013C3 - Polishing preparation - Google Patents

Description

Ii) 10 to 100 parts by weight of an un-

'Soluble addition polymer that by

. * Emulsion polymerization at least one

moaoäihylenisch unsaturated monomers

has been received

b) 0 to 50 parts by weight of an alkali-soluble . Resin, provided that the

alkali-soluble resin not in an amount of> ■ more than 50 percent by weight based on the weight of ä) is present,

c) 0 to 90 <> part by weight of a wax,

d) Benetznngs-, emulsifier and dispersing agent in an amount of 0.5 to 20 _m per cent by weight based on the sum of a), b) and c), and

e) at least one complex of a polyvalent metal in an amount of about 1 up to 50 percent by weight, based on a)

characterized in that the multivalued Metal complex is a polyvalent metal chelate a bidentate ammonium acid ligand or a polyvalent metaUammonium chelate Lines is bidentate amino acid ligands.

2. Preparation according to claim 1, characterized in that the polyvalent metal cation of the polyvalent metal complex consists of zinc

3. Preparation according to claim 1, characterized in that the ligand of glycine, alanine, / f-aanine, VaUn, leucine, proline or phenylalanine consists

4. Preparation according to claim 1, characterized in that that the polyvalent metal complex consists of zinc glycinate.

soil, where

sÄtssaKÄ

Öberzge with gianzenaem ex-

ρ «« i beKanni. a »rm <v« ~~ i.; --—

κ- t ^ J ^ Tverwendai, which is an aqueous polymer, o ready to use ^, _{ösHchen Emu} ] _sions .

of an In ₁ What ^ _{n | ύωπωωΜ? Haf2} , polyvalent me-

the

^ A lack of perspective on the use of polyvalent metal compounds.

rUS-PS 3308078 as well as in »Paint Manu- <November 1? 66. Pp. 58 to 60 and 63 and 64, 'also damaged polishing preparations of the type mentioned at the beginning, to which, however, the SSE adheres that their quality of detergency & * renewed coatability as well as their good removability is not yet completely guaranteed.

The invention relates to a polishing preparation comprising a coating film with a Knoop hardness number of capable of forming at least 0.5 and

a) 10 to 100 parts by weight of emetin water-insoluble ÄadiÜunspuiyiircicH, uöö oi »« »· ^ SSJi.-

Sion polymerization of at least one monoethylenically unsaturated monomer has been obtained is

b) 0 to 50 parts by weight of an alkali-soluble resin, provided that the älkalüosliehe Resin not in an amount greater than SO% by weight based on weight

- yonä), vcrigt,

'cj 0 to 90Gewichtsteile a wax dBeireizBiigs-, Ensalgienjngs- and dispersing tftoA in an amount of 0.5 to 20Gewichts-, percent, based on the sum of a), b) and c), and

Containing) at least one Kompjex a polyvalent metal in an amount of unf "^ \ a 1 to 50 weight percent, based on a).

Aoe of the invention is therefore the creation of a polishing preparation of the type described at the outset, which produces coatings with a high gloss and high detergency, with the fact that a layer that has been applied can be easily re-coated and applied layers can also be easily removed. According to the invention, this object is achieved in that the polyvalent metal complex is a polyvalent metal chelate of a bidentate amino acid ligand or a polyvalent metaUammonium chelate of a bidentate amino acid ligand. According to the invention, in contrast to the known preparations, ier metal complex does not reduce the gloss of the coated substrates. Coatings produced using the preparation according to the invention can be carried out using practice. ⁿ Remove ammonia-containing cleaning agents, but these coatings are resistant to attack by detergents such as those commonly used in households. The preparation according to the invention contains water up to a total solids content of 8 to 45%. The total of components A, B and C should be 10%. The amount of component C can be between 1 and 50% based on the weight of the copolymer component A, the amount preferably being about 5 to 25% based on the weight of the copolymer component A.

To produce a non-polishable, self-shining preparation, the wax should not be in an amount of more than 35 parts by weight, preferably 0 to 25 parts by weight, per 100 parts of the poly

mereß 'plus wax are available. Satisfactory non-polishable floor polishing formulations have been obtained without the addition of a wax is therefore not an essential component of a self-shining preparation. To produce a polishable polishing preparation, the wax should be present in at least an amount of 35 parts by weight, based on such a total amount. Examples of wetting and dispersing agents are alkali and amine salts of higher fatty acids with 12 to 18 carbon atoms, such as sodium, potassium, ammonium or morpholine oleate or ricinoleate. The usual nonionic surface-active agents can also be used. An additional wetting agent improves the application of the polishing agent.

To polish floors, the coating, welctiar is obtained from the preparation, a Knoop hardness steel from 0.5 to 15, measured on one Have a film with a thickness of 12.5 to 62.5 μ on glass. This hardness range enables good abrasion and wear resistance * .. It can pass through achieve an appropriate selection of the monomers to be polymerized.

The polyvalent metal chelate used according to the invention consists of a polyvalent metal, an organic two-like amino acid ligand and, if the chelate, the preparation in solubilized Form is added, an alkaline part. The polyvalent metatlionesi grains * from beryllium, Cadmium, copper, calcium, magnesium, zinc, zirconium, barium strontium, aluminum, bismuth, antimony, lead, cobalt, iron, nickel or one of them other polyvalent metal exist, which the preparation in the form of an oxide, or hydroxide of a basic, acidic or neutral salt can be added, the added compounds must have such a noticeable solubility in water that at least about 1 percent by weight is. The alkaline portion can consist of ammonia or an amine. The bidentate amino acid ligand preferably consists of an aliphatic amino acid, but it can also be a heterocyclic amino acid.

The bidentate amino acid ligands can be represented by the formula

R,

NI-R.-Γ

OH

". Reproduced in which R ₁ and R 2 independently y-ii ^ p each other for hydrogen, alkyl, phenyl or benzyl '" ^, R _{1 is} a straight or branched alkyl, yijAlityHden or aralkylidene radical with 1 to 12 carbons Molecular atoms, preferably 1 to 6 carbon atoms, "," means, provided that at least one carbon atom, but less than 4 carbon atom, is present in a straight chain, which: V 'connects the nitrogen atom to the carbonyl atom,' - "V and R ₁ and R _{3 can represent} a 5- or o-membered heterocyclic ring with the nitrogen atom to which they are ί linked, with the proviso that R _{2 is} hydrogen. If Ri and R _{2 are also} preferably hydrogen, there are suitable substituents of this type nevertheless also from alkyl radicals with 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl and butyl. R ₃ is preferably methylene, but can also be made from ethylene, propylene, ethylidene,

n-Pfopyliden, isopropyliden, Butyliden or Phenyläthyliden exist.

Representative bidentate amino acid ligaments are for example glycine (aminoacetic acid), alanine (tt-aminopropionic acid), / Ϊ-alanine (/ (- aminopropion-

acid). Valine («-iso-propylaminoacetic acid), norvaline (a-ii-propylaminoacetic acid), «-aminobutyric acid, Leucine (2-amino-4-methylpentanoic acid), norleucine (2 - aminohexanoic acid), N - methylaminoacetic acid, N -ethylaminoacetic acid, dimethylaminoacetic acid, Diethylamine acetic acid, N - η - propylaminoacetic acid, N-iso-propylaminoacetic acid, N-butylamine, inoacetic acid, phenylalanine, N - phenylaminoacetic acid, N - benzylaminoacetic acid, proline, nicotinic acid and tetrahydronicotinic acid.

Preferred polyvalent metal complexes are, for example, cadmium glycinate, nickel glycinate, zinc glycinate, zirconium diycinate, cobalt alaninate, copper alaninate, zinc alaninate, zinc alaninate, zinc / i-alaninate, nickelnon / alinai zinc valinate and copper di- methylaminoacctate.

The complex or coordination compounds of polyvalent metals are in the beginning aqueous medium of the polishing preparation in a simple V / ice soluble, in particular at a pH of 6.5 to 10,5, i'nd have the advantage that they create a *. Dry the polishing coating that is essentially is insoluble in water but still removable. The multi-valued metal! containing complex can also the water-insoluble emulsion copoly mers are added in solubilized form. this is achieved in that the nitrile complex in an alkaline solution, for example in dilute aqueous ammonia, is solubilized. Since that Ammonia containing a polyvalent metal trending coordination connection form a complex Because of this, a compound such as cadmium glycinate, after it is solubilized in an aqueous ammonia solution, can be referred to as cadmium ammonium glycinate. Other complexes

of polyvalent metals, as they are according to the invention bescl live can be referred to in a similar way.

The complexes containing a polyvalent metal must be stable in an alkaline solution.

However, a complex that is too stable is undesirable because diaaoziaiicr. of the allions during the Film formation of the coating would be delayed.

The amount of the polyvalent metal-containing compound added may be from about 1 to 50 percent by weight, and is preferably about 2 to 20 percent by weight, based on based on the weight of the water-insoluble addition polymer in the formulation. The ver turned, obtained by emulsion polymerization Polymers insoluble in water must have such a hardness that the preparation containing this polymer contains a film having a Knoop Hardness Number (KHN) of at least 0.5, and preferably about 1.2 to 15 forms. In many cases, the Knoop hardness number of the applied coating film can be 16 or be more if this number is on a film with a thickness of 12.5 to 62.5 μ on a glass plate

is determined. The emulsion co-polymer should also a minimum film forming temperature (MFT) of less than about 85 ° C, and preferably less than less than about 80 ° C.

The water-insoluble polymer can be prepared by emulsion polymerization of one or more monoethylenically unsaturated monomers, for example by emulsion polymerization of acrylic esters of acrylic acid or methacrylic acid, the alcohol content of the ester of methyl alcohol, phenol or a saturated " - · '- τ'·; en aliphatic alcohol, especially t '". · i with 1 to 8 carbon atoms, such as * ■ · j? Cyclopentanol, cyclohexanol, methane ',. ■ a; "n-propanol, isopropanol, n-butanol, isobutane oil, sec-butanol, tert-butane ¹ , one of the pentanols, hexanols, octanols, decanols, dodecanols, oxadecanols or one of the octadecanols. Preferred polymers are copolymers which contain at least one of these esters of acrylic acid with one or more monomers consisting of (C ₁ -C ₄ ) -alkyl methacrylates, acrylonitrile, methacrylonitrile, vinyl acetate, styrene, vinyl toluene (o-, m- or p-), vinyl chloride or vinylidene chloride In place of part or all of the acrylic ester component, the preferred type of polymer may include (Cs-CjsJ-alkyl methacrylate. Mixtures of these copolymers can be used. The polymers can also be graft copolymers, including grafts of the mentioned monomers onto shellac.

The polymers can contain 1 to 18% of a monoethylene unsaturated acid, such as maleic acid, fumaric acid, aconitic acid, crotonic acid, Acrylic acid, methacrylic acid or itaconic acid, the latter three acids being preferred, contain, around the applied coatings in a simple manner by allowing an alkaline medium to act, for example a dilute aqueous ammonia to remove. If necessary, it can Polymers in minor amounts, generally less than about 10% and preferably about 1 to 6%, polymerized units contain at least one monomer containing the amine runpen to the applied coatings in a simple manner by the action of acidic media, for example from dilute aqueous acetic acid solutions. Examples of amine-containing monomers are: One of the vinyl pyridines or a compound of the formula

Alkylengruppc with 2 to 10 KdliletiMlolultUiiiuij ^ | «symbolized. The substituents IK ₁ küimuii fti; | jjl | _r , |, different occurrences in the juw «illpi | V (Ji JÜH> fertilize be identical or different. Examples of monomers of the Ftirniul 1 ftlml ·

N- (3-Dimeihy! Air.ino} -propylrni: tIiuut'yllil,

terL-butylaminoethyl methacrylate.

Dimethylaminoäthylmclhacrytot,

N-C / i-DimethylaminoMthylJ-acryliutilil,

N - (/ i-DimethylaminoäthyI) -mcthatiryliiiviliJ,

10-aminodecyl / ynyl ether,

10-aminodecyl vinyl sulfide,

8-aminooctyl vinyl ether,

Diethylaminohexyl methacrylate.

Diethylaminoethylvinylether,

Diethylaminoethylvinylsuliid,

5-aminopentyl vinyl ether,

3- aminopropyl vinyl acetate jr,

2-aminoethyl vinyl ether,

2-Aminoätliylvinylsulfid,

2-aminobutyl vinyl ether,

4-aminobutyl vinyl ether,

Dimethylaminoethyl methacrylate,

Dimethylaminoethyl vinyl ether,

Dimethylaminoethyl vinyl sulfide,

N- (3,5,5-trimethylhexyl) aminoethyl vinyl ether N-cyclohexylaminoethyl vinyl ether, /i-(tert.-butylamino) ethyl acrylate, 2- (l, l, 3,3-tetramethylbutylamino) -ethyl-

methacrylate,

N-tert-butylaminoethyl vinyl ether, N-methylaminoethyl vinyl ether, N-2-ethylhexylaniinoethyl vinyl ether, N-tert-octylaminoethyl vinyl ether.

Other amines fall under the formula

(II)

(R °) "

(I) where R 'is H or alkyl of 1 to 12 carbon atoms and η is an integer from 1 to 4. Examples are:

2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, 5-methyl-2-vinylpyridine, 4-met'wiyl-2-vinylpyridine, 2-ethyl-5-vinylpyridine, rihlSil

where R .ur H, Cl or CH ₃ , R _{2 is} H or saturated hydrocarbon groups with 1 to 10 carbon atoms, such as methyl, ethyl, butyl, 2-ethylhexyl, cyclohexyl or tert-octyl, A - O-, S,

Il

-C-O-SAS.oTetray

3-eth> 1-5-vinylpyridine,

S'-Ätfayl-S-vinylpyridine,

2> diethyl-4-vinylpyridine,

2-IsopΓopyl-5-vinylpyridin,

2-methyl-5-undecyl-3-vinylpyiidin,

SDdlAvinylpyridine

or

OR ₂

Il I

-C-N-

65

and R 'is a straight-chain or branched S-dodecylAvinylpyrid,

2,4-dimethyl-5,6-dipentyl-3-vinylpyridine,

2-decyl-5- (o-methylvinyl) pyridine.

Further examples of monoethylenically unsaturated monomers which lead to the formation of water-insoluble addition polymers can be copolymerized, are partial esters of unsaturated aliphatic dicarboxylic acids,

11th

the alkyl half esters of such acids may be mentioned in particular - Examples of such partial esters are alkyl halo esters of iteconic acid, fumaric acid and maleic acid, where ^{T contains} the alkyl group libiseesi carbon atoms. Representative examples of these compounds are methyl acid itaconate, butyl acid jtaconate, methyl acid fumarate / i-butyl acid fumarate, and methyl acid maleate. "" ■ '■ "'

the relative proportions of the polymer are in the preparations according to the invention the wax between 100: 0 to 10:90 by weight, and preferably between about 40:60 and 95: 5.

Changes in these relative proportions create different polishing properties. The amount one or more emulsifying or dispersing agents generally varies from 0.1 to 30 and preferably from 1 to 25% based on the combined weights of the copolymer and of the wax. The concentration of the aqueous dispersion can be between a solids content of 8 and 45%, and preferably varies from about 10 to 20 weight percent solids. The dispersion should have a pH of at least about 3.0 have, the pH up to 11.0 or above 2s can be. Most advantageously, the pH will vary from about 7 to about 10, since the maintenance of lower pH values the use of a nonionic emulsifier for the wax requires and generally the addition of a substantial amount of ingredient C of the above Table excludes The most common wax emulsions available are based on alkaline dispersants, so a pH of 7-10 is normal is most convenient. For special purposes, however, the pH can also be between 3 and 6.5. In the event of of vinyl acetate copolymers, a pH in this range initiates hydrolysis of the vinyl ester units a minimum. Suitable alkaline agents or buffering agents such as borax, sodium hydroxide. Ammonia, or amines, can be used to Adjusting the pH to the desired value can be added.

The copolymer is preferably prepared by emulsion copolymerization of the various monomers in the appropriate proportions; customary emulsion polymerization methods are described in U.S. Patents 2754280 and 2795 564. The monomers can be emulsified with an anionic, cationic, or a nonionic dispersant, about 0.5-10% of which is used based on the weight of the total monomers. The acidic monomers or the amino acidity! (fells, see Monomers Used) are of course soluble in water, so the dispersant serves to emulsify the other monomers. A free radical generating type polymerization initiator such as ammonium or potassium persulfate can be used alone or in conjunction with an accelerator such as potassium metabisulfite or sodium thiosulfate. The initiator and accelerator, commonly referred to as catalyst, may be used in amounts of from ^l / ₂ to 2%, each based on the copolymerisiercnden be monomers, based on the weight. The temperature can vary from room temperature to 60 ° C or above.

Suitable anionic: dispersants are, for example, the sodium salts of the higher fatty acid sulfates, for example those of lauryl alcohol, the higher fatty acid salts, for example dieiOleate or Stezrate? of: -Morpholine, 24PyTrOUdOn; "Triethanobmini or mixed ethanolamines, -or non-ionic types such as - modified alkylphenols, * of which itert-octylphenol modified by 20 to 40 ethyl oxide units, representative is ethylene oxide-modified higher Fatty alcohols, such as, for example, lauryl alcohol, which contains 20 to 50 ethylene oxide units, in a similar way Wisely modified long-chain mercaptans. Fatty acids, amines or the like.

The polymer is initially made by emulsion polymerization with exclusive use If an anionic emulsifier is prepared, then it may be advantageous to add a nonionic emulsifier to the polymer dispersion before the addition the compound that makes the polyvalent metal cations available to add. The amount The nonionic emulsifier required depends on the amount of anionic present Emulsifier and the amount of the compound containing a multipolar metal to be added away. In general, 0.1 to 10% or more of the nonionic surfactant is sufficient.

If the wax (if one is used) is dispersed separately, then in a similar manner the above-mentioned dispersants can be used, but also amine salts of soaps, such as ethanolamine oleate or stearate, have been shown to be very satisfactory. Suitable homogenizing mills can be used to promote dispersion.

The waxes or wax mixtures that can be used are vegetable waxes, animal, synthetic and / or mineral origin or mixtures of such waxes, such as for example carnauba wax, candelilla wax, Fischer-Tropsch wax, microcrystalline wax, lanolin, cocoa butter, cotton acne wax, stearin wax, Japanese wax, myrika wax, myrtle wax, macis wax, palm kernel wax, beensa wax , pure whale fat, Chinese insect wax, Algae, oxidized polyethylene wax. Polyethylene emulsions, polypropylene, copolymers of ethylene and acrylic esters and acids, waxes which are hydrolyzed by coconut or soybean oils are preserved, as well as the miceraüschen waxes, such as paraffin, caresin wax, montan wax, ozokerite wax or the like.

The preparations are suitable for the formation of clear and glossy coatings. However, if necessary also a semi-thick AösrasS or an as » transparent or colored appearance due to the addition of matting agents, soluble in water or oil-soluble dyes, pigments or fillers can be achieved in appropriate amounts. Examples of suitable water-insoluble pigments which can be used are titanium dioxide. Carbon black, iron blue, phthalocyanine blue and green, metal oxides, hydroxides, sulfides, sulfates, silicates and -chromates, organic maroon colors, Aluminum flakes, bronze powder, fish silver and various fillers or extenders such as talc, barite, clay or diatomaceous earth.

709 625/72

P ^w ίο

The amount of pigment can vary triicuiich, 50%, based on the weight of the copolymer.

depending on the desired effect. The examples of wax soluble materials are terpenes?

Amount by weight of the pigment, based on the amount of phenolic resins, hot process ("run") - Congo, wood colo-

Wfcht dea organic, film-forming material, can phonium or the like. In general, the alkali = ·

between about 2% for light, highly hiding 5 soluble resins acid numbers of about 100 to

«Gmait ^ such as carbon black ^ andi about 100% 300 and average molecular weights of

you heavy, weakly opaque! pigments, like at-about -200 to about 50ΛΟΟ and preferably

ipieSe two lead chromate, fluctuate. about 800 to 5000.

"The ^ äSrigea DispefaoaeaiäöaaeH ba about examples door alkali-soluble resins are shellac,

75 percent by weight, based on the total weight ro Manilagum, Lobagum, copolymers of styrene or

of A, B and C, contain a plasticizer, provided Viayltoluol with at least one α, / f-monoethylene

such a plasticizer for a particular unsaturated acid or anhydride, such as

Purpose of use is to be added to a spatula-wise styrene / acrylic acid resin or styrene / material

Lower temperature of the film formation from the emulic anhydride resins. In addition, alkaline

to be able to adhere to sion polymer dispersions. 5 15 soluble alkyds in question, which are essentially poly-

up to 35 percent by weight of the plasticizer, based on esters of aliphatic dicarboxylic acids with aliphatic ones

• On the weight of the copolymer, are common. represent polyhydric alcohols and with C ₈ -C ₈

Since the purpose of the plasticizer is usually in fatty acids, glycerol esters of Q-Qe fatty acids and consists to facilitate the film formation, uid since there are resin acids such as abietic acid or • It is not always necessary to use the copolymer preparation 20 rosin, which can be modified in the tang, if tough and pliable, a pliability resin described in U.S. Pat. No. 2,063,542 To lend, as is often the case, a can can be used. Examples of dicarbon Maleic acid, fumaric acid, adipic acid are some of the most volatile or color-volatile plasticizers nal instead of a permanent plasticizer and sebacic acid and its anhydrides. That are more drawn. However, permanent soft alcohols can be obtained from glycerine pentaery Can also be used without producing films such as trimethylolethane and glycols with 2 to 8 carbon atoms, which have poor smoke resistance, including dietary glycol and and poor water resistance to triethylene glycol

Other alkali-soluble resins are rosin

■ is relatively low in most cases and 30 maleic anhydride adducts, which are mo-

ni are generally not differentiated above about 30 weight, as well as rosin-fumaric acid-ad-

percent based on copolymer solids. products which are modified with polyols

_k Certain plasticizers, such as trisentative polyols, are ethylene glycol, glycerine,

butoxyethyl phosphate, also serve as gradient pylene glycol, pentaerythritol and mixtures of these

«Ittel. Mixtures of volatile and permanent 35 of these compounds. The alkali-soluble resin will

Plasticizers can also be used. generally the polishing formulation as a resin compound Certain existing ai »fluorohydrocarbons were added. Such a blend is one

Surfactants also act as an aqueous alkaline solution, which by solubilization

hoofs. Che ^ Matenalien are m the USA, - of the alkaline resin with an alkaline sub-

PatOTtschnft 2-37 098 described. 40 punch, such as ammonium hydroxide, Examples of thick plasticizers are the mono- will hold. uiuuyuiuAju,

ethyl or monomethyl ether of diethylene glycol. The concentration of the aqueous dispersion

^ phoren, benzyl alcohol and 3-methoxybutanol-l. fluctuates appropriately for application

Examples of essentially permanent soft between a solids content of 8 to 45 weight

A few which are suitable according to the invention are 45 percent and preferably from about 10 to 20 percent

Benzyl butyl phthalate, dibutyl phthalate, dimethyl weight percent l uu _S «am iuuuiuu

ίϊ! ⁴ ! ^ J ¹ Sa * ¹ ?? ⁰ ^ . 2-Athylhexylbenzyl- Di _e preparations can for impregnating

phthalate, butyl cyclohexyl phthalate, mixed ben- textiles, leather, paper or other such

: zoesaur _e - and fatty acid esters of pentaerythritol, materials are used. You can also use luf

/Poly-ipropylenadipatHl.benzoat, Dietylen ^ ykold, - 50 plastic films, such as cellophane, poly-

oenzoate, leiraDuxyitniomsuccmat, uutyipntnaiyi- äthylen, Polyäthyleneglyko'ltereohthalat. Sara death. del

butyl glycolate, acetyl tribu ^ lcitrate, Dibe ^ ylseba ^ t, «Ä» ^ U3SK2SSSfÄSfco £:

Tncresylpnosphat, Toluolathykulfonamij the d, - surfaces are applied, on all metals,

2-ethylhexyl ester of hexamethylene glycol diphthalate, such as steel, aluminum, and brass. dWethylcycl ^ ₅₅ Bronze ^ Tin, ChroT ^^^ SS 'SS

phate and butyl phosphate. The respectively used one Aufb ringun g ^ u

_: Plasticizer as well as the amount in which it is incorporated- Glass, 'ΜΪΖ ££

lhk

^ ird, depending on the contractability as well as the cement and concrete surfaces, as for example

Efficiency with regard to the reduction of the film floors, or the like, possible. The preparations are

educational machine selected 60 especially suitable for polishing floors, for example

-; In addition to the copolymers, the MetaHkompIex and wise made of wood, linoleum, rubber and all of them

a suitable dispersion or emulsification type of plastic material, for example made of lin-

medium as well as the optionally added wax, leum, asphalt, vinyl and vinyl / asbestos

, Pigments and the fillers, as above examples of wetting and wetting agents

_; remembers, the inventive preparations 65 are alkali and amine salts with higher fitness acids

'' also contain other components, for example 12 to 18 carbon atoms, such as Na

• Resins or gums which can be removed from wax or alkali, potassium, ammonium or morpholine oleate

Soluble resins, in an amount from 0 to or -ricinoleaL. In addition, these can be used

Ιθ 11 013

nonionic surfactants in question. An additional wetting agent improves the spreadability of the polishing agent.

For polishing floors, the coating obtained from the preparation should have a Knoop hardness number of 0.5 to 15, measured on a film with a Thickness of 12.5 to 62.5 μ on glass. This The hardness range enables good resistance to wear and tear. He can get through an appropriate selection of the monomers to be polymerized can be achieved. . The copolymer and wax (and resin, if used) can be mixed in any order desired. For example, the wax or the resin in the aqueous Polymer dispersioa by adding a dispersion of the wax or resin or by adding both Components are added to the copolymer dispersion or vice versa. Preferably that will Copolymers are added to a dispersion of the wax, whereupon the resin is mixed in. The wax dispersion can be made using the anionic or nonionic dispersants as mentioned above for use in copolymerization. However are also Amine salts of soaps, such as, for example, ethanolamine or morpholine oleate or stearate, are satisfactory. In addition to the incorporation of wax into floor polishing preparations, another plasticizer can be used or a volatile flow aid can be used, in order to achieve the desired minimum film-forming temperature of the preparation.

The complex containing a polyvalent metal can be added to the preparation at any point in time during the formulation. In general it is expedient to add this complex containing a polyvalent metal to the water-insoluble addition polymer.

The formulations have good storage stability under normal temperature conditions. They can be applied in the usual way by wiping cloths, by brushing on or using cleaning rags. They dry up quickly clear or, if pigmented, too opaque films and have hard and tough glossy surfaces. Generally occurs with aging no discoloration of the films. By applying the preparations to surfaces that have previously applied coatings made of alkali-removable s wear preparations, no noticeable amounts of such coatings are removed affects the viscosity or consistency of the preparation according to the invention in a disadvantageous manner. The preparations can be applied to surfaces in a uniform and simple manner, without stripes or other irregularities appear.

h The preparations which contain copolymers which contain carboxyl groups (acid or salt) can be removed by certain ammonia-containing cleaning agents such as ammonium hydroxide or tetramethylammonium hydroxide, as will be explained in more detail below. Amines such as monoethanolamine can also serve as stripping agents. The following examples, in which the parts and percentages are by weight, unless otherwise stated, illustrate the invention.

Example I.

a) An emulsion copolymer is made using 2% sodium lauryl sulfate (based on the

s total weight of monomers) as emulsifier and prepared in compliance with a customary emulsion polymerization method, the copolymer has (in percent by weight) the following composition ' setting:

Methyl methacrylate 55% Butyl acrylate 38% Methacrylic acid 7% The final polymer solids content of the emulsion is

is 40%. The emulsion wi i with water on one

Polymer solids diluted by 15%. The pH

the emulsion is made using 14%

NH ₄ OH adjusted to 6.5.

b) A mixture of 40 parts of an emulsifiable low molecular weight polyethylene, which melts at about 75 ° C, and 8 parts of oleic acid is melted and 8 parts of morpholine are added to the mixture. The finished melt is slowly added to 184 parts of water heated to 95 ° C. with vigorous stirring. the The emulsion is allowed to cool and then diluted to a solids content of 15%.

c) A resin blend solution containing 15 parts of a alkali-soluble glycerine-modified rosin /

Contains maleic anhydride adduct, this adduct having a molecular weight of about 1000 and an acid number of about 140, in 62.5 parts of water, which contains 3.75 parts of a 28% NH ₄ OH solution, by heating the mixture 50'C manufactured. The solution obtained is filtered and then diluted to a solids content of 15%.

d) 72.5 parts of the final polymer dispersion according to a) (Solids content 15%) are made with 11 parts of the wax emulsion according to b) (solids content 15%) and 16.5 parts len the alkyd solution according to c) (solids content 15%) mixed. The mixture obtained is further through the addition of 0.35 parts of tributoxyethyl phosphate, 1.5 parts of diethylene glycol monoethyl ether, 1.5 parts

Ethylene glycol, 0.6 parts nonylphenol, modified having an average of 10 ethylene oxide units, and 0.004 part of a fluorinated hydrocarbon surfactant of formula

C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) CH ₂ COOK

hereinafter referred to as surfactant F, modified.

e) 50 parts of the floor polish obtained by adding 2.55 parts of zinc ammonium Niumalaninat modified. The zinc ammonium alaninate is made by mixing 42 parts of alanine, 40 parts of a 28% ammonium hydroxide solution, 22 parts of zinc oxide and 100 parts of water up to Obtaining a clear homogeneous solution made.

f) A homogeneous vinyl floor tile with a dimension of 228 χ 228 mm is divided into two equal Parts divided. One half will be at a thickness of 37.5 μ coated with the finished floor polish according to d), while the other half has a coating with a thickness of 37.5 μ a »- * s the zinc calanate-modified polish according to e)

A period of 60 minutes at 25 "C with a relative The flow halves become moisture of 50% coated again with the corresponding formulations in a thickness of 37.5 μ. Included the following observations are made: s

■ l'ß Bie -with der'Fußbodenpölituf, the soft contains Zinkalariinat) coated tile, in comparison with the with the yergtekhspeütür d>, which contains no metal complex, coated tile already bsi the application of a layer of a good gloss.

2. The polish containing zmkalaninat can be tn Excellent way to coat again, while the comparative polish is dull, has many rough spots and is difficult to recoat. This is undoubtedly due to an irregular part redispersion of the first polishing coating when a new coating is applied.

3. The metal-containing polish has a water resistance kit, which is equivalent to that of the comparative polish.

4. The comparative polish has no detergency, while the metal-containing system exhibits a high degree of detergency resistance.

5. Both floor polishes can be easily done using a 3% aqueous Remove ammonium hydroxide solution.

Test methods for the investigation of soil politicians, namely to determine the water resistance, the detergent resistance, the gloss, the Removability, re-coatability and film hardness are discussed in detail in "Resin Review". Vol. XVl, No. 2, 19bo, published by the Rohm and Haas Company, Philadelphia, Pa. 19 105, described.

and a common emulsion polymerization method is observed:

Example 2

The polymer dispersion from Example 1. Part a), diluted to a solids content of! 5%, is in formulated as follows:

Polymer dispersion (solids ^{content, part}

15%) 100

Tributoxyethyl phosphate 0.8

Diethylene glycol monoethyl ether 1.5

Ethylene glycol 1.5

Surfactant F 0.6

Zinc alaninate (solubilized in ammonium hydroxide) 3.0

pH adjusted to 8.9

Ethyl acrylate 42%

Methyl methacrylate 53%

Methacrylic acid 5%

The final polymer solids concentration of the emulsion is 33%. The emulsion is made with water diluted to 15% polymer solids. 100 parts of the emulsion are through the Addition of 10 parts of zinc ammonium alaninate, prepared according to the method of Example 1 e), modified.

b) 80 parts of the polymer dispersion from part a) are with 20 parts of an alkali resin, namely a styrene / acrylic acid copolymer resin with a Molecular weight of about 2500 and an acid number of about 205. The mixture obtained is also by the addition of 0.9 parts of tributoxyethyl phosphate, 2.0 parts of diethylene glycol monoethyl ether, 1.5 parts of 2-pyrrolidone, 0.1 part of formalin and 0.4 part of surfactant F modified. The pH of the final formulation is adjusted to 8.7 using ammonium hydroxide. The polishing formulation is investigated in the manner described in Example 1 f), wherein similar results can be obtained.

Example 4

a) An emulsion polymer is made using!% sodium lauryl sulfate with the following composition (Weight percent) produced:

Butyl acrylate 30%

Methyl methacrylate 20%

Acrylonitrile 20%

■ «-Methylstyrene 20%

Methacrylic acid 10%

The final polymer solids content in the emulsion is 40%.

b) 100 parts of the emulsion polymer dispersion according to a) are obtained by adding 10 parts of zinc ammonium / i-alaninate modified and then diluted to a solids content of 15%. then there is a further modification in the following * Veise:

Polymer dispersion (solids ^{content Tcile}

15%) 80

Alkali-soluble resin [Example 1,

Part c)] 8

Wax emulsion [Example 1, part b)] .. 12

Tributoxyethyl phosphate 0.75

Surfactant F 0.5

Diethylene glycol monoethyl ether 1.5

uiäthyiengiykoi 1.5

55

The above polishing formulation is used according to
the method described in Example 1 f) under An investigation of the floor polish after

seeks. Excellent flow properties and the method described in Example 1, Part 0, results in running properties, although the results are similar to the polishing method, and neither wax nor an alkali-soluble resin 60
contains.

jr example 3

a) An emulsion copolymer is produced with the following composition (percent by weight), 3% sodium lauryl sulfate (based on the total weight of the monomer) being used as the emulsifying agent

Example 5

An emulsion sense polymer is made using 1% sodium lauryl sulfate. It owns the following composition (in percent by weight):

Ethyl acrylate 27%

Styrene 68%

Methacrylic acid 5%

The final polymer solids content of the emulsion polymer dispersion is 40%. 100 parts of the emulsion are mixed with 3.3 parts of zinc ammonium N-methylaminoacetate modified and then diluted to a FesisioiFgehali of 15%. Then one follows further formulation in the following way:

Emulsion polymer (solids ^{content parts}

15%) ..... '72.5

Alkyd resin from Example 1, part c) 16.5

Wax emulsion from Example 1, part b) 11.0

Ethylene glycol monoethyl ether 1.5

Diethylene glycol 1.5

Tributoxyethyl phosphate 0.35

Surfactant F 0.4

Dibutyiphthaiate ί, ϋ

Nonylphenol, modified with an average of about 40 oxyethylene

groups (emulsifier) 0.3

The test results are equivalent to the results obtained when the formulation was tested according to Example 1 can be obtained.

Example 6

Cadm: ammonium glycinate is manufactured and used in in the manner described in Example 1, instead of zinc ammonium alaninate, cadmium ammonium glycinate is used is made by mixing 8.4 parts of glycine, 8.0 parts of a 28% ammonium hydroxide solution, 20 parts of water and 4.4 parts of cadmium oxide until a homogeneous solution is obtained manufactured

100 parts of the emulsion according to Example 1, part a), are diluted to a solids content of 15% and modified with 3.2 parts of cadmium ammonium glycinate. The modified ones with cadmium ammonium glycinate and zinc ammonium N-methylaminoacetate Formulations are comparable in terms of their floor polishing properties.

Example 7

A copolymer dispersion is obtained from a mixture in the manner described in Example 3 made from 40% ethyl acrylate, 39% methyl methacrylate, 13% styrene and 8% methacrylic acid. The solids concentration is adjusted to 15% using water.

According to the formulation according to Example 2, the floor polish is according to that described in Example 1 f) Method investigated, with similar results

Example 9

A copolymer dispersion is made from a mixture according to the procedure described in the example from 25% 2-Ethy! hesylasr "! äi, 72% styrene and 3% itaconic acid. Similar results as in Example 1 are obtained if this copolymer is used in both the procedure described in Example 1.

.-

Example 10

a) An emulsion copolymer is made using 4% (based on the total weight of Monomers) Octylphenol, modified with an average of 30 ethylene oxide units, as - emulsifying agent, being a common emulsion polymerization method is applied. The copolymer has the following composition (in percent by weight):

"° butyl acrylate 26%

Methyl methacrylate 20%

Styrene 30%

Methacrylic acid 4%

Methacrylonitrile 20%

The final polymer solids content of this emulsion is 40%. The emulsion is allowed to cool and then diluted with water to a solids content of 15%

b) 100 parts of the emulsion polymer dispersion from a) are further formulated in the following way:

Polymer dispersion (solids content ^parts

15%) 76

Alkali-soluble resin [Example 1 c)], which is 4 parts by weight the polymer dispersion,

Zinc glycinate contains 14

Wax emulsion 10

Diethylene glycol 1.5

Ethylene glycol monoethyl ether 1.5

Tributoxyethyl phosphate 0.5

Surfactant F 0.4

In this example, a modification is carried out by adding zinc glycinate in the form of a powder the alkali-soluble resin blend, which contains such a sufficient excess of alkali that the zinc glycinate is solubilized. Satisfactory results are found.

50

Example 11

35

40

Example 8

a) An emulsion copolymer is made using 3% (based on the total weight of Monomers) Octylphenol, modified with an average of 30 ethylene oxide units, as an emulsifier, using a conventional emulsion polymerization method. It has the following Composition (in percent by weight):

Methyl acrylate 60%

Vinyl toluene 37%

Acrylic acid 3%

b) The emulsion polymer according to a) is used in place of the emulsion copolymer in Example 1. Results similar to those in Example 1 are obtained.

The emulsion polymer of Example I is au! diluted to a solids content of 15%, whereupon 5 aliquot portions with the following metal complexes!], Which are first solubilized in ammonium hydroxide, be modified:

a) cadmium glycinate (2.8 parts),

b) zirconate glycinate (3.5 parts),

c) zinc alaninate (8.0 parts),

d) zirconium-0-alaninate (3.0 parts),

e) copper dimeihylaininose acetate (5 * 5 parts).

Any of the above modified emulsion copolymers is formulated in the following way:

Modified polymer ^{dispersion part}

(Solids content 15%) 80

Alkali-soluble resin [Example Ic)] ... 5

739628/72

η 40

TeOe meren) Octylphenol, modified with average Wax emulsioa [Betspid Ib)] IS 40 EthyienoxydeiiAettcn, al · emulsifier, whereby Multi-valued mulkhdat a) to e) a common EiEuIsiofupolyineriMtioM method. Ethylene glycol 1.5, produced Dm Copolyniere possesses Diethylene glycol monoethyÜtiKT ip S füigeade ZsisssssSsslssüg {in Gtwkhisproscrsi}:

' Tributoxyethyl phosphate 0 ^ 5

- GrenznacheBäiktiws MittelF * ....-. 0.4 AthyUcrylat '. 41%

I An Examination of the BcdoipoUennmittel lidert ^ i ^^ S ^^ ^

Results which correspond to the results given in Example 1, o DSSn ^ noathyimeihacrylai ' WW 2% linsen.

Example 12 q, - »Eodiofl concentration of the emulsion is A mubionscopoiymsres is using 40.0%. The emulsion is mixed with water on a. Poly-

diluted from 6% to the total of the Möco- i $ incissfcsistcfTgchalt of 15%

Claims (1)

r ^ lf- 18 Π Patent claims: ^ i ^ .v polishing spread that has a coating film with a Knoop hardness number of at least 0.5 able to form and