DE1811012A1 - Polishing preparation - Google Patents

Description

Ss is "known as Bo & enpoliermittel a preparation to use ₉ comprising an aqueous polymeric dispersion of a water-insoluble emulsion copolymers _s contains a wax, © in alkslilösliches resin, a Diepergierungsmittel and a compound of a polyvalent metal.! Such compositions are described in US Patent 3 328 described 325th There are also various other polishing compositions are known which contain a water-insoluble Emulsionscopolymeres. These copolymers ^, usually have a ^ t milky-white appearance, the fully formulated © alkaline polishing composition a cloudy suspension is -aid the applied polishing agent dries to form a clear film.

The main aim of the invention is to create polishing preparations which are essentially water-clear solutions. The invention creates a polishing preparation which produces a clear and dry surface which, in an advantageous orphan, has balanced properties with regard to high gloss, resistance to detergent, and renewed smoothness _. Has abrasion resistance, pilm hardness and removability.

The analytical method given below is used to quantitatively determine the clarity of the polishing compositions. For the purposes of the invention, "essentially what is clear" or "essentially clear" is to be understood as meaning the appearance of polishing preparations which contain 15 to 18 $> pesticides and which are measured on a Bausch and Lomb Spectronic 20 colorimeter, which is between 0 and 100 # is calibrated, when using either methanoi or distilled water at a wavelength of 600 ma have a light transmission of at least 50 # contains

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BAD ORIuINAU

and a

t of at least $ 35> owns.

The polishing accessories according to the invention generally have the following composition;

A) Water-insoluble addition polymers

B) wax

0) Alkali-soluble resin

D) Wetting, emulsifying and dispersing agents

E) Polyvalent metal compound

F) water

30-100
Gawioht parts

0 - 70
Part by weight

0-70

Weight part ©

Op5-20 Jf ₉ based on the weight of Α + B + G

1 - 50 °, related to the size of A

Cessation of • your cresam fiber content from $ 8- $ 45>

For the production of non-polishable, glossy drying or elbet polishing preparations, the weight should not exceed 35 parts by weight and preferably 0-25 parts by weight, based on 100 esl of the polymer plus wax according to the formulation in the table above. Satisfactory non-polishable floor polishing formulations could be produced without adding any sines Waohees. Dab.er wax is not an essential component of a self-polishing preparation »To produce a preparation pclierbaren polishing the wax eolith least 35 Gewiohtstail3 ₅ based on such a Gesamtme ^ go, make up.

The water-insoluble polymer which is used according to the invention and is produced by emulsion polymerization,

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must have such a hearing that the preparation in which it is contained, after application in the form of a film, has a Knoop hardness number (KHN) of at least O _f 5 and preferably of about 1.2-16 or above, if the Measurement is carried out on a film on a glass plate having a thickness of 12.5 - 62.5 γ. (O "5 -. 2» 5 mils) which Bas emulsion copolymers should also a minimum fUmbildende (Demperatur (MFI) of less than about 85 ° and preferably less than 0 have approximately 8O ⁰ G, M

The water-insoluble polymer can be obtained by emulsion polymerization at least one hydrophilic monoethylenically unsaturated monomer with at least one hydrophobic monoethylenically unsaturated monomers, for example with acrylic acid or methacrylic acid, the alcohol content the ester of benzyl alcohol, phenol or a saturated monohydric aliphatic alcohol, in particular an alkanol with 1-18 carbon atoms, for example Oyclppentanol, cyclohexanol, methanol, ethanol, n-propanol, Isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, one of the pentanols, hexaioles, octanols, becanols, ^ Dodecancls, hexadecanols or octadecanols, derived from β be asked. Preferred acrylic esters are methyl acrylate, Ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl » methacrylate, ethyl methacrylate and butyl methacrylate.

Are the hydrophilic mono-ethylenically unsaturated monomers a _y S-mono-ethylenically unsaturated acids _? such as acrylic acid, methacrylic acid, sharkic acid, fumaric acid, aconitic acid, crotonic acid or itaconic acid, with methacrylic acid being preferred. Other hydrophilic monoätkyienisch unsaturated monomers are hydroxyalkyl esters of both methacrylic acid and acrylic acid, such as 2-hydrosyethyl methacrylate, 2-hyaroxypropyl methacrylate,

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Acrylamide and methacrylamide. Other hydrophilic unsaturated Monomers are for example the alkyl half esters from Itacou » acid, maleic acid and fumaric acid. Preferred half esters are the lower alkyl ethers (Cj-Cg), such as "for example methyl acid aitate, Butyl acid aoonate, methyl acid fumarate, butyl acid fumarate, Methyl acid maleate or butyl acid maleate.

Optionally usable monoäthyleniech unsaturated monomers ^ those used to produce the water-insoluble addition poly ~ mers can be used »are Monovinyliden-aromatic® ■ Compounds such as styrene and vinyl toluene (o-, m- or p ») as well as acrylonitrile, methacrylonitrile, vinyl acetate, Vinyl chloride or vinylidene chloride, As the pH of the fer * ~ If the daily formulation is alkaline and usually exceeds 7 * 5, a potential hydrolysis of the vinyl ester is used reduced to a minimum.

For the production of the water-insoluble Additionscopolymer® A. the proportion of or of the hydrophilic monomer can be from about 5 - _t, based on the total weight of the monomers vary, $ 15 - 20 i> and preferably from about. 9 The hydrophilic monomer makes it possible for the coatings on the substrate to be removed in a simple manner by the application of alkaline media, such as, for example, dilute aqueous ammonia. The vast majority of the hydrophilic. Monomers is derived from the mono-ethylenically unsaturated acid. The acid content of the water-insoluble addition poly / ~ .meren preferably fluctuates from about 9-15%, based on the total weight of the monomers.

The intrinsic viscosity of addition, which is insoluble in water? - polymer must be between about 0.1 and 0.7, and preferably between 0.15 and 0.40, determined in setrahydrofuran at 20 * 0 ,. lie. Control of molecular weight is required

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~ 5

■ to obtain the desired clarity of the polishing formulation » Chain transfer agents are used to lower and control molecular weight. Suitable chain transfer agents are aliphatic ^ mercaptans, such as n-butyl mercaptan and isopropyl mercaptan, as well halogenated hydrocarbons, such as trichloromethane, Carbon tetrachloride, tetrachloroethane, bromotrifluoromethane and butyl chloride. Other satisfactory chain transfer agents are! thioglycolic acid and isopropylbenzene meroaptoethanol.

View of the addition copolymers which are insoluble in water can be used. The polymers can also be made from graft polymers including grafting of the monomers mentioned on Schsllak. The water-insoluble copolymer, which contains an acid can be soluble in aqueous alkaline media with a pH of 7 »O - 11 or above. Such polymers are nonetheless referred to as in ¥ water insoluble polymers.

The polyvalent metal compound used in the floor polishing formulation can consist of either a metal complex or a metal chelate. The polyvalent metal ions can consist of beryllium, cadmium, copper, calcium, magnesium, zinc, zircon, barium, strontium, aluminum, Wis.amth, Antimony, lead, cobalt, iron, kick! Or any other polyvalent metal, which is added to the composition in the form of an oxide, hydroxide or a basic, acidic or neutral salt. The added compound must have a noticeable solubility in water , namely at least ± n an amount of about 1 wt ^. the selection of the polyvalent metal and the anion is determined by the Iiöslichkeit of Metallkomplexea obtained to a corresponding clarity of the fully formulated polish mi GeV / ährlei-

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BATH ORIGINAL

sten. Zixac and cadmium are particularly preferred polyvalent metals. The Aamioniak- xmd amine complexes. (<,: A3L>3;3O3iai;> re the coordinated with NEW * Complex) of these metals are "particularly suitable amine, which are able to enter into a complex formation, are morpholine, Moaoäthanolnsnin _s diethylaminoethanol and ethylenediamine Polyvalent metal complexes. (salts) of organic acids that are solubilized in sinom alkaline pH range kö "NNAN ₈ can be further used, anions, such as" for example, acetate ₉ - Glutamate, Porraiat, Garbonat, salicylates glycollate ,. Octaat, lBöiiaoat _s Gluoonat, oxalate, and _s lactate are satisfactory .. Mehrv / srtige metal chelates in which represents a ligand sveisälmige amino acid, such as "for example, G-lycine oäex alanine, may also be used warden.

Preferred polyvalent metal complexes and chelates aind beispielsv / siae Zintacetat, Oacliniianiacetat, ZinlL-glyolnat, Ondiniuiaglycinat, Xialicarbonat _v cadmium, zinc benzoate, Zinksalioylat, Zinkglycollat and GadmiumglycollEt. If the polyhydric Mstallverbindtmg the polish composition in dry form, for example in the form of a powder are added KATIN _{y P} it is nevertheless preferable to ₉ ssuerst the polyvalent metal compound using a volatile Iiigands-n to solubiliaisren as beispislavreiss ammonia.

For this purpose, a ligand is considered to be volatile if at least a part of the Mgande-i that heigu possesses evaporates under normal pilfering conditions. If the ammonia is able to enter into a complex with the polyvalent metal compound, a compound such as, for example, cadmium glycinate, if it is dissolved in a Tördünntsri aqueous Axumoniaklösuiig v ± x as Oadmiuffiammoniumglycinat wsrden, ■ -.- -

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- BAD ORIGINAL

The polyvalent metal compound is in such a Amount used that the ratio of polyvalent Me « tall to the α, β-äthylenisoh unsaturated acid of in Water-insoluble addition polymer A and any free carboxylic acid of alkali-soluble iron C present between about 0.1 and 0.5 and preferably between about 0.2 and 0.3 varies.

In the preparations according to the invention, the relative proportions of the polymer to the wax are between 100: 0 and 30:70, based on the weight. Changes in these relative proportions result in different polishing properties. The amount of an emulsifying agent or a dispersing agent or several such agents generally varies between 0.1 and preferably between 1 and 20 ? * _T based on the combined weight of copolymers! » and wax. The concentration of the aqueous dispersion may a Peststoffgehalt of 8 - # 45 have, wherein the .feststoffgehalt preferred rates is about 10-25 G-ewiöiits-ji, rlJLe After dispersion as a polishing composition formulated iertig i £ ₉ st they should have a pH of at least about 7 , 0, but the pH can also be 10.0 or more. Most advantageously the pH will vary from about 8.5 to about 9.5. Suitable alkaline agents or buffer agents manure _r such as borax, sodium hydroxide ,, ammonia or amines may be added to adjust the pH to the desired value.

The copolymer x is preferably made by emulsion copolymers of the various monomers in the appropriate proportions using a transfer agent manufactured. Suitable emulsion polymerization methods are described in US Pat. No. 2,754,280 ■ and 2 795 564 described. The polymerization under

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Use of a chain transfer agent is described by EH Riddle in "Monomeric Acrylic Esters" on pages 56-58 (Heinhold 3 Publishing Corp., Hew York, NY ₀ 1954).

In this catfish the monomers with an anionic or a cationic non-ionic Dispergierungsxoittel © be mulgiert ^, with about O ₉ 5 - 10 ^ ₉ based on the weight of the G-esamtmonomeren used. The acidic monomer is of course soluble in water, so that the dispersing agent! serves to emulsify the other, two-tone tone. A polymerization initiator dee free radical 'type, such as ammonium .or potassium persulfate * alone oäsr in Yerbin & ftng with a Besohleiniger _y such as Kaliummetabisuliit or üTatriwathiosulfat- be used. 3) @r initiator and sliming agent "generally referred to as catalyst, can be used in amounts of 1/2 to 2 #", each based on the G-ewioht. of the monomers to be copolymerized. The temperature can vary from room temperature to 60 ° 0 or above.

Sound suitable Dispergierungsmittelii-be anionic types "such as the Hatritiiasalsse the higher Fetteäuresulfate" such as those of lauryl alcohol, the higher 3? Ettsäur © salse as beiapielsweis © DL® oleates or stearates of Morpholisi _s 2 ~ Pyrroiidon, triethanolamine or overall ® i.schten Ithanolaminen ,, or aalonisehen Sypea "such as ethylene oxide-modifiiaierte alkylphenols wherein _s = ₀ tert Ootylphenol modified with 20 - 40 £ thylenoxydeinheiten representative is £ thylenozyd-modifizlerte higher 7ettalkonole _f. such white Leurylalkohol, the 20 - 50 £ thylenozyd- 'units' similarly includes modifissisrte long chain mercaptans, fatty acids, amines or the like mentioned! ".

If the polymer is initially un ~

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S ORIGINAL

If only an anionic emulsifier is used, it may be convenient to add a non-ionic emulsifier to the polymer dispersion before adding the compound which provides the polyvalent metal cations. The amount of nonionic emulsifier required depends on the amount of anionic emulsifier present and on the amount of polyvalent metal compound to be added. Generally about 0.1-5 % or more of the nonionic surfactant is sufficient. · ■

Will the wax (if used) be separated dispersed, then the mentioned dispersing agents can be used in a similar manner, but using amine salts of soap such as ethanolamine oleate or stearate, are also very suitable. Suitable homogenization mills can be used to support the Dispersion can be used.

The waxes vein the Waohsmisohungen, the present invention can be used are waxes of plant, see of animal M, synthetic and / or mineral origin or blends of such waxes such as carnauba Waohs, Candelilla Waohs, Pischer-JDropsoh wax, microcrystalline wax , lanolin wax, cocoa butter wax, cottonseed waohs, stearin waohs, Japanese wax, myrika waohs, myrtle wax, mace wax, palm kernel wax, beeswaohs, pure whale fat, Chinese insect wax, shaft algae, oxidized polyethylene wax, copolymers made from xylene emulsions and acrylics, polypropylene and acids, Waohse, which are obtained by the hydrogenation of coconut or soybean oils, and the mineral waxes, such as paraffin, ceresin wax, montan wax, ozokerite wax or the like,

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The preparations are suitable for the formation of clear and glossy coatings. If necessary, however, a colored appearance can also be achieved by incorporating water-soluble or oil-soluble dyes in suitable proportions. Examples of suitable dyes that can be used are iron blue, phthalooyanine blue and green, and organic brown® dyes. The amount of dye can vary considerably, depending on the desired effect.

The aqueous dispersions can be up to about 75 weight ^ contain .One plasticizer, if required for a special Anwendungszweak * a deeper temperature of Eilmbildung from the Emulsionspolymerendisper emissions ssu @rzielen _a 5 - 35 weight ^ of the plasticizer, on beaogen the weight of the copolymers are completely sufficient in practice, "

Since the purpose of the plasticizer is generally to facilitate film formation, and it is not always necessary to "impart flexibility to the polymer preparation, " it is itself tough and pliable, as is often the case, can Sometimes a volatile or permanent plasticizer can be used instead of a permanent plasticizer. However, permanent plasticizers can be used without producing films with poor abrasion resistance and thus higher water resistance is low and generally does not exceed about 30% by weight of the polymer solids. Certain plasticizers * such as eributoxyethylphosphate also serve as leveling agents, mixtures of volatile and permanent plasticizers can also be used

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Surfactants also serve as leveling agents. These materials are described in U.S. Patent No. 2,937,098.

Examples of volatile softeners are the monoethyl or monomethyl ether of diethylene glycol, isophorone, benzyl alcohol and 3-methoxybutanol-1. Examples of essentially permanent plasticizers are Seneylbutylphthalat, dibutyl phthalate, dimethyl phthalate, Iriphenylphosphat, 2-lthylhexylbenzylphthalat, Butyloyclohexylphthalat, mixed benzoic acid and EettÖlsäureester w of pentaerythritol, poly (propylene adipate) dibenzoate, Diäthylenglykoldibenzoat, Tetrabutylthiodisuccinat, Butylphthalylbutylglyoolat, acetyl trlbutyleitrat, dibenzyl , Trieresyl phosphate, Soluoläthylsulfonamid, the di-2-Xthylhexylester of hexamethylene glycol diphthalate, di- (Methyloyolohexyl) -phthalate, Trlbutoxyäthylphosphat and! Bributylphosphat. The particular plasticizer and the amount in which it is used are selected depending on the requirements with regard to compatibility and effectiveness in reducing the piling temperature .

Lift the copolyraeren, the metal complex and a suitable dispersing or emuig? erungsmittel and optionally a wax v.nä the above-mentioned dyes, the preparation according to the invention also alkali-soluble resins in an amount of 0 to 70 $ by weight, based on the total weight of the _copolymer} and Waohses alkaJ-ilÖsli-higher. Resin as thai th Generally alkali.löaiichen harae SäursssaSilen have weights between ungefälu x 100 and 300 and average molecular of about 500 to about 10,000, and preferably about 800 -. 5000.

Examples of alkali-soluble ears are oopolymers of styrene or vinyl toluene with at least some α-α-iaonoethylene

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BATH ORIGINAL

unsaturated ». Acid or an anhydride of such an acid, such as, for example, styrene / acrylic acid resin © or styrene / malelic acid hydric resin. In addition, alkali-soluble alkyds, which are essentially polyesters, aliphatic acidic dicarboxylic acids and aliphatic polyhydric alcohols, are suitable, with fatty acids and oleoerines starring with Cg ~ O ^ «-! Modified by Cg-O-jQ fatty acids © a, examples of dicarboxylic acids are maleic acid,! fumaric acid, adipic acid or sebacic acid as well as & ®r®n anhydrides. As polyhydric alcohols, glycerol, pentaerythritol, trimethylolethane or glycols may be used. 2-8 carbon atoms, including diethylene glycol and Xriäthylesglykol, mentioned.

The concentration of the aqueous dispersion varies expediently between a solids content of 8-45 $ _s , the solids content preferably being approximately 10-25% by weight.

Di © preparations can for impregnating Sextiliea. ,, Iieder, paper or other porous or fibrous Sfflaterialien "used wereasn You can also films on plastic ^ j such as Oellophanj, polyethylene» Polyäthyl.englykolt @ r @ phthalate ₉ Saran or the like. They can also be applied to rigid surfaces and can be applied to all types of metals, such as © Stall !, Aluminum ₉ · _{Copper 9} M © ssing _s Bronze ₉ Tin _p Ghrom or Söhmifödeeiseri.]? © rs, gr is © in © application to HoIs ₈ Stain®j masonry ₉ ! Seal * Glass, asbestos / Ztsment-Schinaeln or panels «Mosaic, Eeaie? at · = ο des? Be ton surfaces, such as® TasBh'aäBUs or such as possible, "the? ex'-binding®" are particularly suitable. for bollards iron footballs, for example from HoIiS ₉ linoleum _s rubber as well as all sorts of Zuftststcfflisssn, for example from Mnol-eum, asphalt "vinyl or Yinyl asbestos,

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SAB ORIGINAL

1Ä11012

Examples of wetting and dispersing agents are Alkali and amine salts of higher fatty acids with 12-18 carbon atoms, such as sodium, potassium, ammonium or morpholine oleate or ricincileate. Also come the usual non-ionic surface-active agents in embossing, additional wetting agents improve the appearance * » bring the polish.

For polishing floors, the coating that comes from the Preparation is obtained a Knoop hardness number of 0.5 or own about it. This hardness is measured on a film on a glass plate, the film having a thickness of 12.5-62.5 »(0.5-2.5 mils). This hardness range enables good resistance to abrasion and wear and can be achieved through an appropriate selection of the to be polymerized to achieve monomers.

The copolymer as well as the polyvalent metal compound (and the wax and / or resin, if such materials are used can be in any order be mixed. For example, the wax or the resin (or both components) in the aqueous polymer dispersion by adding a dispersion of the wax or the resin or a dispersion of the same constituents to the Oopolymerendispersioji or vice versa. A wax and a resin are used then the copolymer is preferably added to a dispersion of the wax, whereupon the resin is mixed in. The wax dispersion can be prepared using an anionic or non-ionic dispersant, as mentioned above in connection with the copolymerization. the. However, amine salts of soap, such as, for example, ethanolamine or morpholine oleate or stearate, are also suitable. . , : Lifting the mixture of wax in floor polishing

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another plasticizer or a volatile flow Medium can be added »around the required minimum film temperature the preparation

The multi-valued © metal complex can be used in preparation. "can be added at any time. In the last® of the essential B
Mulling included daily

The preparations have mater aoxmalea a gate storage stability. They can be brewed by wiping cloths, or by means of a sweetening strachea. in case they are pigmented slnfij, too hardened Filman and _ Ibesitisen, hai? t © measure. iahe glossy © Q "b®T £ läßken» In the weaentliehen there is no © Terfäiiyaag dsy film © during aging, Ms application of the preparation to surfaces - which are applied before made of alkali <° @ nt: £ @ mable preparations wear, _B has keiae removal of noticeable mengaa of such Ülb & s? » KÜge sur Folg®, foreigners will not affect the viscosity or the consistency of erfindimgsgtmäasen preparation adversely Weiee; therefore lassea Sidla the preparations in glslctaässiger Weis © on surfaces muster _s ifofcai the application easily carried and occur ünregelmässigkeiten no streaks or anything other ">

The accessories which contain polymers with oxy-caxylate groups (S & vxe or SaIs) ₉ can be removed by cleaning agents containing ammonia, as explained in more detail below

The following examples illustrate the invention. All! Hatchet and Prozentaagaban relate ,, unless otherwise ni'eht BXigeg @ ben _g weight. "-

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For example, 1.

a) A Emulsionsoopolymeres is obtained using 2 i> sodium lauryl sulfate (based on the total weight of the monomers) as an emulsifying agent "1 # n-Butylmeroaptan (" manufactured based on the total weight of the monomers) as chain transfer agent and in compliance with a conventional emulsion polymerization method. The copolymer has the following composition (in weight ^);

Methyl methaorylate 65

Butyl acrylate 25

Methacrylic acid 10

The polymer solids content of the final emulsion is 40 $> wobs.i the copolymer a I & trinsioviskosität of OjSsgemessia in tetrahydrofuran at ⁰ 2O g,. The emulsion is diluted with water to a polymer solids content of 15 °. The pH of the emulsion is adjusted to 6 * 5 using 1.4% NELOH.

b) A resin blend j of 18 parts of an alkaline 8 looking β styrene / acrylic acid resin with a molecular weight of about 1,400 and an acid number of about 160, in 62.5 ropes of water, containing 3 _r 75 ropes of a 28 J & gen NH ^ OH , contains, is prepared by heating the mixture to 50 ⁰ G. The solution obtained is filtered and then diluted to a 3-branch content of ': 5 $>.

c) A solution of zinc ammonium carbonate is prepared by mixing 95 g of ammonium carbonate, 73 ml of a 28% ammonium hydroxide solution, 54 g of zinc oxide and 535 ml of water. Mixing is carried out until a clear, homogeneous solution of zinc ammonium ^y j} osrOGnat has been obtained.

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BATH ORIGINAL

d) A polishing preparation is formulated in the following way: i

Polymer dispersion of rope a), diluted

to a solids content of $ 15 78

Alkaliloslich.es resin from part Ij) ₉ diluted

on a plague content of T5 $ 22

Tributoxyethyl phosphate 0.8

Sinkansmoniimcarbonat from rope c) 2 ₉ 5

Ethylene glycol monoethyl ether 2, -0

Npnylphenol, modified with an average of 10 ethyleneoxy & some Oj. β

Surface-active agent consisting of a fluorinated hydrocarbon of the formula OgJ ¹ ^ SOgH (OgH ₅ ) GHgCOOK, hereinafter referred to as the surface-active agent P beaeicimet 0 _? 5 Sormalin (37 $ ± ge solution) as a protective agent 0.1

The final pH of 9 ₉ 1 is adjusted with Asaoniuaihydroxyd / Has the appearance of the polierfoCTiuliarung is water-clear, Di® per centual © Itichtdurohiässigkeit is advised to use a Bausoh and Loiab Speotronie 20 colorimeter. ⁴ ? determined «, Dae Instrument vJLrd using desatilled water at a wavelength of 600 -mn to inn O. 100% ig permeability standardized. A Reagenssglas is la © ntspr ^ "ohender manner is Polierformulieru" filled ^ d) and diluted to a solids content of 15 $>. Thereby a 93% Mohtdurclassigkeit is bsobaphtet "The polishing form" can therefore be regarded as essential "

e) line homogeneous ¥ inylfugß "bodeiiflieee with a dimension of 228 2 £ 228 aim (9'x 9 inches) is coated with 1.5 ml of the finished pusebodenpoli'feur d). Laughing at 25 ° C during a a period of 60 minutes under a relative humidity of 50 $ , the plies is again with i _d -5 ml of the

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BEI ORIGINAL

ν ι ;. i |! ii | <. ': ■■ ■. ' ■ ·: - ■■ ·' ·: ■>■■.;'■ ■ ■ ■■''■' ■■ ■ '■'-; . »:,; :( ':'! ·: Ä!» F !!!

glelchea PornraXierung "bösohichtföt. The coated® J? Iiese 'is examined according to SiaMarflin methods _? whereby the following? * observations are made: I. The tile" has a high gloss, 2. vi @ polish leaves sieve, sshs? g, ivfc smeut, ie there is no such thing as a lazy renewal bi.sparslon ü @ b Poliertiljeraiigs "b.in the application of a new (!" bersugs), 3. the Politux Iseeitzt an excellent water resistance, 4. the The polish has a high resistance and 5. The outer floor polltur can easily be removed by using a 3% aqueous ammonium hydroxide solution.

. "The! Test methods for determining the puss-floor polishes. Namely the methods for determining the water resistance, the Döt @ rgena resistance ₉ the oil anise, the removability, the re-paintability and the hardness are described in more detail in" Hesin Review, Volume XVI, No. 2 "1966 published by the Rohm and Haas Company, Philadelphia, Pa. 19105.

Example ,, ^

a) An emulsion copolymer is generated using 3 $> Λ

3SratriUBilaurylsulfat (based on the total weight of the mononation) as an emulsifying agent, 2 $> n-Butylrasrcaptan (based on the total weight of the monomers) as a chain transfer agent as well as using a conventional SmulBionspolymeriaationsverfahren. The oopolyjnsre has the following composition {in

Butyl aorylate 45

Methyl methacrylate. 30th

Styrene 10

Methacrylic acid 15

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ie.-

The Endpolymerenfeststofikonaseri.t ^ ation eier Ihtralsion '38 # _} while the IntrlnsicviskoBitaij ^ emesssr.'; Ln Setrsv- ■ hydrofuran at 2O ⁰ G ₉ & n 0.1i? is determined. Di? The emulsion is diluted with water to a polymer content of $ 15,

b) a mixture of 4 ropes of a smulgierbarsn polyethylene with low molecular weight having a melting point of about 75 ⁰ C and O "is oleic acid ₉ 8 ropes gösohmolssn ,, whereupon 0 ^ 8 [Peile DSorpholin the mixture are augesetst, Me 'ready-to-melt is slowly 19 dents water »! heated to 95 ⁹ O (2o5 ° f)" eye under vigorous Rühron "tst _e The emulsion is allowed to cool to xmü ansQhiiessend alnen solids contents ■ halt of 15 ^ 9 diluted.

c) A polyvalent metal complex of zinc tetraamine acetate is produced by mixing 8 "5 ropes of zinc oxide into 70 ropes of a 2% ammonium hydroxide and by gradually adding 23 parts of acetic acid.

d) A bollard preparation with the composition given below is produced

Polymer diapörsion (solids content $ 15) 15 Alkaline solution resin (Example 1b) 20

Wax emulsion b / jjerßümit on a foot

stoffg €? hold from 15 $>'5 ·

Zinc tetrommine acetate according to o) 3 _s 0

Tributoxyethylphoaphat O ₅ 8

Dipropylene glycol monomethyl ether 0.7.

Ethylene glycol monoethyl ether 0.8

Diethylene glycol 1 * 5

2-pyrrolidone 1.0

Boundary area aesthetic0S Medium ϊ. 0.6

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Bc? R Bnd-pH works using voa Awmoni ^ zibyüvoxyü. on 9 _f 3

A sample of the finished, water-clear polishing preparation gives a 65% SiGhtdurcliläesig'igkeit. If the ido-permeability is determined by the colorimetric method described above. Me specified Polierformu ~-regulation is determined according to Example 1 t) "method described above. The applied polish has a satisfactory gloss ₉ is a good water resistance, good Detergenzbsständigkeit and good re Beschichtbarlceit and removability,

BeJSf) IeI ₁ 5

a) © in emulsion polymer using $ 1 (based on the total weight of the monomers) sodium lauryl sulfate as an emulsifier} $ 1 (based on the total weight of the monomers) bromotrichloromethane as a chain transfer agent and using a conventional emulsion polymer isation method. manufactured. The polymer has the following composition (in weight ^) »

3-butyl acrylate 45

Methyl methaoriylate. 45

2-hydroxypropyl methacrylate 3

Methacrylic acid 7

The Endpolymerengehalt the emulsion is 40% _t while the intrinsic viscosity to 0.22, as measured in üetrahydro "- furan at 20 ⁰ O ₉ is determined.

b) A resin blending solution containing 20 ropes of an alkali-oil, partially esterified styrene

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BAD ORtGlNAL

Adduct with a molecular weight of irag & föUu? 2 100 and an acid number of 160 in _a 62.5! Beile water, containing 3.75%! Belle 'of a 28% M-OIK solution, is prepared by bringing the mixture to 50 ° Ö. The resulting solution is filtered off and atischlaessead & v £ © inen solids · = - content of 15 ^ diluted.

c) Zinc carbonate is in a 28 ^ ig © n Ämmoniimbydro ^ ydlß " sxing solubilizes.

d) A floor polish is formulated in the following way:

Polymer dispersion (solids content 15 ^) 80

Alkali-soluble resin (solids content 15 SO 20 zinc carbonate (solubilized in 28 tigern ÜH ^ OE) 1 _Ρ 5 propylene glycol _{moaomethyl ether 1 f} 5

Ethylene glycol 1.5

Iributoxyethyl phosphate 0.55

Büttel active at the boundary surface F 0 ^ 4

Dibutyl phthalate 1.0

Konylphenol »modified with average about 40 oxyethylene groups. (Snuiglexmlttel) 0.3

Of the. The final pH value is set using τοη Amaaoniuauiydrozyd aiif 9 ₉ 3, The polishing foam appears water-clear and "has a Mphth permeability of $ 90. Results found in Example 1.

Example ,,, 4 - '■'. "■ - ■■""" ■ -, - .:. ■■ [..; _, '■ / .; ■ _ / a) An emulsion polymer is made with an average of -. "4 $, (based on the total weight of the monomers) OotylphenoX, modified with an average of 30 ithyleno ^ rdgruppen, 1 ^ (based on the total weight of the monomers) Tetrachloräthajet

909829 / U47

as a chain transfer agent as well as in compliance with a customary Emulsified polymerisation method produced. The polymer has the following composition (in weight- ^) t

Butyl acrylate 40

Methyl methaorylate 40

Vinyl toluene 5

Methacrylic acid 12

Acrylic acid 3

The final polymer solids. the emulsion is 40 #. The intrinsic viscosity, measured in tetrahydrofuran at 2O ⁰ O, is found to be 0> 4.

b) A resin treatment solution. which contains 20 ropes of an alkali-soluble partially esterified styrene / maleic anhydride adduct with a molecular weight of about 2,100 and an acid number of 160 in 62.5 ropes of water containing 3 »75 ropes of a 28 # HH.OH solution is through Heating the hybrid to 50 ⁰ C produced. The resulting solution is filtered and then diluted to a pesticide content of $ 15

q) Zinc ammonium glutamate is made by mixing 24 g of glutamic acid, 13 g zinc oxide, 41 ml of a 23 # Lgen ammonium hydroxide solution and 45 ml of water. The Yermishen takes place . until a homogeneous solution is obtained.

d) A floor polish is formulated as follows!

Ropes

Polymer dispersion (pesticide content 15% ) 80 alkali-oil resin (solids content 15 SO 20

^ 1 τη) τα ^ γηη η f ^ T ffg ltl fffliet ■ 2.6

909829/1447

ethylene glycol monoethyl ethyl

Biäthylsnglylcol ■ 1.5

Tributoxyethyl phosphate 0.35

Surface active agent P 0.4

Dibutyl phthalate 1.0

Ronylphenol modified with average about 40 ethylene groups

(Emulsifier) 0.3

The final pH is adjusted to 9 "3" using. The polishing formulation appears serfclar and gives a permeability of 88 #. The results obtained in testing correspond ä ^ n results, according to the Formulation Example 1 were fsstgestellt.

a) an emulsion copolymer is made using τοη 3 wiolits-9S, based on the öasamtmonomerea, beard. modified with an average of 30 ethyleneoxy units as emulsifier, 2 parts by weight, based on total monomers, bromotriochloromethane as chain transfer agent, 250 parts by weight of water, 0.5 part by weight of potassium metal sulfite and 0.5 part by weight of potassium persulfate. The polymerization temperature is produced by cooling over a period of about 2 hours at 50 -. 55 ⁰ O supported th Ansohliessend the Gopolymerendispersion is cooled to 30 ° 0 and filtered.

Methyl methacrylate, 42

Ithyl aylate 50

Meiacrylic acid 8

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- 25 -

The pile kicked gives a solids gel of approximately 40 #. This solid consists of an Enmlsionscopolymer, Das Copolymers has an intrinsic viscosity of 0.22 when measured in tetrahydrofuran at 20 ° 0. The emulsion is diluted to 15 # polymer solids with water. Of the The pH of the emulsion is determined using a 14 Digest M.OH set to 6.5.

b) A resin blend containing 18 ropes of an alkaline styrene / acrylic acid resin with a molecular weight of about 2140 and an acid number of about 226 in 62.3 parts of water, containing 3 »75 parts of a 28% HH * OH. holds is prepared by heating the mixture to 50 ⁰ O. The solution obtained is filtered and then diluted to a solids content of 15 #,

c) A solution of tin morpholine acetate is made by mixing of 1.5 files of zinc acetate, 1.5 cables of a 28 # ammoiiiiuiLhydrosydlSung, 3.0 üCeileii water, 1.5 ropes morpholine and 1.5 ropes of tert-octylphenol modified with average. 40 ethylene oxide groups. The Yermisehen takes place until a clear and homogeneous solution of zinc » morpholine acetate has been obtained.

d) A polishing preparation is formulated in the following way!

Polymer dispersion of rope a),

diluted to a minimum content of $ 15> 78

Alkaline oil-free resin from rope b),

diluted to a solids content of $ 15> 22

Tributoxyethyl phosphate 0.8

Zinc morpholine acetate from Seil o) 3.0

Propylene glycol monomethyl ether I ₉ O

909829 / U47

Propylene glycol & olffiono-ethyl ether 1 " O

Ionylphenol ₉ molten with average

licli 10 Ithylenoscydeiiiiheiten Q., 6

Medium F 0.5

Formalin (57 # ig © solution) as a protective

medium 0.1

The pH is below Yerwenfcftg -vom. Ajamoniizjabyärosyd set to 9 p © _s Dalsei becomes a • wasserkia.res .tossehea © raielt. Uater Eiabalinmg dar vorstehsäd aagegelserasn teoloajime-triscHexi. Method based on Meseimg ter Idolite permeability, the Barcla "permeability of the water-declared poli ^ rfosmialieriHig" is set at 38 $.

The polish is naturally the same as in Example 1 f) Ijesohriebexien Metlioäe, with satisfactory results being achieved.

A polishing facility "will be produced. You" will have to follow @ a de Pormulisnaiigi

Polymer dispersion (solids content 15 ^) from example 1a)

WaohsemLsion _ff diluted on a & a. Pest content of 15 ^ ₉ according to Example 2b)

8.4 ropes dlyein, 8 ₉ 0 filing a 28

ABfflaonituahydrdaiyäe, 20 ropes of water imd

7.1 iDeile öateioimoacyd) 2.5

O ₉ B

Ethylene glycol monoethyl ether 1.5

Diethylene glycol 1.5

2 «pyrrolidone, 1 ₉ 0

Surface active agents litt®l PO ₉ β

9/14 4 f

The Ead-ρΉ is made using ammonium hydroxide 9.3 set,

A sample of the finished polishing loaf results in 80 Eick-permeable cool. when the above "described colorimetrisone Method is adhered to. The polishing preparation can be described as essentially water-clear. the Above-specified polishing formulation is according to the in Example 1f) described method investigated. The received Results are satisfactory.

Example 7

A polishing preparation without a polyvalent metal compound is produced in compliance with the formulation described below!

horny

Polymer dispersion (! Solids content $ 15>)

according to example 5a) 80

Alkali-soluble resin (pesticide content $ 15>)

according to example 5b) 20

Ethylene glycol monoethyl ether 1 »0

Propylene glycol monomethyl ether 0.5

Diethylene glycol 1 _r 5

aiributoxyethyl phosphate 0.35

Surface active agent F 0.4

Dibutyl phthalate 1.0

Nonylphenol, modified with durohydomoral about 40 oxyethylene groups (emiü.giermittel) 0.3

The final pH is adjusted to 9.2 using ammonium hydroxide. The polishing formulation appears water-clear and gives a Liohtdurohlohlkelt of 90 &> An investigation according to the method described in Example 1 f) shows a high level of GKLana and good removability. However, no detergent resistance is determined. The water resistance is lower and the renewed visibility is unsatisfactory.

9Q9829 / U47

Example “8

Contains Bine PolierEubsreiinmg, dia neither alkalilösliohee Hara yet, a wax, uatsr compliance will constitute na, ehs ^r G <she: a: .l formulation described ι made

Part®

Polymer dispersion (solids content 15 fi)

according to example la) 100

Sributoxyethyl phosphate 0.8

Zinc bimonium glyeinate 2.5

Ethylene glycol monoethyl ether 1 »5

Dipropylene glycol monomethyl ether 0.5

lioaaylphenol, modified with ucsaiilic

10 ethylene oxide units 0.6.

Fluorinated hydrocarbon surfactant of the form ©! OQE ₁ ^ SO ₂ N (O ₂ Hk) OH ₂ OOQK, "aohstöhenä" as a surface-active agent 1 "extremely costly. 0" 5 formalin (37 $ solution) as a Sohutzi agent ₅ O ₉ I

The final pE is adjusted to 9.1 using isMO3iiumhydro3rya. The appearance of the polishing substrate is clear as water. A sample of the polish produces a light permanent impermeability tone 91 $> if the method described in the table is followed by the colorimetric method. An examination of the polish according to the methods described in Example 1 () gives results which are similar to the results obtained using the polish of Example 1.

909829/1447

BAB ORiGfMAL

Claims (1)

- 27 claims 1.Preparation, which includes polishing the bottom of the barrel, Furniture or the like is suitable, this preparation forming a PiIm with a Knoop hardness number of at least 0.5 au and is able to assume an essentially clear to essentially water-clear appearance "thereby characterized in that they are essential components 1. An aqueous polymeric dispersion of an insoluble in water Enmion copolymers with an intrinsic viscosity from about 0.1-0.7 »where the copolymer of at least one α, β-monoethynically unsaturated carboxylic acid and at least an alkyl ester of a, S-monoäthyleniseh unsaturated Carboxylic acid, and 2. contains a polyvalent metal compound. 2 «Preparation according to claim 1», characterized in that the polyvalent McyalX compound is used in such an amount * that the molar ratio of the polyvalent metal ± 0318 kit of the total carboxylic acid in the preparation is between approximately 0 _t 1ί1 and 0 ₅ 5: 1 ephased, 3. Preparation according to claim 1 _e thereby gelcennaeichnet that the copc'Xpolymer has been prepared from about 5-18 $ at least one α, β-ethylenically unsaturated acid. 4. Preparation according to claim 1, characterized in that the α, β-ethylenically unsaturated acid is methacrylic acid. 5ο preparation according to claim 2, characterized in that the Copolyaere extensively to at least one ethylenically unsaturated Acid from at least one ester of aöryl acid or methacrylic acid has been produced " 9/144 ^ bad original 6. Preparation-, msh: -Aass.p ^ eh. 3> "characterized in that that copolymers of methacrylic acid and at least © inem from Ethyl aorylate, butyl acrylate or methyl methaorylate " unsaturated ester has been produced. 7. Preparation according to claim 1, characterized in that as an additional component made from copolymers of styrene or vinyl toluene with at least one a ^ ß-ethyleniBoh unsaturated carboxylic acid consisting of an alkali-soluble resin holds, with the alkali-soluble hara having an acid value of approximately 100 - 300 and an average liolecular weight has from about 500 ~ 3000 » 8. Preparation according to claim 1, characterized in that the polyvalent metal complex of ammonia or amine complexes a polyvalent metal ordered. Is 9. Essentially tfasserklare preparation, di © inter alia for polishing FuBsböaen, furniture, or the like, characterized in 'that it has a pH of about 7.0 to 10 and dasu ± n the lag © is a coating film having a Knoop ~ Hardness of at least 0.5 to bildanp - this preparation a) 30 .- 100 & ewichtst © liö of an ia. Wasöer insoluble. Addition polymer © !!, which is produced by emulsion polymeriBation vos. has been obtained at least 2 inonoäthylöniseh unsaturated monomers, wherein one of the monomers is an A _s B "monoethyl @ nisoh unsaturated acid -GewichtB- ^ is eingesetst based on the entire ^ Monomerenj in © © r in amount of about 5 ■, and the addition poljpaere © ine intrinsic viscosity. of about 0.1 0 _e 7, b) 0 - 70. Parts by weight © ines made of copolymers from © iner vinyl · » aromatic compound with an a, ß- »äthylenisca unsaturated acid existing alkali-soluble resin, whereby the alkali 909 829/14 47 * 29 - soluble resin has an acid number of about 100-300 and a average molecular weight of about 500-5000 owns, o) 0-70 parts by weight of a Waohsea, d) Wetting, dispersing or dispersing emittol in one Amount of 0.5 - 20 Gewlohts-56, "based on the sum of a), b) and c), as well as e) at least one polyvalent metal complex in an amount from about 1 - 50% by weight, based on a). ^ 10. Preparation naoh claim 9 »characterized in that 70 - 90 parts a), 10 - 30 parts b) and 0 - 10 parts o) contains and has a pH range that fluctuates between 8.5 and 9.5, 11. Preparation which consists of a mixture of water., An Aoryladditioneoopolymeren, which is dispersed or dissolved in the water, and a water-soluble ammoniacal zinc compound, characterized in that the acrylic resin by emulsion polymerization of methacrylic acid and at least one of ethyl acrylate, butyl aorylate or methyl methacrylate existing ester has been prepared and (Jj has an intrinsic viscosity of 0.15-0.25, the molar ratio of the zinc of the zinc compound to the total carboxylic acid in the preparation varies from about 0.2t1 to 0.3: 1 and the copolymer as well aromoniakalisehe the zinc compound to be in dtr capable of forming "the clear solution in water at a Polyaerenfeststoffgehalt 15 f, and a pH of 9.5. 909-829 / 1.447