DE2114843A1 - Floor care products - Google Patents

Description

Patent application "Floor care products ¹¹

Applicant: Werner & Hertz GmbH, Mainz

The invention relates to an improved floor care product the basis of aqueous plastic dispersions with a content of active detergent and the usual additions of emulsifiable wax for such agents, possibly suitable resins, Plasticizers and wetting agents, which increased through Cleaning power while maintaining the self-shine effect

There are three main groups of floor care products currently in use;

1.Typical self-shine care products (primers and shine agents)

2, self-shine agent with cleaning effect (wiping agent) 5 agent without self-shine effect (cleaner)

Basis of all self-shine agents, that is, the _agents of the first and second group are aqueous dispersions of plastics (Styrolakrylaten and the like ·) ·

The typical self-shine care products of the first group do not necessarily need wax, but they can. _: (Natural waxes, synthetic waxes and modifications) with which a polishing ability is achieved. The synthetic waxes used for floor care products include the emulsifiable polyethylenes with low molecular weight, which owe their ability to give aqueous dispersions with the help of emulsifiers ■ to oxidative cracking (see e.g. Soap & Chemical Specialties,

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1969 »Pages 41 - 47) · In the case of wax-free or low-wax agents of extreme hardness and durability, but little possibility of polishing, one speaks of primers (polymer primers); In the case of agents with a lower resistance to stress, but the possibility of compensating for the traces resulting from the stress by polishing, one speaks of polishable self-shine agents (gloss agents); for agents with a high wax content of easily polishable self-shine agents

The agents of the second group, i.e. the self-shine agents with a cleaning effect, contain based on the aqueous Dispersions of plastics and waxes another additive,

fc namely washing active substances (WAS). These means unfold a more or less pronounced cleaning effect on soiled Documents, especially in relation to soiled films of comparable products, in which those incorporated in the film Cleaning agents support the cleaning process The prerequisite for the practical implementation of cleaning is: that there is an aqueous phase in which the cleaning care product can be dispersed together with the dirt Dirt is thinned out via the aqueous phase (wiping effect). Such a cleaning procedure has an adverse effect however, more or less, but so far inevitably, the gloss · This is also the reason for using this self-shine with cleaning effect in a special group.

"in summary

The third group is the so-called "cleaners", i.e. agents without a self-shine effect, either emulsion-based (oil-in-water) or solvent-based

Their structure: All of these agents are based on waxes (with or without plastic) which are at least partially dissolved in solvents and which can be dispersed or emulsified in the aqueous phase _o The solvents are organic compounds of largely non-polar structure in which the are partially dissolved, partially dispersed (floor polish

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grow) · So the salary is characteristic of these funds of volatile organic solvents

The existing PiIm is dependent on each hay order the mechanical impact and the product composition more or binders attacked. This will make the more polluted ones The upper layers of the film have largely been removed and replaced with new material to such an extent that the surface appears clean (Cleaner cleaning) · This oldest and most tried and tested product group in the field of floor care, namely the cleaner - which also includes floor wax in its various forms - enables the floors to be kept clean in an optimal way, but does not achieve a gloss effect automatically, but requires mechanical post-processing (e.g. polishing) after the solvents have evaporated

The object of the invention was to create agents with the cleaning power of product group 3 (cleaner), which also have product features of group 1 (self-shine and durability) and those for cleaning not only by means of the aqueous Phase can be cleaned (wiping method), but the typical cleaner method (dissolving method) can also be used can · The new product sought should combine the advantages of cleaning care with a long-lasting shine and also Allow wiping with diluted solutions of the product itself - while maintaining the self-shine effect.

This objective is achieved according to the invention by a floor care product on the basis of aqueous plastic dispersions with a content of detergent active substance and for such Means customary admixtures of emulsifiable wax, if necessary of suitable resins, plasticizers and hardening agents, which is characterized in that, as an emulsifiable wax, it has a proportion of 0.5-50 wt .- ^ of the dry substance of the care product contains oxidized, linear low molecular weight polyethylene, which has a molecular weight between 5.OOO and 2O.OOO, an acid number between 2o and 5o and one

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Has a softening point between 12o and 15o ° C.

The agent according to the invention therefore belongs to product group 2, because it is a wiping agent due to its structure as a plastic dispersion in water and its content of active detergent When the wiping process is carried out, however, it differs from the currently known wiping means primarily in that the shine after wiping with aqueous solutions of the product bfcinato. emerges in its original strength while at the previous means will be significantly or severely impaired.

It has surprisingly been found that the properties described can be obtained if and only if as a wax additive, the oxidized polyethylene is used with the characteristics indicated, which in its properties is between a Wax and a plastic material · It was not to be expected with this waxy, not previously used in floor care, at the outermost limit of the polyethylenes still to be designated as low molecular weight under the prerequisite, that it has the specified above-average high oxygen content, an above-average high density and an extreme Has hardness, a cleaner-like wiping agent can be produced, which in the gloss stability with lieuaufgabe and also the typical self-shine care products in the resistance to traffic marks reached

The other Eesept components, such as plastic, plasticizers, Wetting agents, Wasohaktivstoff, emulsifiers, belong to the for substances already used in this sector, although - as usual - coordination is necessary and careful selection is allowed a maximization of the recipe leads.

In the case of the waxy one necessary for the new cleaner-like weighing agent The component is a low-density polyethylene, which was preferably produced by the Phillips process and, after oxidative cracking, an average chain length 5oo to 6oo carbon groups in a molecular

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has a weight of about 8000 with the lower limit of about 6000 and the upper limit of about 10,000 "to 2o, ooo ·

The oxidation of this polyethylene is up to an oxygen content of about 3% by weight, an acid number of 2o to 3o (26.1) and an ester number of 1o to 2o (15.5) being achieved. In addition to the oxygen present as acid and ester, about 1/4 of the amount absorbed is bound in some other way, especially as Hydroxyl, then as carbonyl and in traces also as peroxide.

The Phillips method provides a practically linear one, as a result crystalline, hard and dense polyethylene with high Softening point These characteristics remain the oxidized Obtained polyethylene, so that a body is created that neither the waxes nor the plastics can be directly attributed to osfc and through the following Data described can be:

Hardness: 0.5 dmm (Eadel penetrometer hardness according to ASTM D 1321 (D-5); 100 g / 5 sec / 25 ° C)

Softening point: 138 ° -147 ° (according to ASTM E-28) D ₂₀ : 0.99

Viscosity: 9ooo ep (149 ⁰ O according to Brookfield) or 15oo cp at Ho ⁰ C.

(The corresponding values for a pronounced hard wax with a similar acid number are: hardness 2-3J, softening point 1Go-Ho ⁰ ; D ₂₀ 0.92-0.93; molecular weight 2ooo-3ooo; viscosity 2oo-4oo at Ho ⁰ C).

The linear polyethylene becomes emulsifiable through the oxidation. If it is to be used in a floor care product from which a high gloss is expected, the emulsion must be very finely divided and be even. The quality of the emulsion depends on the one hand on the physical data of the polyethylene to be emulsified and on the other hand the emulsifying agents of importance. The prerequisite for the usefulness of polyethylene is its uniform oxidation; the process conditions for this oxidation must therefore be observed very precisely or it

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must if the results differ among the batches received oxidized polyethylene a selection with regard to emulsifiability be taken empirically. But it is in itself possible To manufacture batches of the type required here in a targeted manner · Such a product is currently being supplied by Pirma Allied Chemical S.A »(see the article" Polyethylene Waxes in Paints and Varnishes "E. Dysseleer in Paint Manufacture 197o, page 24) under the designation A-C 392. The special position of the product A.C 392 with regard to viscosity, density, hardness and melting point can also be clearly seen from the work cited in this cited work Table 1.

A suitable emulsion is obtained, for example, when the oxidized Polyethylene with a non-ionic emulsifier belonging to the alkylphenol polyethylene oxide group emulsified, e.g. with a product from Rohm & Haas, Philadelphia, with the name "Triton X 1oo ", an iso-octylphenol polyethoxyethanol with 1o mol of ethylene oxide. Long-chain glycol ethers and de.rgl serve as an aid. Due to the high melting point of polyethylene, emulsification must be carried out under pressure. The following proportions by weight are used as the emulsification recipe specified:

Emulsification regulation

Polymer wax (AC-392) 19.1 wt. Nonionic emulsifier

(Triton Χ-Ι00) 4.7 wt.

Glycol ether

(Dowanol DPM) 2.2 wt.

Potassium hydroxide (KOH) 0.5 wt.

Sodium thiosulfate

(Na ₂ S ₂ O ₃ ) O.2 wt .- #

Water, distilled73.3 wt.

I00.0

A wax emulsion with 25% by weight solids, one Yiscosity of approx. 15o cP and a transparency of approx. 80.

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The polymer waxes used (supplied by Allied Chemical S.A. under the designation A-C. 392) had a total acidity st off content of 2.84 wt .- # where 0.5 wt .- ^ as hydroxyl, 0.05 wt .- # were present as peroxide and 0.25 as carbonyl. the The oxygen number was 26.1 and the ester number was 15-5. Despite the Due to the high acid number, the increase in surface tension is assumed of the polyethylene to be used according to the invention by about 20 dynes / cm is insignificant use in the emulsification process made by the acid groups. The carboxyl groups support the emulsification process, especially when the groups with Alain- / alkali are neutralized. The real emulsifier is but not ionic even with the emulsions of this wax; In the old recipe, a glycol ether is used as a coupling agent. The glycol used is diethylenefjbipropylen-, ethylene glycol or alergj. and Variants of the ether group are, for example, monomethyl ethers, Monoethyl ether, monoethyl ether acetate, monobutyl ether, monobutyl ether acetate, Dibutyl ether, dimethyl ether or the like.

Plastic dispersions can be used to mix the polyethylene that have proven their worth for floor care products and which usually belong to the group of polymerized acrylates, mostly with styrene content. A copolymer with the main components ethyl acrylate and was found to be particularly suitable Styrene and a content of butyl acrylate, one of which is responsible for the gloss formation has favorable minimum film-forming temperature. Leave it however, other acrylates can also be used if certain changes to the product properties are accepted. Cf. see Table 1 below with the only slightly different results when using different for Floor care products made from conventional plastic dispersions.

The same applies to the selection of the resins as to the plastic dispersion. The plasticization, the improvement of the agitation, the selection of the cleaning substances happens according to the state of the technique. A styrene-maleic anhydride resin proved to be particularly suitable, plasticizing with phthalic acid ester and a glycol ether, fluorinated as wetting agent

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Carboxylic acids and, as cleaning substances, alkyl-phenol-ethylene adducts, as well as cleaning phosphates, especially trisodium phosphate.

Some examples of the composition of the floor care product according to the invention are given below!

Examples I. and II.

Recipe shares I. II oxidized polyethylene 4-.O 5 «3 plastic 1o.o 9.6 resin - 1.0 Washing active ingredient ο. Τ o. 7 Plasticizers 2.9 2.5 cleansing salt 1.15 t.15 Wetting agents O.01 o.o1

The composition II * the proves to be particularly suitable will also be made the basis of assessment A in the following grading tables.

In terms of commercially available finished products, the composition can be realized as follows:

Commercial product denomination wt .- ^

AC 392 ' emit i.gj .β, Γΐ ΜΪ & Ύ ⁽ ~ ¹ " ¹ " * Ρ ~ £ ^{: ι} ? Ϊ́ ΊβΤ1Γΐ £ φ ^< ί3θ1'νΓ'3 ft T) OTT · £ -3θ9θ

Allied Chemical Comp., New York, June 17

"Ohem, ITompV ^ Ohikago 24. ο

Water, dist. 42.9

Alresat KH 64o C (i6 £ ig), Chem. Works Albert, Wiesbaden 6.5

Iutensol AP 1o (BASF) as a washing active ingredient o.7

Palatinol C (BASF) as permanent plasticizer 1.5 Diethylene glycol monoethyl ether as clutch plasticizer 1.ο

Trisodium phosphate (io $ ig) as a cleaning salt 4.5

FC 128 solution (i $ ig) (3 M-Compaiay, Düsseldorf) 1.o

as a wetting agent

Perfume etc. o.3

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Instead of the used Alresat, a styrene-maleic anhydrite resin, The pentylene resin 261 sold by the Hercules company can just as well be used as the resin.

Instead of lutensol as a detergent, an ifonylphenol-ethylene oxide adduct with 1o ethylene oxide groups, another alkylphenolethylene oxide adduct with an alkyl radical of C ^ -C- and 6-12 ethylene oxide groups are used; for example "Arkopal" from the Hoechst A.G.

Lalatinol is dibutyl phthalate and counts among the so-called. Permanent plasticizers, while the Ethyldiglykol used is a substance that is between the permanent and to be classified as temporary plasticizers; it acts as a coupling substance in the emulsification of the oxidized Polyethylene and can be replaced by various other variants already mentioned.

The FC-128 solution used as a wetting agent contains a perfluorinated one Carboxylic acid and can also be replaced by other common wetting agents.

The dry matter remaining on the ground then has the composition as given above as Example II «, The The proportion of waxy polyethylene used can be varied within wide limits. Both products with only 1 wt .- # as well as products with 15% by weight prove to be extremely useful; one can through this modification of the proportions Floor care products with various specific properties produce, whereby the polishability by increasing the amount of the proportion increases, while decreasing the dirt repellency and scratch resistance increases.

By changing the proportion of the active detergent, specific property adjustments can also be achieved; increasing the proportion increases the cleaning power and decreasing it increases the durability against water wiping.

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In the following, some grading tables should be on the one hand the slight influence due to modification of the plastic component (Table 1) can be shown and, on the other hand, a comparison to the comparable floor care products currently on the market carried out (Tables 2 ff.).

For the grading in these tables, the following should be sent in advance!

The relevant finding is assessed visually and in each case in divided into five categories, both in terms of improvement and. Deterioration:

Track better or worse + 1 slightly better or worse +2 significantly better or worse + 3 much better or worse + 4 extremely much better or worse-. _c

ter ± ⁵

One of the together (i.e. simultaneously or products checked under the same conditions; the properties of one of these products are set equal to WwU (O).

Table 1

Influence of the use of various commercially available copolymer materials as plastic dispersion components

Copolymer A. B. C. D. E. Networks O O O O O course O -1 O -1 -2 shine O -2 -1 -2 -3 Rubber lines O -1 O -1 O Stripes O O O O +2 Scratch resistance O O O O +2 Polishability O O O O O Schmutζaufnähme O +1 + 1 +1 O Powder O O O O O Water-wiping O —2 O -1 -2 Alkali-WHAT-Wis chen O + 1 +3 +2 O Removability-Soap-WHAT O -1 -3 -1 + 1

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You can see from the table in which the properties of the recipe of Example II serve as a reference point (Ifull value in recipe A), that, for example, one could also work with the copolymer C, but then a slightly weakened gloss and less removability with soap-WAS, a slightly better behavior against dirt pick-up and a better resistance to alkaline Got cleaner.

Table 2

Influence of the use of various waxy polyethylenes.

middle A (new) BCD

Networks 0 0 0 0 course + 1 0 0 0 shine +3 0 0 0 Dirt pick-up 0 0 0 0 Rubber lines +2 0 0 0 Stripes +3 0 0 +4 Scratch resistance +3 0 0 +3 Polishability ~ 1 0 0 -1 Powder + 1 0 0 + 1 Water wiping 0 0 0 0 Alkaline wiping +2 0 0 +2 Removable with soap-WAS -2 0 -1 -1

This table clearly shows the superiority of the formulation according to Example II, which contains the new polymer (A). Particularly in the gloss and in the resistance to traffic marks, which is expressed in the values for rubber streaks, stripes and scratch resistance come) shows the superiority. The product examples B and C are compatible with other poly-

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ethylene waxes (emulsion polymerized) and the product example D made with a softer copolymer (from the Phillips process).

The superiority of the floor care products according to the invention
can also be seen in the comparison with commercially available products. In the following tables the comparison with the three
Wiping agents, which are currently the largest market importance and together supply about $ 80 of the market.

Table 3

Conduct in practice

Gloss +

Dirt pick-up +

Dirt adhesion "+ ·

Inclusion of black rubber lines

2/3 2/3 1/2

2/3

The marks represent the result of beginner attempts in large objects with 1,000 to more than 10,000 inspections, for example in schools. The comparison was made with a tried and tested standard ' Product carried out as a reference (O value).

Table 4 CVl shine repeated filming ■ · + 2/3 Self-shine effect at + 2/3 • Assignment Solving the overall picture 0 1 " Assignment 0 0 - 2 middle course 0 0 - 3/4 A. 0 0 - 1/2 X 0 - 3 Y 0 Z 0

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Explanation of terms:

Course: uniformity of the order

Gloss: visual gloss assessment

Solution: Promotion or disruption of the order image by new ones being added Mass (time interval 2o min)

Overall picture: sum of flow and gloss, depending on the dissolving behavior

The agent A according to the invention shows up compared to the commercially available ones Means X, Y and Z clearly, superior »

Table 5

Access behavior with at least I,000 inspections Medium Shine Soiling Footprints Overall rating

A. + 2/3 + 3 + 3 + 3 X 0 0 0 0 Y 0 - 1/2 - 2 - 2 Z 0 - 3 - 3 - 3/4 Table 6

Cleaning with the agent

(Wiping with the above solutions without subsequent polishing)

ttel shine Dirt and dirt Traces of the Overall judgment walking track remover Wiping tion A. + 3/4 + 1/2 + 2/3 + 3 X 0 0 0 0 y - 1/2 - 1 - 1/2 - 2 Z - 1/2 - 3 0 - 3

Note: Hach the wiping occurs with all previous means a gloss drop a; with product A according to the invention, the original gloss is practically achieved again

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The properties of the floor care product according to the invention . therefore differ fundamentally from the current products and are to be described as follows:

1. The ability to dissolve itself, i.e. the limited but effective attack of the agent itself is already dried on the surface Films of the same agent are particularly pronounced, but leave the structure of the connecting film intact.

Up to now this was only possible with the use of solvents and is successfully used with floor waxes and EmuMonscleaners. These agents in turn have a soft film consistency, do not give a self-gloss and contain solvents.

The ability to dissolve itself is more or less also with the current ones Self-shine agents with cleaning effect (wiping agents, group 2), are given, but the dissolving disturbs the structure of the remaining film (loss of gloss). The stability of this Medium is inferior to that of the typical self-shine care products (group 1).

2. The agent according to the invention achieves the cleaning ability of a cleaner on a purely aqueous basis and delivers at the same time a flawless self-shine, as was previously only possible with agents in groups 1 and 2 that were not used as cleaners are to be addressed.

The real cleaner-like agents of the previous type contain solvents and do not give a self-shine · They are sensitive to stress and have to be polished immediately after application and relatively often later. The disadvantages of organic solvents such as attack on sensitive substrates, odor nuisance and flammability, do not apply to an aqueous agent.

3e The erfiadung @ g © Mi, Se means arises in the Resistens Gegea "Yerkehrsspurea iea typical self-care & maintenance products (Grupp® 1)"

It behaves - compared to group 2 - as if it did not contain any additional active detergents, and - compared to Group 3 - as if it contained solvents, since, despite the presence of organic solvents, the tempering effect especially "at higher dilutions, is fully developed,

4. The agent "forms active detergents in the interaction of plastic Substances, wax, resin and additives not the usual skin-like, but a "short" solid film - it is better to be from ι one layer. speak - high stability, the film acquisition unit Apart from the hardness, corresponds more to a floor wax covering than the application from the usual self-polishing agents, has: ": but in all other properties the advantages of the self-shine agent. The structure of the film, or the care layer, makes this covering is particularly suitable for the use of the cleaner and the wiping process, because it becomes the existing care film depending on the intensity of the mechanical cleaner effect and the amount of product used, only more or less strong from above attacked without the structure of the underlying film part is significantly impaired.

More detailed investigations of the interaction of washing active substances and extremely hard polyethylene with the plastic dispersion and the additives mentioned above have shown that a film is obtained which - in contrast to the films from previously known self-gloss emulsions - is "short", i. e. shows practically no viscoplastic behavior. While other care product films are damaged with a pointed, sharp Lift the object more or less than skin, or arch it up elastically and partially deform back when the disruptive effect subsides, occurs with the care product according to the invention layer-like removal, similar to scratching a compact piece of wax, instead. Presumably it is in this one right now Film property to see the actual cause of the excellent wiping and cleaning behavior of the new agent, because the These processes necessarily occurring film disturbance makes itself due to the less coherent film structure only in Area of the disturbance itself noticeable and does not propagate within that film area that after the Gleaner or WiocliTorgang should be preserved. Claims

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Claims (8)

Werner & Mertz GmbH Reference: We-15-P -ifc. Date: "26th Mara -1 ψΛ q, ^ Pat ehtanspriiche 1. Floor care products based on aqueous plastic dispersions with a content of active detergent and the for such agents usual admixtures of emulsifiable wax, optionally suitable resins, plasticizers and lubricants, characterized in that it as emulsifiable wax a proportion of 0.5 to 5o G-ew - ^, preferably 1 to 15% by weight of the dry substance of oxidized, contains linear low molecular weight polyethylene, which has a molecular weight between about 5 · oοο and 2p.ooo, an acid number between 2o and 5o and a softening point between 12o and 15o ° P has. 2. Floor care product according to claim 1, characterized in that it is the emulsifiable wax in aqueous Contains dispersion, this dispersion using nonionic emulsifiers of the compound class of the alkylphenolethylene oxide addition products, possibly with the use of Glycols, VzUr; Glykölderlvaten, is produced. 3 · Floor care product according to one of Claims 1-2, characterized in that it contains plastic dispersions Contains based on copolymerized styrene acrylates Floor care product according to claim 3, characterized in that it contains synthetic dispersions based on copolymerized ethyl acrylates and styrene with the addition of butyl acrylate. 5. Floor care product according to one of claims 1-4, characterized characterized in that there are resins based on styrene maleic anhydride contains. 6 »Floor care product according to one of claims 1-5, characterized by characterized in that it is based on detergent active ingredients 209842/0933 21U843 Nonylphenolethylene oxide adducts, optionally with the addition of cleaning agents Contains phosphates 7 · Floor care product according to one of claims 1-6, characterized characterized in that there are plasticizers based on phthalic acid esters, optionally with the addition of glycols and / or Grlycoleafcer contains. 8. Floor care product according to one of claims 1-7, characterized in that it is based on wetting agents Contains chlorocarboxylic acid » Dr. EyiDö. 209842/0933