JP3065559B2 - Fluorosiloxane-containing care composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an aqueous care composition containing a fluoroorganopolysiloxane for hard surfaces.

[0002]

BACKGROUND OF THE INVENTION Care compositions based on fluoroorganopolysiloxanes for hard surfaces, for example for automotive bodies, are already known. In this connection, reference can be made, for example, to JP-A-4-202389, in which a hydroxyl-containing methyltrifluoropropylsiloxane having a fluorine content of 0.1 to 26.5% by weight is crosslinked with a silicon alkoxide. Described are fluorinated organopolysiloxanes synthesized by reacting with dimethylsiloxane and care compositions obtained by a method of dispersing a wax or wax-like substance in water. Fluorinated organopolysiloxanes are solid, branched silicone rubbers whose aggregation state is no longer reversible.

[0003] JP-A-3-227383 discloses a trimethylsilyl-capped polymethyl (trifluoropropyl) siloxane and carnauba wax 12, Hoech.
A care composition is described that includes a wax, such as stwax PE 1303 and MINK 5, and an aliphatic solvent. Fluorinated organopolysiloxanes are liquid siloxanes that can be easily washed away or re-emulsified due to their agglomerated state. European Patent (EP
-A) 0 548 789 describes hard surface care compositions prepared using organopolysiloxanes which are essentially free of organic solvents and are solid at room temperature.

[0004] German Patent (DE-C) 3635093
No. 1 describes the preparation of a fluorine-containing siloxane by the reaction of an alcohol containing a fluorine group with a Si—H-containing siloxane. However, the product thus produced reacts by hydrolysis in aqueous systems to form silanols due to the newly formed Si-OC crosslinks, which are then polymerized by condensation. The fluorine-containing alcohol used is again obtained as a further fission product. Furthermore, this document describes, as prior art, the production of fluorine-containing products by reacting a SiH component with a fluorine-containing olefin.

[0005] Known fluorine-containing organopolysiloxanes have very low application because they can be washed out again with water or re-emulsified when they are liquids and their agglomeration state can no longer be changed when they are crosslinked. It is difficult, because it cannot be liquefied again due to the frictional heat generated during the application. In addition, they sometimes contain organic solvents, which are undesirable because of their toxicity and the risk of fire.

[0006]

Therefore, in addition to a care composition containing an organopolysiloxane as a main component and a solvent, it is substantially free of an organic solvent and can change its aggregation state reversibly. Can and therefore has good hydrophobic action
There was the problem of providing a care composition which also shows good oleophobization at the same time as (hydrophobation).

[0007]

SUMMARY OF THE INVENTION The present invention can be produced by using an organopolysiloxane which is solid at room temperature and contains a fluorine atom, and its aggregation state can be reversibly determined based on a change in temperature. It relates to a hard surface care composition that can be changed.

In the present invention, the reversible change of the aggregation state means that the solid state of aggregation changes reversibly to the liquid state of aggregation and conversely, the liquid state of aggregation changes to the solid state of aggregation.

The aqueous care composition according to the invention is preferably free of organic solvents. However, these compositions
Organic solvents can be included in small amounts, such as less than 2% by weight, based on the total weight of the care composition, as in, for example, preservatives.

In the following, room temperature is to be understood as meaning a temperature of 20 degrees.

Is solid at room temperature, contains a fluorine group, and
The organopolysiloxanes used according to the invention are preferably
Preferably the formula R_aR¹ _bSiO_{(4-ab) / 2} (I)  Wherein R may be the same or different and are monovalent
A hydrocarbon group or a hydrocarbon group containing a fluorine group
R¹May be the same or different and fluorine
A is a hydrocarbon group containing a group, wherein a is 0, 1, 2, or
3, 0.75 to 1.5 on average, preferably on average
0.9 to 1.1, b is 0, 1, 2, or 3, average
0.0 to 1.1, preferably 0.01 to an average
0.07 where the sum of a + b is less than 3
Or charcoal equal to 3 and containing fluorine groups in all molecules
There is at least one unit containing a hydride group]
Having the following unit.

Is solid at room temperature and has the formula R ₃ SiO (SiR ₂ O) _x [(SiRR ¹ O) _r (SiRR ² O) _s ] _y SiR ₃ (II) wherein R and R ¹ are based on Has the meaning given above and R ² may be the same or different and is a monovalent hydrocarbon radical, and r is a value from 0 to 100, preferably from 0.1 to 20 Value, particularly preferably an integer having a value of 0.5 to 10, wherein s is 0 to 179
Value, preferably 10 to 120, particularly preferably 40
X is an integer having a value of 0 to 90, x is a value of 0 to 300,
Preferably 10 to 180, particularly preferably 20 to 80
Wherein the sum of x + y is from 0 to 300, preferably 200, particularly preferably 100, provided that at least one group R in formula (II) has at least 1
Having the meaning of a hydrocarbon group having 8 carbon atoms, x +
When y = 0, at least one group has the meaning of R ¹ ].

The radical R is preferably a hydrocarbon radical having 1 to 24 carbon atoms.

Examples of radicals R are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert.
Alkyl groups such as -butyl, n-pentyl, isopentyl, neopentyl and tert-pentyl groups, n-
Hexyl group such as hexyl group, heptyl group such as n-heptyl group, octyl group such as n-octyl group, isooctyl group such as 2,2,4-trimethylpentyl group, and n-nonyl group Decyl group such as nonyl group, n-decyl group, dodecyl group such as n-dodecyl group, octadecyl group such as n-octadecyl group and n-eicosyl group; alkenyl group such as vinyl group and allyl group; cyclopentyl O, cycloalkyl groups such as cyclohexyl and cycloheptyl and methylcyclohexyl groups; aryl groups such as phenyl and naphthyl and anthryl and phenanthryl groups;
Alkaryl groups such as-, m- and p-tolyl groups, xylyl groups and ethylphenyl groups; aralkyl groups such as 0 and benzyl groups and α- and β-phenylethyl groups.

R is particularly preferably a methyl group and n
An octadecyl group.

Examples of radicals R substituted by fluorine radicals are preferably the substituents mentioned for R ¹ .

The group R ¹ is preferably an alkylene-R _F group, wherein the alkylene group is preferably an ethylene or propylene group. R _F is preferably having 1 to 12 carbon atoms, a linear or branched, perfluorinated radicals.

[0018] Examples of radicals R _F is preferably: a trifluoromethyl group or a perfluorohexyl group.

The radical R ² is preferably a hydrocarbon radical having 1 to 18 carbon atoms, the methyl radical being particularly preferred.

Examples of radicals R ² are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert.
-Butyl, n-pentyl, isopentyl or ter
alkyl groups such as t-pentyl, hexyl such as n-hexyl, heptyl such as n-heptyl, octyl such as n-octyl, and 2,
Isooctyl such as 2,4-trimethylpentyl, nonyl such as n-nonyl, decyl such as n-decyl and dodecyl such as n-dodecyl; vinyl and allyl Alkenyl groups; cycloalkyl groups such as cyclopentyl, cyclohexyl and cycloheptyl groups and methylcyclohexyl groups; aryl groups such as phenyl, naphthyl and anthryl and phenylanthryl groups; o-, m- or p-tolyl groups, xylyl And alkaryl groups such as ethylphenyl group; and aralkyl groups such as benzyl group and α- and β-phenylethyl groups.

Although not shown in the above formula, up to 10 mol% of the diorganosiloxane units may be substituted by other siloxane units. However, these siloxane units are usually more or less difficult to avoid,
For example, it is present only as an impurity such as an R ₃ SiO _1/2 , RSiO _3/2 or SiO _4/2 unit, where R has the meaning given above for this group.

The organopolysiloxanes which are solid at room temperature and which are used according to the invention are described, for example, in GB 68
No. 5173A (announced December 31, 1951, Dow
Corning Ltd), U.S. Patent No. 2,842,521 (published July 8, 1958, Wacker-Chemi).
e GmbH), French Patent No. 1475709A (published April 7, 1967, General Elec)
tric Company) U.S. Pat. No. 3,668,180 (published on June 6, 1972, Stauff-Wack)
er-Silicone Corporation),
U.S. Pat. No. 3,792,071 (published February 12, 1974, Wacker-Chemie GmbH); U.S. Pat. No. 3,846,358 (published Nov. 5, 1974, Ge
general Electric Company) and U.S. Pat. No. 4,298,753 (published Nov. 3, 1981, Wacker-Chemie GmbH). In the process described there, analogously, a product containing fluorine groups is preferably added to the H-siloxane in a first step and an unsaturated olefin is added in a second step.

The polysiloxanes according to the invention containing fluorine groups are preferably of the general formula III

[0024]

Embedded image

Wherein R ³ is the same or different monovalent,
Optionally a halogen-substituted C ₁ -C ₁₅ -hydrocarbon group or a hydrocarbonoxy group or a hydroxyl group, a is 0, 1, 2 or 3;
1.2, especially 0.1-1; b is 0, 1, 2, or 3, on average 1.0-2.0, especially 1.4-1.8
Where there is at least one Si-bonded hydrogen atom per molecule.

Examples of C ₁ -C ₁₅ -hydrocarbon groups are methyl,
Alkyl groups such as ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl and tert-pentyl groups; hexyl groups such as n-hexyl groups; n
Heptyl group such as heptyl group; octyl group such as n-octyl group and isooctyl group such as 2,2,4-trimethylpentyl group; nonyl group such as n-nonyl group; n-decyl group and the like. Decyl group such as n-dodecyl group; alkenyl group such as vinyl group and allyl group; cycloalkyl group such as cyclopentyl, cyclohexyl and cycloheptyl group and methylcyclohexyl group; phenyl, naphthyl, anthryl and phenanthryl An aryl group such as a group; o-, m
Alkaryl groups such as-and p-tolyl groups, xylyl groups and ethylphenyl groups; and aralkyl groups such as benzyl groups and α- and β-phenylethyl groups.

Examples of halogen-substituted C ₁ -C ₁₅ -hydrocarbon groups are 3,3,3-trifluoro-n-propyl, 2,
Alkyl groups substituted by fluorine, chlorine, bromine and iodine atoms, such as 2,2,2 ', 2', 2'-hexafluoroisopropyl and heptafluoroisopropyl, and o-, m- and p-chloro It is a haloaryl group such as a phenyl group.

Unsubstituted C ₁ -C ₆ -alkyl groups, in particular methyl and phenyl, are particularly preferred.

The C ₁ -C ₁₅ - Examples of hydrocarbonoxy groups, divalent above via an oxygen atom to a silicon atom of the C ₁ -C ₁₅ - hydrocarbon radical. Preferably,
5% of the radicals R ³ or less, not particularly anything a hydrocarbonoxy group or a hydroxyl group. Particularly preferred H-
Siloxane is a methyl hydride polysiloxane terminated by trimethylsilyl.

The H-siloxane is preferably 3 ° C. at 25 ° C.
300 mm ² / s or less, preferably 5 to 100 mm ² / s, particularly preferably has a viscosity of 15 to 25 mm ² / s. Linear H-siloxanes are preferred. The hydrogen content is preferably between 0.05 and 5.0% by weight.

The H-siloxane is preferably used in an amount of 5 to 25% by weight, preferably in an amount of 10 to 20% by weight, particularly preferably in an amount of 15 to 18% by weight. The H-siloxane is preferably heated in an organic solvent such as toluene or xylene to a temperature of 80-120 ° C. while passing an inert gas, preferably nitrogen.

Perfluorohexylethylene is particularly preferred, in which a fluorine-containing olefin such as, for example, trifluoropropene, perfluorohexylethylene or tetrafluoroethylallyl ether is added to the mixture.

The fluorine-containing olefin is preferably used in an amount of 0.1 to 80% by weight, preferably in an amount of 1 to 60% by weight, particularly preferably in an amount of 5 to 40% by weight.

A known platinum catalyst is also added. Platinum group metals and / or compounds thereof, preferably platinum and / or compounds thereof, are used. Here, all catalysts used to date for adding hydrogen atoms directly bonded to Si atoms to aliphatically unsaturated compounds can be used. Examples of such catalysts are finely divided metal platinum, which may be supported on a carrier such as silicon dioxide, aluminum oxide or activated carbon, and platinum compounds or complexes such as platinum halides, for example PtCl ₄ , H ₂ PtC
l ₆ . 6H ₂ O or Na ₂ PtCl ₄ . 4H ₂ O, platinum -
Olefin complexes, platinum - alcohol complexes, platinum alcoholate complexes, platinum - ether complex, a platinum - aldehyde complexes, platinum - (including H ₂ PtCl6.6H ₂ reaction products of O and cyclohexanone) ketone complexes, platinum - vinylsiloxane complex, In particular, platinum-divinyltetramethyldisiloxane complexes with or without detectable inorganically bound halogen content, bis- (γ-picoline) -platinum dichloride, trimethylenedipyridineplatinum dichloride, dichloride dichloride Reaction products of cyclopentadieneplatinum, dimethylsulfoxide-dichloromethane-ethyleneplatinum (II) and platinum tetrachloride with olefins and primary or secondary amines or primary and secondary amines, such as 1-octene Products of platinum tetrachloride and secondary butylamine dissolved in water Or European patent (EP-
B) Ammonium platinum complex according to 110370.

The platinum catalyst is preferably 0.5 to 500 ppm by weight, calculated in each case as elemental platinum and based on the total weight of H-siloxane present in the composition.
(Parts per million by weight), in particular in amounts of 2 to 400 ppm by weight.

The fluorinated olefin and the platinum catalyst are preferably added within a period of 30 minutes and are preferably stirred at a temperature of 120 ° C. for 2 hours.

Then, in a second step, alkylenes such as, for example, n-octadecene and n-eicosene are added to the mixture. The alkylene is preferably 10
An amount of ８０80% by weight, preferably an amount of 20-70% by weight,
It is particularly preferably used in an amount of 30 to 60% by weight.

The mixture is preferably added within a time period of 30 to 120 minutes, then the mixture is heated to 100 to 140 ° C.
At a temperature of preferably 30 to 12 minutes. Finally, also alkylenes having 6 to 10 carbon atoms, preferably n-octene, are also preferably present in an amount of 0 to 20% by weight, preferably in an amount of 1 to 15% by weight, particularly preferably 5 to 10% by weight. And the mixture is preferably stirred at a temperature of 100-140 ° C. for 30-120 minutes. At the end, the mixture is preferably 120-150 ° C.
The final product is 8% of the calculated theoretical yield.
It is obtained in an amount of 5-99% by weight.

The organopolysiloxane which is solid at room temperature and has units of the formula (I) is preferably (RSi0
_3/2 ) units of organopolysiloxane and (R ₃ SiO
_1/2 ) and (SiO _4/2 ) units of organopolysiloxanes, where R has the meaning given above.

Preferably, 10 to 50%, particularly preferably 25 to 50%, in particular 35 to 50%, of the number of radicals R in the organopolysiloxane of the formula (II) are at least 1%.
A hydrocarbon group having 8 carbon atoms. Other groups are preferably methyl groups for easy availability.

An example of an organopolysiloxane of the formula (II) which is solid at room temperature and which is used according to the invention is Me _{3
SiO [MeSi (n-C 18} H 37) O] m [MeSi (C
H ₂ CH ₂ (CF ₂ ) ₅ CF ₃ ) O] nSiMe ₃ [where m is 10
To 150, preferably 20 to 120, particularly preferably 4
N is an integer of 0 to 90, and n is 0 to 30, preferably 0 to
20, particularly preferably an integer of 1 to 12, preferably an m: n ratio of 30: 1 to 1: 1;
A ratio of 1 to 4: 1 is particularly preferred].

The organopolysiloxane of the formula (II) which contains fluorine groups and is solid at room temperature is preferably B: Me ₃ SiO [MeSi (n-C ₁₈ H ₃₇ ) O] ₅₇ [M
_{eSi (CH 2 CH 2 (CF} 2) 5 CF 3) O] 3 SiMe 3 C: Me 3 SiO [MeSi (n-C 18 H 37) O] 54 [M
_{eSi (CH 2 CH 2 (CF} 2) 5 CF 3) O] 6 SiMe 3 D: Me 3 SiO [MeSi (n-C 18 H 37 O] 48 [M
The organopolysiloxane of formula (II) containing eSi (CH ₂ CH ₂ (CF ₂ ) ₅ CF ₃ ) O] ₁₂ SiMe ₃ fluorine groups, which is solid at room temperature and is used according to the invention is preferably at least 1000, particularly preferably 100
It has a molecular weight of 00 to 30,000.

The organopolysiloxanes which contain fluorine groups, are solid at room temperature and are used according to the invention have a waxy consistency and a melting point of from 25 to 60 ° C.

The care compositions according to the invention are particularly preferably solid at room temperature and organopolysiloxanes having units of the formula (I) or compounds of the formula (I) which are solid at room temperature.
It is prepared using the organopolysiloxane of I) or a mixture thereof.

For the preparation of the care compositions according to the invention, the organopolysiloxanes which are solid at room temperature and contain fluorine groups are in each case based on the total weight of the care composition according to the invention. Preferably 0.1 to 5.
It is used in an amount of 0% by weight, particularly preferably 0.5 to 2.0% by weight.

The organopolysiloxanes which are solid at room temperature are preferably used for the preparation of the care compositions according to the invention in the form of aqueous emulsions.

Organopolysiloxanes which contain fluorine groups, are solid at room temperature and contain units of the formula (I)
When used for the preparation of the care compositions according to the invention, the emulsions are preferably solid at room temperature and contain an organopolysiloxane containing fluorine groups and containing units of the formula (I) using an emulsifier. It is manufactured by emulsification in water.

The emulsification of the organopolysiloxane which is solid at room temperature and contains fluorine groups can be carried out in customary mixing equipment suitable for the production of emulsions.

All ionic and non-ionic emulsifiers known to date (both alone and as a mixture of different emulsifiers which until now were able to produce stable aqueous emulsions of organopolysiloxanes) are solid at room temperature. And organopolysiloxanes containing fluorine groups which can be used according to the invention as emulsifiers in the production of aqueous emulsions. These emulsifiers can also be used as described in German Patent 3613384C and the corresponding US patent application (classification number USSN 19988). Preferably, nonionic and cationic emulsifiers are used. Here, fatty alcohol polyglycol ether, nonylphenol polyglycol ether, tri-n-butylphenol polyglycol ether and quaternary ammonium salts of saturated and unsaturated fatty acids are particularly preferably used. An organopolysiloxane which is solid at room temperature and contains fluorine groups, which is used according to the invention;
The aqueous emulsions contain the emulsifier in an amount of preferably 2 to 8% by weight, particularly preferably 3 to 5% by weight, based on the total weight of the organopolysiloxane used, which is in each case solid at room temperature.

The organopolysiloxanes which are solid at room temperature and contain fluorine groups, which are used according to the invention,
Aqueous emulsions are in each case preferably from 10 to 60% by weight, in particular from 1 to 60% by weight, based on the total weight of the emulsion.
It has a solids content of 5-42% by weight.

The temperature required for the melting depends on the organopolysiloxane used and is preferably between 20 ° C. and 60 ° C., particularly preferably between 40 ° C. and 50 ° C.

The emulsification of the melt components is carried out by customary methods in silicon chemistry.

The organopolysiloxane according to the invention, which is solid at room temperature and contains fluorine groups, is dissolved in an organic solvent and, if appropriate, with the addition of suitable additives as described below by way of example, with the aid of a care composition. It can be used as an object. The organic solvent is preferably petroleum benzine. A solution is produced having a content of preferably 0.1 to 20% by weight, preferably 0.1 to 10% by weight, particularly preferably 0.1 to 5% by weight, of the solid organopolysiloxane containing fluorine groups. .

Depending on the intended use, the care compositions according to the invention may contain additives such as, for example, silicon-free waxes, thickeners, abrasives, preservatives and additives and, where appropriate, also silicones or their derivatives. It may contain an emulsion.

Examples of waxes which do not contain silicon are waxes of plant origin which occur naturally, such as carnauba and candelilla waxes, montanic acid and montan ester waxes, partially oxidized synthetic paraffins, polyethylene waxes, polyvinyl ethers. Waxes, metal-soap-containing waxes, are preferred with carnauba, paraffin and polyethylene waxes, and paraffin waxes are particularly preferred.

If waxes are used for the preparation of the care compositions according to the invention, the waxes are preferably in each case 0.1 to 5.0% by weight, based on the total weight of the care composition, in particular Preferably it is used in an amount of 0.1-1.0% by weight.

Examples of thickeners are simple polysaccharides, complex polysaccharides,
Polyacrylates, with polyacrylates being preferred and polysaccharides being particularly preferred.

If thickeners are used for the preparation of the care compositions according to the invention, these thickeners are in each case 0.1 to 1.5% by weight, based on the total weight of the care composition. %, Particularly preferably 0.3 to 0.6% by weight.

Examples of abrasives are polished alumina, so-called siliceous chalk, pyrogenic silicic acid and, for example, Lehm
"Snow Floss" from Ann & Foss
And diatomaceous earths which occur naturally, such as siliceous chalk and polished alumina.

When using abrasives for the preparation of the care composition according to the invention, these abrasives are preferably
In each case, 1 to 1 relative to the total weight of the care composition
It is used in an amount of 10% by weight, particularly preferably 3-5% by weight.

Examples of preservatives are formaldehyde, parabene, benzyl alcohol, salicylic acid and its salts and isothiazolinone, with formaldehyde and isothiazolinone being preferred, with formaldehyde being particularly preferred.

If preservatives are used for the preparation of the care compositions according to the invention, these preservatives are preferably in each case 0.1%, based on the total weight of the care composition.
01 to 0.30% by weight, particularly preferably 0.05 to
Used in an amount of 1.10% by weight.

Examples of additives are fragrances and dyes.

If additives are used for the preparation of the care composition according to the invention, these additives are preferably present in each case based on the total weight of the care composition.
01 to 0.50% by weight, particularly preferably 0.05 to 0.5%
It is used in an amount of 0.50% by weight.

From each of the abovementioned substance groups as possible components for the liquid care composition according to the invention, it is also possible to use in each case one substance of this group or a mixture of at least two different such substances as a component. it can.

The care compositions according to the invention preferably contain water, preferably 85 to 99.9% by weight, in particular 93 to 9% by weight, based in each case on the total weight of the care composition.
Water, preferably in demineralized water, in an amount of 9.5% by weight.

The individual components of the care composition according to the invention can be mixed with one another in any desired way. Thus, for example, the additives can be mixed with the organopolysiloxane that is solid at room temperature before the emulsification step.
However, the additives can also be mixed with organopolysiloxanes which are solid at room temperature and, where appropriate, with ready-to-use emulsions of organopolysiloxanes which are preferably liquid at room temperature.

The emulsification or mixing of the components which can be used for the preparation of the care composition according to the invention is preferably carried out at ambient pressure, ie between 900 and 1100 hPa, at a temperature of from 20 to 50 ° C. Will be implemented. However, higher or lower temperatures and higher or lower pressures can also be used. The emulsification process is carried out by means of customary mixing equipment suitable for the production of emulsions, for example P.P. as known by the trade name "Ultra-Turrax". It can be implemented in a high speed stator / rotor stirrer by Professor Willem.

The care composition according to the invention additionally comprises
It has the advantage of having excellent resistance to oils, fats and solvents. This is particularly important in the case of surfaces which are exposed to heavy contamination, for example by oily carbon black from internal combustion engines, or which come into direct contact with solvents, for example at the fuel tank filling of motor vehicles.

Furthermore, the care compositions according to the invention are non-flammable (water-based), easy to use and have good color depth and high gloss on treated solid surfaces. It has the advantage of giving.

[0071]

EXAMPLES In the examples set forth below, all parts and percentage data are by weight unless otherwise indicated. In addition, all viscosity data relate to a temperature of 25 ° C. Unless otherwise stated, the examples below were performed under the pressure of the surrounding atmosphere, ie, a pressure of about 1000 hPa and at room temperature, ie, about 20 ° C. or at the temperature established when the reactants were combined without additional heating or cooling.

The wetting angle measurement was performed as follows: 0.0
A water drop having a volume of 1 ml is applied to the surface to be tested from a height of 15 mm and the wetting angle is measured with the aid of a goniometer (Model 100-10 from Rame-Hart Inc., NJ, USA). I do. The measurement is repeated four times to obtain an average of five measurements.
The measurement of the wetting angle on a support which has not been treated with the care composition according to the invention is referred to below as the blank test value.

[0073] the following abbreviations are used: Me: methyl group Et: would have using ethyl _{group: A: Me 3 SiO [MeSi} (n-C 18 H 37) O] 60 -
_{SiMe 3 B: Me 3 SiO [} MeSi (n-C 18 H 37) O]
₅₇ [MeSi (CH ₂ CH ₂ (CF ₂ ) ₅ CF ₃ ) O] ₃ Si
Me ₃ C: Me ₃ SiO [MeSi (n-C ₁₈ H ₃₇ ) O]
₅₄ [MeSi (CH ₂ CH ₂ (CF ₂ ) ₅ CF ₃ ) O] ₆ Si
Me ₃ D: Me ₃ SiO [MeSi (n-C ₁₈ H ₃₇ ) O]
₄₈ [MeSi (CH ₂ CH ₂ (CF ₂ ) ₅ CF ₃ ) O] ₁₂ S
iMe ₃ Example 1: Benzine formulation Hydrophobization test: wax AD dissolved in Petroleum Spirit 100/140 ゜ (available from Merck) in 2% strength amount and the solution applied to the painted laminate of the car body Apply and rub in a contact angle of 66 ° with water using wadding.
After standing at room temperature for 15 minutes, the wetting angle of the treated surface with respect to water is measured, and then the support is treated at room temperature with 10 l / 100 cm ² of surface water in a mains water having a temperature of about 6 ° C. from a distance of 20 cm in each case. And sprinkle four times for 15 minutes.
Table 1 shows the results of the wetting angle measurement.

Table 1 Sprinkled wax A wax B wax C wax D time (wetting (wetting (wetting (wetting [minute] angle) angle) angle) angle) 0 101 102 104 105 15 102 102 105 105 106 30 100 100 100 104 106 106 45 98 98 102 102 60 60 97 98 102 105 Test for oleophobicity: wax A-D, petroleum spirit
100% / 140 ゜ (available from Merck) 2%
Dissolve to a degree and pack the solution into a thin painted car body.
Applied with paraffin oil at a contact angle of 20 ° using cotton
Then rub. Let stand for just 15 minutes at room temperature, then treat
The wetting angle of paraffin oil on the wetted surface is measured. Conclusion
The results are given in Table 2: Table 2 Wax A Wax B Wax C Wax D  (Wetting (wetting (wetting angle) angle) angle) angle) 45 51 53 48
Show the best compromise between.

Example 2: Aqueous formulations Ready-to-use formulations Polyacrylic acid (C from Neuss, Goodrich)
Disperse 0.3 g in 96.4 g of deionized water with stirring, then 2.0 g of the emulsion described in A, 1.0 g of the emulsion described in B, 0.2 g of triethanolamine and 0.2 g of triethanolamine. 0.1 g of formalin solution (concentration 40%) is added.

The hydrophobic and oleophobic active composition thus obtained is applied and rubbed into the body of a car body using cotton wool at a contact angle of 66 ° with water and a contact angle of 20 ° with paraffin oil. After standing at room temperature for 15 minutes, the wetting angles with respect to water and paraffin oil are measured, and then the lamellas are washed four times with a mains water having a temperature of about 6 ° C. from a distance of 20 cm in each case at 10 l per 100 m ² of surface for 15 minutes. Sprinkle water. The results of the wetting angle measurements for water and paraffin oil are found in Table 3.

A) Fatty alcohol polyglycol ether emulsifier (“Genapo” from Hoechst AG)
1 ") can be purchased from the formula Me ₃ SiO
_{[MeSi (n-C 18 H} 37) O] 54 [MeSi (CH 2
_{CH 2 (CF 2) 5 CF} 3) O] was added to the ₆ SiMe ₃ organopolysiloxane 175 g, the mixture is stirred. This mixture is then emulsified by the addition of 300 g of deionized water with the aid of an emulsifier, with constant stirring. Aqueous emulsions of fluorine-containing organopolysiloxanes which are solid at room temperature are obtained at a solids content of 38% by weight, based on the total weight of the emulsion.

B) Fatty alcohol polyglycol ether emulsifier (from Hoechst AG "Genapo"
15 g of dimethylpolysiloxane terminated with trimethylsiloxy units and having a viscosity of 350 mm ² / s (Wacker, Munich)
(Available under the name "AK350" from Chemie GmbH) and add 175 g and stir the mixture. The mixture is then emulsified by adding 310 g of deionized water, with constant stirring, with the aid of an emulsifier. An aqueous emulsion of dimethylpolysiloxane which is liquid at room temperature is obtained at a solids content of 37% by weight, based on the total weight of the emulsion.

Table 3: Watering time Paraffin oil related to water [min] Wetting angle Wetting angle 0 106 35 15 102 51 * 30 102 51 * 45 101 52 * 60 100 52 ** A component that is liquid at room temperature and has good compatibility with paraffin, such as the dimethylpolysiloxane used in B, so claims The oleophobic effect of the formulations described in section applies only when these components, which are liquid at room temperature, are washed away.

Continuation of the front page (72) Inventor Franz Wimmer, Germany Burghausen a Sternweg 1 a (56) References JP-A 8-48942 (JP, A) JP-A 4-202389 (JP, A) Kaihei 3-227383 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09G 1/00 C08G 77/24 C09G 1/02 C09K 3/00 C09K 3/18

Claims (11)

(57) [Claims] 1. Use of an organopolysiloxane which is solid at room temperature, contains fluorine groups and has a melting point of from 25 to 60 ° C., whereby the state of aggregation can change reversibly on change of temperature. A care composition for hard surfaces that can be manufactured. 2. A may be the room temperature organopolysiloxane containing solid at and fluorine radical of the formula ^{_{R a R 1 b SiO (4}} -ab) / 2 (I) [ wherein R is the same or different And a monovalent hydrocarbon group or a hydrocarbon group containing a fluorine group, R ¹ may be the same or different, and is a hydrocarbon group containing a fluorine group, and a is 0, 1, 2 or 3, averaging 0.75 to 1.5, b is 0, 1, 2, or 3, averaging 0.0 to 1.1, provided that the sum of a + b is less than 3 Or at least one unit having a hydrocarbon group containing a fluorine group which is equal to 3 is present in the whole molecule]. 3. The organopolysiloxane which is solid at room temperature and contains fluorine groups is solid at room temperature and has the formula R ₃ SiO (SiR ₂ O) _x [(SiRR ¹ O) _r (SiRR
² O) _s ] _y SiR ₃ (II) wherein R ¹ and R ² have the meanings given above for these groups, and R ² may be the same or different and are monovalent of a hydrocarbon group, and r is an integer having a value of 0 to 100, s is an integer having a value of 0 ~ 179 [, x is an integer having a value of 1 to 300, y is 1 Is an integer having a value of １８０180 and the sum of x + y is from 0 to 300, provided that at least one group R in formula (II) has the meaning of a hydrocarbon group having at least 18 carbon atoms, and the case of x + y = 0, at least one group R is a straight-chain organopolysiloxane have the meanings of R ^1, claim 1 care composition. 4. For the preparation of the care composition, the organopolysiloxane which is solid at room temperature and contains fluorine groups is present in an amount of from 0.1 to 5.% based on the total weight of the care composition.
4. The care composition according to claim 1, wherein the care composition is used in an amount of 0% by weight. 5. A care composition wherein the organopolysiloxane which is solid at room temperature and contains fluorine groups is used in the form of an aqueous emulsion. 6. The care composition according to claim 1, wherein the organopolysiloxane which is solid at room temperature and has a fluorine group is used in the form of a formulation containing a solvent. 7. For the preparation of a care composition, additives such as non-silicon-containing waxes, thickeners, abrasives, preservatives and additives such as fragrances and colorants, 7. The care composition according to claim 1, further comprising, if appropriate, a silicone or an emulsion thereof. 8. The care composition according to claim 1, wherein water is included in an amount of 85 to 99.9% by weight, based on the total weight of the care composition. Stuff. 9. The method according to claim 1, which does not include an organic solvent.
And a care composition according to any one of 7 or 8. 10. A method for treating a hard surface, comprising applying the care composition according to any one of claims 1 to 9 to the hard surface. 11. The hard surface is selected from the group consisting of a metal surface, a painted surface and a plastic surface.
The described method.