WO2016023613A1

WO2016023613A1 - Particles coated with fluorosurfactants, and use of these particles

Info

Publication number: WO2016023613A1
Application number: PCT/EP2015/001517
Authority: WO
Inventors: Jens Kersten; Alfred Hennemann
Original assignee: Merck Patent Gmbh
Priority date: 2014-08-14
Filing date: 2015-07-23
Publication date: 2016-02-18
Also published as: EP3180400A1

Abstract

The present invention relates to coated particles, more particularly to particles coated with fluorosurfactants, to a method for producing these particles, and also to the use thereof, preferably in powder coatings.

Description

FLUORESIDE COATED PARTICLES AND THEIR USE

The present invention relates to coated particles, more particularly to fluorosurfactants coated inorganic particles, a process for their preparation and their use.

Inorganic particulate materials are often used as additives or fillers in coating compositions and bulk materials and serve there to improve a variety of properties, such as the increase in mechanical strength, the improvement of scratch and abrasion resistance, the improvement of color properties, the reduction of manufacturing costs or the

Improvement of the flowability of finely divided materials, to name but a few.

In particular, in coating compositions of various kinds, it is also known to use surface-active substances to influence, for example, the surface tensions of substrates and coating compositions such that the coating process and the subsequent solidification of the layer can proceed without flow disturbances, so that the coatings produced no surface damage such Crater, fish eyes, pinholes and the like and the coatings produced neither shrink nor dissolve from the ground. Such surfactants may have nonionic, anionic, cationic or amphoteric functional groups.

Preferably used as surface-active substances are organically modified polysiloxanes, acrylates, fluorosurfactants or special esters which either reduce the surface tension or float in a controlled manner on the respective film surface. Fluorosurfactants are generally more effective than the organically modified polysiloxanes commonly used. However, this only applies if the fluorosurfactants contain fluorinated hydrocarbon chains with a sufficiently high number of fluorine atoms for a sufficiently long time. However, the latter are disadvantageous for environmental reasons as well as from a physiological point of view, since they can be degraded only with the formation of environmentally harmful perfluorocompounds (Perfluorlalkylcarbonsäuren and perfluoroalkylsulfonic acids) and also enriched in living bodies (bioaccumulation).

Powder coatings have the great advantage over other coating compositions that they can do without the use of organic or aqueous solvents. In view of ever stricter legal measures for the reduction of volatile organic constituents in application media for the protection of man and the environment, powder coatings have therefore become increasingly important in recent decades, for example for the coating of metal surfaces in general, for household appliances, facade coatings, automotive coatings or furniture coatings. In addition to the established methods for coating of

In the meantime, metal surfaces have also been developed by means of which non-conductive plastics can also be coated with powder coatings.

Powder coatings are applied to the respective substrates in an electrostatic application process. In this case, an electrically charged powder cloud is produced from the powdered powder coating from the same powder charged powder particles, which is transported by means of a powder spray gun to the, usually grounded, material surface and is reflected there. The charging of the powder particles can be effected both by an applied high voltage (corona charging or ionization) and by friction on the inner surface of the spray gun (triboelectric

Charge). The powder particles adhere electrostatically to the Material surface and form a powder coating layer, which is subsequently cured by baking or UV curing. The layer formation is initially linear, but then breaks off at a certain layer thickness due to charge effects. It also leads to the so-called Rücksprüheffekten that manifest themselves among other things in surface damage of the powder coating layer. For this reason, powder coating layers can only be produced up to a maximum thickness of 150 μm. Technologically, this maximum layer thickness is generally well below due to the feared paint damage. Therefore, powder coating layers can only be produced in good quality up to a thickness of approximately 120 μm.

With the optimum particle size distribution of the powder coating for electrostatic application, it is difficult to produce homogeneous, thin and, in addition, glossy powder coating layers. Since it is difficult to deposit the necessary fine powder coating particles in the electrostatic application on the substrate, a sufficient uniformity of the layers is also expected only from a certain minimum layer thickness, which is about 60 μητι. In terms of process and total costs and for special

Applications, for example for the production of special protective layers, it would be desirable to be able to produce powder coatings, which can be applied by means of conventional application methods and applicators on substrates in such layer thicknesses are smaller than said minimum layer thicknesses or greater than the said

Maximum layer thicknesses.

Powder coatings consist of binders, additives, colorants and fillers. As additives, for example leveling agents, degassing agents, waxes and / or structurants are used. As leveling agent polyacrylates are often used, which are produced for a reduced surface tension and thus for a good surface quality Powder coating surfaces provide. Occasionally, the use of fluorosurfactants has also been described, which are usually used when platelet-shaped effect pigments which are difficult to incorporate into the powder coating are to be contained therein.

The object of the present invention is to provide an agent which can be used as an additive in conventional paints, lacquers, printing inks, etc., in particular in powder coatings, and is preferably suitable for use in powder coatings for the formation of particularly thin or particularly thick powder coating layers without any risk of permanent damage to humans and the environment caused by toxic or bioaccumulative decomposition products in the manufacture, use or recycling of the product or products produced therefrom. Another object of the present invention is to provide a process for producing such an agent.

An additional object of the present invention is to disclose the use of such an agent as well as products that can be advantageously prepared using the agent.

The object of the present invention is achieved by particles consisting of a core with a surface coating, wherein the surface coating comprises at least one compound of the formula (I):

(I) in which

X is a hydrophilic group,

R = linear or branched alkylene, wherein one or more nonadjacent C atoms may be replaced by O, S, and / or N, r = 0 or 1,

B = a single bond, O, NH, NR ', CH ₂ , C (O) -O, S, CH ₂ -O, OC (O), O-C (O) -O, NC (O), C ( 0) -N, 0-C (0) -N, NC (0) -N, SiR ' ₂ -, SiR' ₂ -0, 0-S0 ₂ or S0 ₂ -0, where R '= linear or branched Alkyl is,

R ¹ and R ² = independently of one another are hydrogen or -Chb-COY ³ - L ³ - (A ³ ) n ₃ ,

Y ¹ , Y ² and Y ³ = independently of one another are O, S or N,

L ¹ , L ² and L ³ = are independently linear or branched alkylene, wherein one or more nonadjacent C atoms may be replaced by O, S, and / or N,

A ¹ , A ² and A ³ = independently of one another are hydrogen or a group of the structure -Z ⁱ (CR ³ R ⁴ ) miRf ⁱ , where i = 1, 2 or 3,

Z 'is O, S or N and is bonded to a C atom of U or is a single bond,

R ³ and R ^{4 are} independently hydrogen or an alkyl group,

Rf "is a fluorine-containing radical,

n1, n2 and n3 = are independently 1-6,

m1, m2 and m3 = are independently 0-5,

and the compounds of formula (I) at least one Rf group

contain.

The object of the invention is likewise achieved by a process for the preparation of the abovementioned particles, in which a particulate core material kept in motion is intensively mixed with at least one compound of the formula (I) and the mixture, optionally under protective gas, is dried. Furthermore, the object of the present invention is also achieved by the use of the previously described particles as an additive in paints, lacquers, printing inks, protective coatings, paper coatings, synthetic resins, sealants, bulk solids, toners, floor polishes or adhesives and by paints, varnishes, printing inks, protective coatings , Paper coatings, synthetic resins, sealants, bulk materials, toners, floor polishes or adhesives containing the previously described

Particle. The core of the particles according to the invention preferably consists of an inorganic material and is in particular homogeneous therefrom

Material composed.

Particulate materials of inorganic material with homogeneous

Compositions are used in paints, lacquers, protective coatings, toners and the like in a variety of embodiments, for example as inorganic color pigments, as fillers, extenders or as fluidization aids. They are usually in granular, irregular particle shape, rarely spherical or platelet-shaped. Depending on the application, they are available in different particle sizes. In principle, all of the particulate materials listed here are suitable for forming the core of the particles according to the invention.

However, particularly suitable and preferred according to the invention are cores which consist of a metal oxide or metal oxide mixture. In this case, particles of titanium dioxide, various iron oxides, chromium oxide or cobalt oxides can be used. However, according to the present invention, particular preference is given to using cores which consist of

Alumina (Al2O3), silicon dioxide (S1O2) or mixtures thereof consist. The cores of the particles according to the invention can consist both of individual particles and of agglomerates of individual particles. In this case, the individual particles preferably have primary particle sizes of less than 1 μm, in particular less than 500 nm.

Cores of alumina, silica or mixtures thereof are preferably used, in which the primary particles have a primary particle size of less than 1 pm, in particular of less than 500 nm, more preferably of less than 300 nm and most preferably of 5 to 200 nm.

In this case, the core material is present as a starting material for the preparation of the particles according to the invention in powder form and has large specific surface areas (BET) in the range from 50 to 600 m ² / g.

Such materials are commercially available, preferably as fumed silica (fumed silica) and as fumed alumina. They are offered by different manufacturers in different qualities, for example, under the names

AEROSIL® and AEROXIDE® Alu from Evonik Degussa GmbH, as CAB-O-SIL®, SpectrAI® or CAB-O-SPERSE® from Cabot Corp., as HDK® pyrogenic silica from Wacker, and the like more. According to the invention, the fumed silica and the fumed alumina are used either as individual substances or else as a mixture in order to form the cores of the particles according to the invention.

These starting materials should be in untreated form, i. as pure oxides without precoating, are used.

According to the present invention, a coating comprising at least one compound of the formula (I) is present on the core particles. These compounds of the formula (I) are fluorosurfactants.

(I)

in which

X is a hydrophilic group,

B = a single bond, O, NH, NR ', CH ₂ , C (O) -O, S, CH ₂ -O, OC (O), O-C (O) -O, NC (O), C ( 0) -N, OC (O) -N, NC (O) -N, SiR ' ₂ -, SiR' ₂ -0, 0-S0 ₂ or S0 ₂ -0, wherein R '= linear or branched alkyl .

R ¹ and R ² = independently of one another hydrogen or -CH ₂ -COY ³ - L ³ - (A ³⁾ _n3 are

Y ¹ , Y ² and Y ³ = independently of one another are O, S or N,

Z 'is O, S or N and is bonded to a C atom of U or is a single bond,

R ³ and R ^{4 are} independently hydrogen or an alkyl group,

Rf is a fluorine-containing radical,

n1, n2 and n3 = are independently 1-6,

m1, m2 and m3 = are independently 0-5, and the compounds of formula (I) at least one R group

contain.

Preferred compounds of formula (I) are those in which two or three Rf groups are included. However, compounds with at least four Rf groups are also possible, preferably with four, six or nine Rf groups.

As fluorinated groups Rf it is preferred to use branched or unbranched fluorine-containing alkyl radicals, in particular perfluorinated alkyl radicals. Particularly preferred are fluorine-containing alkyl radicals having 1 to 10, preferably 1 to 6, in particular 1 to 4 C-atoms. Particular preference is given to using perfluorinated R groups having 1 to 6, in particular 1 to 4, C atoms. Preferably, R, Rf ² and Rf ^{3 have the} same meaning.

Preferably, R ¹ and R ^{2 are} not simultaneously -CH ² -COY ³ -L ³ - (A ³ ) n ³ .

Preferred compounds of the formula (I) are also those in which Y ¹ , Y ² and Y ^{3 are} preferably O or N, in particular O. Preferably Y ¹ and Y ² or Y, Y ² and Y ^{3 have the} same meaning.

The groups Rf are bonded to a group L ¹ , L ² or L ³ via a group -Z '(CR ³ R ⁴ ) mi. Z 'here is preferably O or N, in particular O. Preference is given to compounds in which all Z' are identical.

Preferred compounds of the formula (I) are those in which n1, n2 and n3 are preferably, independently of one another, 0-4, in particular 1 or 2. Preferred compounds of the formula (I) are also those in which m1, m2 and m3 are preferably, independently of one another, 0-4, in particular 1-4.

Preferred compounds of the formula (I) are also those in which R ³ and R ⁴ independently of one another are hydrogen or an alkyl group having 1 to 6 C atoms, in particular 1-4 C-atoms. R ³ and R ⁴ independently of one another preferably represent hydrogen or an unbranched C ¹ -C ³ -alkyl group. Preference is given to compounds in which R ³ or R ⁴ is hydrogen. m1, m2 and m3 are preferably independently of one another 1-3. Compounds in which all Z \ R ³ R ⁴ and m each has the same meaning are preferred.

L ¹ , L ² and L ³ may preferably be independently of one another linear or branched alkylene having 1 to 10 carbon atoms. In particular, L ¹ , L ² and L ^{3 are} independently linear or branched alkylene having 3 to 8 carbon atoms. One or more nonadjacent C atoms of the groups L ¹ , L ² and L ³ may preferably be replaced by O or N, preferably by O. In a preferred variant of the invention, L ¹ and L ^{2 are} identical. If L ^{3 is also} present, preferably L ¹ and L ² or L ¹ and L ³ or L ² and L ^{3 may be the} same. In a particularly preferred variant of the invention, all groups L ¹ , L ² and L ^{3 are the} same.

Particular preference is given to compounds of the formula (I) in which

at least one group L '= - (CR ⁵ R ⁶ ) ci (CR ⁷ R ⁸ ) _C i) di- with the respective indices ci and c'i independently = 0-10 and di = 0-5, R ⁵ to R ⁸ independently of one another hydrogen or a branched or

are unbranched alkyl group and ci and c'i are not simultaneously = 0.

Particular preference is given to compounds of the formula (I) in which, in at least one group T, the group R ^{5 is} an alkyl group having 1 to 6 C atoms, in particular 1-4 C atoms, and the groups R ⁶ and R ⁷ and R ⁸ = hydrogen.

Also preferred are compounds of the formula (I) in which R ^{7 is} an alkyl group having 1 to 6 C atoms, in particular 1-4 C atoms, and the groups R ⁵ and R ⁶ and R ⁸ = hydrogen. In the compounds of the formula (I), the group R preferably represents linear or branched alkylene having 1 to 12 carbon atoms, in particular having 1 to 4 carbon atoms. Preferably, one or more non-adjacent C atoms may be replaced by O or S, preferably O.

In the compounds of the formula (I) used according to the invention, r may preferably be 0. Preference is furthermore given to compounds of the formula (I) in which B is a single bond, O, S, C (O) -O or O-C (O), in particular one

Single bond.

Particularly advantageous compounds of formula (I), in which one or more of the variables Rf, Y ^j, ZLR ¹ to R ^8, ci, c 'i, di, ni, mi, R, r and B have the preferred meanings, in particular those compounds in which the variables mentioned have the particularly preferred meanings. Particularly advantageous compounds of the formula (I) are those in which all the variables mentioned have the preferred, in particular the particularly preferred, meanings.

In the compounds of the formula (I) used according to the invention, X is a hydrophilic group, preferably an anionic, cationic, nonionic or amphoteric group.

A preferred anionic group X can be selected from -COO ~, -S0 ₃ -, -OS03-, -P03 ² -, -OPO3 ² -, - (OCH ₂ CH ₂₎ s-0- (CH2) t-COO- .

- (OCH ₂ CH ₂ ) s -O- (CH ₂ ) t -SO ₃ -, - (OCH ₂ CH ₂ ) s -O- (CH ₂ ) t -OO ₃ -,

- (OCH ₂ CH ₂₎ s-0- _(CH2) t-P0 ₃ ² -, - (OCH ₂ CH ₂₎ _s -0- (CH ₂₎ t-OP0 ₃ ² - or from formulas A to C .

where s stands for an integer in the range from 1 to 1000, t stands for an integer selected from 1, 2, 3 or 4 and w stands for an integer selected from 1, 2 or 3.

The preferred anionic groups include in particular -COO-, -SO3-, -OSO3-, -PO3 ² -, -OPO3 ² -, the partial formula A, and

- (OCH ₂ CH ₂ ) s-O- (CH ₂ ) t -COO-, - (OCH ₂ CH ₂ ) s-O- (CH ₂ ) t -SO ₃ - and

- (OCH 2 CH 2) s-O- (CH 2) t -O OS 3 ^" , where each of these groups may be preferred per se.

The most preferred anionic groups include -SO 3 ^" , -OSO 3 ^" , -PO 3 ^{2 "} , or OPO 3 ^2" . In particular, a sulfonate group

-SO3 ^" is preferred.

Preferred counterion for anionic groups X is a monovalent cation, in particular H ⁺ , an alkali metal cation or NR4 ⁺ , wherein R = H or C1-C6-alkyl and all R may be the same or different. Particularly preferred are Na ⁺ , K ⁺ and NHV, more preferably Na ⁺ .

A preferred cationic group X may be selected from -NR ¹ R ² R ³ ⁺ Z, -PR ¹ R ² R ^{3 +} Z ^" ,

where R is H or C 1-4 -alkyl in any position,

Z stands for Cl ^" , Br, I ^" , CH3SO3-, CF3SO3-, ChbPhSOs ^" , PhSOs ^"

R, R ² and R ^{3 are} each independently H, Ci-30-alkyl, Ar or -CH 2 Ar and

Ar is an unsubstituted or mono- or polysubstituted aromatic ring or fused ring systems having 6 to 18 carbon atoms, in which also one or two CH groups may be replaced by N.

The preferred cationic groups include in particular -NR R ² R ^{3 +} Z and

each of these groups may be preferred per se.

A preferred non-ionic group may be selected from linear or branched alkyl, wherein one or more non-adjacent carbon atoms replaced by O, S, and / or N may be replaced, -OH, -SH, -O- (glycoside) ₀ , -S- (glycoside) _0, -OCH 2 -CHOH-CH2-OH, -OCH2Ar (-NCO) _P, -OAr (-NCO) _p, -CR = CH2, -OCOCR = CH2, amine oxide

u is an integer from the range of 1 to 6, preferably 1 to 4 o is an integer from the range of 1 to 10,

p is 1 or 2,

R ¹ , R ² and R ³ are each independently of one another Ci-30-alkyl, Ar or -CH 2 Ar, preferably Ci-20-alkyl,

and,

Ar is an unsubstituted, mono- or polysubstituted aromatic ring or fused ring systems having 6 to 18 carbon atoms, in which also one or two CH groups may be replaced by C = O and, glycoside is an etherified carbohydrate, preferably for a mono-, di-, tri- or oligo-glucoside,

and R is H or methyl.

The preferred nonionic groups include in particular linear or branched alkyl, where one or more nonadjacent C atoms may be replaced by O, S and / or N, -OH, -OCOCR = CH 2 and -O- (glycoside) ₀ .

If X = alkyl, where one or more nonadjacent C atoms are replaced by O, S, and / or N, then it is preferably equal to R- (BA) _m - where R = H or Ci alkyl, in particular H or CH 3, A = linear or branched alkylene, preferably having 1 to 10 carbon atoms, in particular having 1 to 4 carbon atoms, B = O or S, preferably O, and m = an integer preferably from the range of 1 to 100, particularly preferably 1 to 30. Particularly preferred as nonionic group X is the group

R- (O-CH 2 CHR) m - with m = an integer from the range of 1 to 100, preferably 1 to 30, in particular 1-15, and R = H or Ci-4-alkyl, in particular H or CH 3. Especially preferred is R- (BA) _m - a polyethylene or polypropylene glycol unit.

A preferred amphoteric group may be selected from the functional groups of the acetyldiamines, the N-alkylamino acids, the betaines, or corresponding derivatives, in particular selected from:

Alkyl radical, preferably methyl or ethyl

Particularly preferred compounds used according to the invention are those which contain as hydrophilic group X one of the preferred anionic groups X, the preferred nonionic groups or the preferred zwitterionic groups.

Particular preference is given to compounds which contain the groups -SO 3 ^" , -OSO 3 ^" , -PO 3 ^{2 "} or OPO 3 ^2" , polyethylene or polypropylene glycols, betaines or sulfobetaines, in particular -SO 3. ^" Preferred counterions here are Na ⁺ , K ⁺ and NhV, especially Na ⁺ .

For the surface coating of the particles according to the invention, compounds of the formula (I) are particularly advantageous.

in which X is an anionic group, especially -SO 3 ~, and one or more of the variables R f ', Υ', Ζ ', U, R ¹ to R ⁸ , ci, c'i, di, ni, mi, R, r and B have the preferred meanings described, in particular those compounds in which the variables mentioned have the particularly preferred meanings. Preferred compounds here are in particular those compounds in which all variables are the preferred meanings, in particular the particularly preferred meanings have.

In one embodiment of the invention, the compounds of the formula (I) can be present as mixtures in which the individual compounds

have different meanings for the variables, in particular for A ', Rf, Υ', ZV, R to R ⁸ , ci, c'i, di and mi.

In a particularly preferred group of compounds of formula (I) R and R ^{2 are} hydrogen and A and A ^{2 is} a -Z ⁱ (CR ³ R ⁴ ) miRf ⁱ group. These compounds are represented by formula (II).

Particular preference is given to compounds of the formula (II) where Y ¹ , Y ² , Z ¹ and Z ^{2 are} identical to O.

In another preferred group of compounds of the formula (I), R ^{1 is} H, R ^{2 is} -CH ₂ -COY ³ -L ³ - (A ³ ) n ³ and A ¹ , A ² and A ^{3 are} each one

-Z '(CR ³ R ⁴ ) miRf group. These compounds are represented by formula (III). Particular preference is given to compounds of the formula (III) where Y ¹ , Y ² , Y ³ , Z ¹ , Z ² and Z ³ are O.

In a further preferred group of compounds of the formula (I), R is -CH ₂ -COY ³ -L ³ - (A ³ ) n ³ , R ^{2 is} hydrogen and A ¹ , A ² and A ^{3 is} a -Z ⁱ ( CR ³ R ⁴ ) miRf ⁱ group. These compounds are represented by formula (IV). Particular preference is given to compounds of the formula (IV) where Y ¹ , Y ² , Y ³ , Z ¹ , Z ² and Z ³ are O.

(IV)

Particularly preferred compounds used according to the invention are compounds of the formulas (II), (III) and (IV) in which X is an anionic group. Particular preference is given to compounds of the formulas (II), (III) and (IV) which contain the groups -SO 3 -, -OSO 3 -, -ΡΟ 3 ² · or ΟΡΟ 3 ² ·,

especially -SO 3 ^" . Preferred counterions here are Na ⁺ , K ⁺ and NH 4 ⁺ , in particular Na ⁺ .

In the formulas (II), (III) and (IV), L, L ² and L ^{3 have} the general and preferred meanings given for the formula (I). L ¹ , L ² and L ³ are preferably, independently of one another, linear or branched C 1 -C 10 -alkylene, in particular linear or branched C 3 -C 8 -alkylene, preferably linear or branched C 3 -C 6 -alkylene. In particular, compounds of formulas (II), (III) and (IV) are preferred in which all L are the same.

Preference is also given to compounds of the formulas (II), (III) and (IV) with perfluorinated groups Rf having 1 to 4 C atoms. Preferably, Rf ¹ , Rf ² and Rf ^{3 have the} same meaning. In the formulas (II), (III) and (IV), n1, n2 and n3 are preferably independently 1 or 2. m1, m2 and m3 are preferably independently of one another 1-4. Preferred compounds of the formulas (II), (III) and (IV) are also those in which R ³ and R ⁴ independently of one another are hydrogen or an alkyl group having 1 to 3 C atoms.

In a preferred variant, R ³ and R ^{4 are the} same. Further preferred are compounds in which R ³ or R ⁴ are hydrogen and m 1, m ² and m ³ are 1-3.

Preference is given to compounds in which all R, R ³ R ⁴ , ni and mi each have the same meaning.

Particular preference is given to compounds of the formulas (II), (III) and (IV) in which all variables have the preferred meanings, in particular the particularly preferred meanings. Examples of compounds of the formula (I) whose use in the surface coating of the particles according to the invention is particularly advantageous are compounds of the formulas (III-1) and (III-2):

The inventively used in the surface coating

Compounds according to the formula (I) can also be present as isomer mixtures (constitution and / or configuration isomer mixtures).

In particular, diastereomeric and / or enantiomeric mixtures are possible.

The compounds of the formula (I) may preferably be prepared by esterification of maleic acid and aconitic acid or their anhydrides or acid chlorides with one or more alcohols of the formula (V)

(V) and subsequent addition to the double bond to introduce the X- (R) _r B group. You can as well through

Esterification of malic acid and citric acid with one or more alcohols of the formula (V) and subsequent functionalization of the hydroxy groups to introduce the grouping X- (R) rB are prepared.

L and A in the formula (V) have the meaning described for L ¹ , L ² and L ³ or A ¹ , A ² and A ³ in formula (I), in particular also the preferred meanings. The alcohols of formula (V) may contain one or more Rf groups. The alcohols used are commercially available and / or their

Preparation is familiar to the person skilled in the art (eg DE 10 2009 030 846 A1; Heilmann et al., J. Fluorine Chem. 1992, 59, 387; Janulis et al

5,157,159 (1992); Carbohydrate Research 1991, 219, 33).

The synthesis of the succinates or tricarboxylates used according to the invention is preferably carried out in a two-stage synthesis via the corresponding maleates or hydroxysuccinates or the corresponding aconitic or citric acid esters. These syntheses are described in WO 2010/003567, WO 2010/149262, WO 2011/082770 and WO 2012/084118. The

Revelations in the cited references hereby expressly also belong to the disclosure content of the present application.

The content of compounds of formula (I), based on the coated particles of the invention, is in the range of 5 to 30 wt .-%, preferably from 10 to 25 wt .-%.

Compounds of the formula (I), and in particular compounds of the formulas (II), (III) and (IV) are fluorosurfactants which, instead of long fluorine-substituted hydrocarbon chains, preferably have short-chain, perfluorinated hydrocarbon end groups in multiple execution within one molecule. Their surfactant action is therefore high, without harmful effects on humans and the environment during their production, use and recycling of the products produced therewith, because these products are not bio-accumulative and the dreaded toxic degradation products of commercial fluorosurfactants are not or only slightly Scope.

In the most preferred embodiment of the present invention, the cores of the particles according to the invention consist of the above-mentioned pyrogenic SiO 2 particles or pyrogenic Al 2 O 3 particles in untreated form, which are combined with at least one compound according to the formulas (111-1) or (III-2) are coated. Even more preferred is the embodiment in which, in addition to the cores, only one compound according to the formulas (III-1) or (III-2) and no further constituents are contained.

Compounds of the formulas (I) to (IV) are already known. They have been described in WO 2014/023397, but there as constituents of special surfactant mixtures for addition to certain application media. Their use in a surface coating of particulate material, in particular as part of the surface coating of inorganic particles, has not been described or suggested.

The present invention also provides a process for the preparation of the particles according to the invention, in which the particulate core material, which is kept in motion by suitable means, for example by stirring, with at least one compound of formula (I) mixed intensively and the mixture subsequently dried. The mixing of particulate core material and the at least one

Compound according to formula (I) preferably takes place over a relatively long period of time in the range from minutes to hours, in that the particulate core material is placed in a container and kept in motion, and the at least one compound of formula (I) is added slowly, for example by dropwise addition , After completion of the addition of the at least one compound of formula (I), the resulting mixture is dried at temperatures ranging from 50 to 150 ° C.

Optionally, drying takes place under protective gas, for example under nitrogen. The drying process is preferably carried out in a period of 30 to 300 min. Suitable particulate core material are all materials already mentioned above, in particular inorganic particulate material. Preference is given to using metal oxides or metal oxide mixtures. Particular preference is given to using particles of SiO 2 and / or Al 2 O 3, most preferably in the form of pyrogenic SiO 2 and / or pyrogenic Al 2 O 3.

The particulate core material used has the shapes and sizes set out above, but in particular a primary particle size of less than 1 pm and a specific surface area (BET) in the range of 50 to 600 m ² / g.

The particulate core material used according to the invention consists homogeneously of the abovementioned materials and preferably has no precoating or other surface treatment when used in the method according to the invention.

Preferred compounds of the formula (I) are compounds of the formulas (II), (III) and / or (IV), but especially compounds of the formulas (III-1) and / or (III-2), but more preferably one

Compound of formula (111-1) or a compound of formula (III-2) used.

The present invention also relates to the use of the particles according to the invention as an additive in paints, lacquers, printing inks, protective coatings, paper coatings, synthetic resins, sealants, bulk solids, toners, floor polishes or adhesives.

Depending on the type of core material used, they assume the function that would take over the uncoated core material in the respective application, for example as white or color pigment, as a filler, as an extender, as a means of improving the abrasion and scratch resistance, etc. The simultaneous content of fluorosurfactants that no Although having long-chain fluorinated hydrocarbon groups, leads to an additional strong surfactant effect, but not to the usually observed in fluorine surfactants harmful degradation products or to an accumulation in living tissue. Therefore, the small amount of surfactants present in the particles according to the invention may already be sufficient to prevent a further addition of surfactants in said application media or may at least lead to a significant reduction of the additional surfactants to be used, regardless of their nature.

However, the particles according to the invention exert a special, completely unexpected function when used as additives in a powder coating composition and via an electrostatic application process with otherwise customary powder coating constituents to the corresponding

Substrates are applied. Therefore, the preferred use of the particles of the invention as an additive in a powder coating composition, in short: in a powder coating instead.

It has surprisingly been found that the particles according to the invention, in particular when it is pyrogenic S1O2 and / or pyrogenic Al2O3, which with a compound according to the formulas (III-1) and / or (III-2), preferably (III-1) or (III-2), as an additive in powder coatings of otherwise conventional composition exert a great influence on the achievable with the electrostatic application method layer thicknesses.

The influences on the production of thick powder coating layers are particularly impressive. It is completely sufficient if the particles according to the invention are added to a conventional powder coating composition as fluidization assistant in a concentration of 1% by weight, based on the powder coating, which is customary for fluidization aids. The concentration of the particles according to the invention is preferably even at <0.5 wt .-%, based on the powder coating, in particular at 0.1 to 0.4 wt .-%.

If the particles according to the invention are added to the powder coating composition in the manner indicated above, it can be observed during the application of the powder coating in an electrostatic process that virtually no re-effect of the effect takes place, i. that the powder coating layer can be applied to the corresponding substrate in a layer thickness of 1 mm and larger, which amounts to almost a tenfold increase in the hitherto technologically feasible maximum layer thickness. A limitation of the achievable layer thickness is therefore given only by the desired application of the powder coating layer or the coated substrate. This is particularly important for the application of anticorrosion coatings or other protective layers of great importance. This eliminates the addition of only very small amounts of the particles according to the invention to conventional powder coating compositions also one of the decisive disadvantages of powder coating technology, namely the technological limitation of the achievable layer thickness. Since the fluorosurfactants used have adverse effects neither for reasons of environmental protection nor in physiological terms, when using the particles according to the invention in

Powder Coatings The benefits of solvent-free powder coating technology synergistically exploited with the benefits of fluorosurfactants used to create a total environmentally friendly and highly effective

To provide coating process.

Similar to the production of thick powder coating layers, the particles according to the invention in powder coating compositions are also suitable for producing particularly thin layer thicknesses with a uniform composition. Conventional powder coatings, as a workable powder, usually particle sizes in the range of about 1-100 pm. Usually, the fine grain fraction is separated before processing the powder coating because it does not deposit on the surfaces to be coated, but pulled into the exhaust air and thus would end up in overspray. But even after the separation of the fine grain content, the proportion of fine powder coating particles in the overspray is greater than the proportion of coarser particles, so that when recovering the overspray must be mixed with coarser powder coating particles so that recycling can take place. The powder coating particles, which precipitate as desired on the substrates and adhere there, so usually have an average particle size in the frame specified above.

By adding the particles according to the invention in powder coating compositions it is now also possible to stably charge and fluidize powder coating particles of generally smaller particle size and thus to enable their deposition on the substrates to be coated. In this way, it becomes possible to produce uniform powder coating layers of good quality already with a thickness of less than 30 μm, which corresponds to about half of the currently technologically feasible layer thickness. It succeeds in applying very thin powder coating layers in good quality, which leads to a reduction of the costs in terms of material usage and process duration. The particles according to the invention can be added to the customary powder coating compositions since their use is not bound to specific binder systems, additives or application methods.

Thus, the commonly used epoxy, polyester, hybrid, polyurethane or acrylate binder systems, as well as the newer, UV-crosslinking binder systems can be used. Also with respect to the commonly used color and / or effect pigments and the other additives, the powder coatings containing the particles of the invention, no restrictions. The same applies to the type of spray guns and nozzle systems used (baffle plate nozzles, flat jet nozzles, finger nozzles or rotary bells).

With the particles according to the invention and their use in powder coating systems, therefore, it is possible to use environmentally friendly and physiological

acceptable manner for the first time the construction of particularly thick or very thin powder coating layers with otherwise conventional compositions and the usual application methods and apparatus.

The present invention will be explained in more detail by means of examples, but not limited to these. Example 1:

Production of particles according to the invention

200 g of CAB-O-SIL® M5 (Cabot Corporation) are introduced into a Henschel mixer (101) and, while stirring (peripheral speed 10 ms ^-1 ), 200 g of a sulfotricarballylate according to formula (III-2) are added slowly. The mixture is rendered inert after addition with nitrogen and dried at 120 ° C material temperature. The drying is complete after about 1 hour. The product consisting of the particles according to the invention is drained off and packed.

Example 2:

Application in powder coating

100 g of powder coating chips based on epoxy resin are intimately mixed with 0.3 g of the product according to Example 1 and then ground.

The resulting powder is screened with a mesh size of 125 pm.

The sieved product is electrostatically applied to metal substrates using a commercially available corona spray gun from GEMA (80 kV) By extending the usual application time, layer thicknesses of up to 1000 pm are obtained. The job will be completed by the end of

Application time determined, rejuvenation effects are not observed. The further processing of the powder coating is carried out under normal conditions. It will be uniform powder coating layers higher

Layer thickness of good optical quality.

Example 3:

Application in powder coating

100 g powder coating chips based on an epoxy-polyester hybrid binder are ground. The milled powder coating composition 0.3 g of the product according to Example 1 was added and the mixture homogenized in a mixer at a peripheral speed of 10 ^{ms' 1.}

The further processing is carried out as in Example 2. The powder coating composition can be applied as described in Example 2, without that even with a longer application time, re-cooling effects can be observed. At a layer thickness of about 500 pm, the test is discontinued. Further processing takes place under normal conditions. Uniform powder coating layers of good quality are obtained.

Claims

claims

Particles consisting of a core with a

Surface coating, wherein the surface coating comprises at least one compound of the formula (I):

0)

in which

X is a hydrophilic group,

R = linear or branched alkylene, wherein one or more nonadjacent C atoms may be replaced by O, S, and / or N,

r = 0 or 1,

B = a single bond, O, NH, NR ', CH ₂ , C (O) -O, S, CH ₂ -O, O-C (O), OC (O) -O, NC (O), C (O ) -N, OC (O) N, NC (O) -N, SiR'2-, SiR _'2 - O, O-SO2 or SO2-O, where R' = linear or branched alkyl;

R ¹ and R ² = independently of one another are hydrogen or -CH ₂ -COY ³ -L ³ - (A ³ ) n ³ ,

Y ¹ , Y ² and Y ³ = independently of one another are O, S or N,

L ¹ , L ² and L ³ = independently linear or branched

Alkylene, wherein one or more non-adjacent carbon atoms may be replaced by O, S, and / or N,

A ¹ , A ² and A ³ = independently of one another hydrogen or a

Group of structure -Z ⁱ (CR ³ R ⁴ ) miRf ⁱ , with i = 1,

2 or 3, are

Z '= O, S or N and is bound to a C atom of U or one

Single bond is, R ³ and R ^{4 are} independently hydrogen or a

Are alkyl group,

Rf is a fluorine-containing radical,

n1, n2 and n3 = are independently 1-6,

m1, m2 and m3 = are independently 0-5,

and the compounds of formula (I) contain at least one Rf group.

Particles according to Claim 1, characterized in that the compounds of the formula (I) used are compounds of the formulas (II), (III) and / or (IV):

(IV) With

X is -SO 3 -, -OSO 3 ^' , -PO 3 ^2' or OPO 3 ² -, especially -SO 3 ^" , Y ¹ , Y ² , Y ³ , Z, Z ² and Z ³ is O,

Rf, Rf ² and Rf ^{3 are the} same perfluorinated groups Rf 'having 1 to 4 C atoms,

n1, n2 and n3 equal to 1 or 2,

m1, m2 and m3 are 1-4,

L ¹ , L ² and L ³ are linear or branched C ³ -C 6 -alkylene, R ³ and R ⁴ are hydrogen or an alkyl group having 1 to 3 C atoms.

3. Particles according to claim 2, characterized in that the

Surface coating comprises at least one compound of the formulas (III-1) or (III-2):

4. Particles according to one of claims 1 to 3, characterized

characterized in that the core consists of an inorganic material.

5. Particles according to claim 4, characterized in that the inorganic material is a metal oxide or metal oxide mixture.

6. Particles according to claim 5, characterized in that the metal oxide or metal oxide mixture is S1O2, Al2O3 or a mixture of these.

7. Particles according to one or more of claims 1 to 6, characterized in that the core has an average primary particle size of <

1 pm.

8. Particles according to one or more of claims 1 to 7, characterized in that the core consists of fumed silica, pyrogenic alumina or a mixture of these.5

9. A process for the preparation of particles according to one or more of claims 1 to 8, characterized in that an agitated particulate core material with at least one compound of formula (I) mixed thoroughly and the mixture, Q optionally under inert gas, dried.

10. The method according to claim 9, characterized in that as the compound of formula (I) at least one compound according to formulas (II), (III) or (IV), preferably according to the formulas (III-1) or (III-2 ) is used.

5

11. Use of particles according to one or more of

Claims 1 to 8 as an additive in paints, lacquers, printing inks, protective coatings, paper coatings, synthetic resins, sealants, bulk solids, toners, Bodenpolitikuren0 or adhesives. Use according to claim 11, characterized in that it is the paint is a powder coating.

13. Use according to claim 12, characterized in that the powder coating contains the particles as Fluidisierungshilfsmittel.

14. Use according to claim 12 or 13, characterized in that the particles in an amount of <1 wt.%, Based on the weight of the powder coating, are contained in this.

15. Paints, lacquers, printing inks, protective coatings, paper coatings, synthetic resins, sealants, bulk materials, toners, floor polishes or adhesives containing particles according to one or more of claims 1 to 8.

16. The paint according to claim 15, characterized in that it is a powder coating.