FUNCTIONAL MULTI-WALLED CORE-SHELL PARTICLES

Abstract

The present invention relates to core-shell particles comprising a core comprising at least one lipophilic compound and a shell comprising at least one layer close to the core and one layer far from the core. The invention further relates to the preparation of such core-shell particles and their use, particularly in the finishing of fibers and textiles.

Claims

1. Core-shell particles comprising (a) a core comprising at least one lipophilic compound and (b) a shell comprising at least one layer close to the core and one layer far from the core, wherein the layer close to the core is obtainable by polymerization of at least one monomer with at least one ethylenically unsaturated group and wherein the monomer with at least one ethylenically unsaturated group does not have a nucleophilic group with active hydrogen atom, particularly no NCO-reactive hydrogen.

2. The core-shell particles of claim 1, wherein the layer far from the core is disposed on the layer close to the core.

3. The core-shell particles of claim 1, wherein the lipophilic compound is selected from pigments, dyes, fragrances, cosmetics, flame retardants, latent heat storage materials, biocides, catalysts, adhesives, adhesive components, hydrophobing agents, polymer building blocks, isocyanates, oils, silicone oils, waxes or mixtures thereof.

4. The core-shell particles of claim 1, wherein the layer close to the core is obtainable by polymerization of at least one monomer with at least one ethylenically unsaturated group having the structure: ##STR00007## with ##STR00008## B=—R.sup.5-R.sup.6 R.sup.1=—C.sub.1-C.sub.6-alkyl or —H, preferably —H or —CH.sub.3, R.sup.2=linear or branched C.sub.1-C.sub.24-alkyl, R.sup.3=linear or branched C.sub.1-C.sub.24-alkylene, ##STR00009## R.sup.7=polyester, particularly obtainable by reaction of C.sub.1-C.sub.6-alkyldiols and C.sub.1-C.sub.6-alkyldicarboxyilic acids, such as e.g. diester, e.g. malonic acid ester, oxalic acid ester, succinic acid ester, glutaric acid ester or adipic acid ester and n=0-20

5. The core-shell particles of claim 1, wherein the layer far from the core contains at least one urethane, allophanate, carbodiimide, isocyanurate, biuret, uretdione, urea, iminooxadiazinedione or uretonimine group.

6. The core-shell particles of claim 1, wherein the layer far from the core is an addition product of at least one polyisocyanate and at least one compound comprising at least two groups with NCO-reactive hydrogen atom, preferably hydroxy, amino, carboxylic acid, urethane and/or urea groups.

7. The core-shell particles of claim 6, wherein the NCO groups of the polyisocyanate are partially blocked, particularly 0.1 to 80%, preferably 1 to 50%, more preferably 1 to 30% of the NCO groups of the polyisocyanate are blocked.

8. The core-shell particles of claim 1, wherein the layer far from the core has at least one functional group, preferably an anionic, cationic or non-ionic group, which is preferably bound to the layer far from the core via a urethane group.

9. Composition, comprising at least one core-shell particle according to claim 1.

10. The composition of claim 9, wherein the composition comprises water and optionally further at least one surface-active reagent, particularly surfactant, a binding agent, a defoamer, a protective colloid and/or a thickening agent.

11. Method for preparing a core-shell particle of claim 1, comprising: (i) providing at least one lipophilic compound, optionally slurried in a carrier oil, (ii) mixing the at least one lipophilic compound and optionally the carrier oil with at least one monomer with at least one ethylenically unsaturated group, water, at least one polymerization initiator, at least one protective colloid, optionally at least one surface-active reagent, optionally at least one chain regulator, under formation of an emulsion, wherein the water forms the continuous phase. (iii) treating the emulsion obtained in (ii) at elevated temperature while stirring, (iv) adding at least one, optionally partially blocked, polyisocyanate and at least one compound comprising at least two groups with NCO-reactive hydrogen atom and optionally adding at least one compound comprising at least one functional group and an NCO-reactive hydrogen atom, (v) optionally treating the mixture obtained in (iv) at elevated temperature, (vi) optionally adding at least one binding agent, defoamer, surface-active reagent and/or a thickening agent and (vii) optionally at least partially removing the water.

12. Core-shell particles obtainable by a method according to claim 11.

13. Use of the core-shell particle of claim 1 for the functionalization of materials, particularly fibers, textile fabrics, construction materials, plastics or plastic foams, paint and varnish.

14. Method for the finishing of materials, particularly of textiles, comprising: (a) providing the core-shell particles of claim 1, (b) applying the core-shell particles or the composition to a material; and (c) thermally treating the material.

15. Materials, particularly fibers or textile materials, comprising core-shell particles of one claim 1.

Description

[0162]

TABLE-US-00001 Parafol 18-97 Techn. n-octadecane (97% Sasol purity) Laromer TMPTA Trimethylol propane triacrylate BASF WAKO V-65B 2,2′-azobis(2,4- WAKO Chemicals dimethylvaleronitrile) WAKO VA-044 2,2′-azobis[2-(2-imidazoline-2- WAKO Chemicals yl)propane]dihydrochloride Desmodur I Isophorone diisocyanate Covestro 3,5- 3,5-Dimethylpyrazole Wacker Dimethylpyrazole Heavy Complex mixture of linear, Dow Deutschland Polyamine XE cyclic and branched ethylene amines (amine content 33-38%) Plextol R272 Binding agent - self- Synthomer crosslinking anionic polyacrylate copolymer (45% dry substance DS) Lutensit A-BO Emulsifier (sulfosuccinate) BASF (75% DS) Strodex PK90 Emulsifier (phosphate coester Ashland of aliphatic alcohols) (90% DS) Silfoam SE47 Silicone defoamer (17.5% DS) Wacker Rohagit SD15 Thickening agent (polyacrylate Synthomer copolymer acrylic acid co-ethyl acrylate) (30% DS) Exxsol D100 Hydrocarbons, C12-C15, n- ExxonMobil ULA alkanes, isoalkanes, cyclic Visiomer MPEG Methoxypolyethyleneglycol- Evonik 750 MA 750-methacrylate (50% in water) Disponil A 3065 Emulsifier (mixture of BASF ethoxylated linear fatty alcohols) (65% DS) Arquad 2.10-50 Emulsifier (Didecyl dimethyl Nouryon ammonium chloride) (50% DS) BYK 7420 ES Thickening agent (modified BYK urea) (40% DS) DISPERBYK 192 Emulsifier (copolymer with BYK pigment-affine groups) (100% DS)

EXAMPLE-1

Partial Blocking of Isocyanate Groups

[0163] 40.00 g isopropyl acetate and 10.00 g (44.98 mmol) isophorone diisocyanate (IPDI) were presented in a round-bottom flask under nitrogen atmosphere.

[0164] While stirring, 2.60 g (27.05 mmol) 3,5-dimethylpyrazole were added and mixed until a homogeneous solution was formed. The mixture was heated to 40° C. and after reaching a constant NCO content was subsequently freed from the solvent under vacuum distillation.

Preparation of the Core-Shell Particles

Aqueous Phase:

[0165]

TABLE-US-00002 530.75 g Water 80.20 g Polyvinyl alcohol solution (12.5 wt.-%, 88% saponified, medium molar weight 128000 g/mol)

Oily Phase:

[0166]

TABLE-US-00003 286.22 g Parafol 18-97 37.50 g Methylmethacrylate 16.55 g Laromer TMPTA 0.49 g Lauryl mercaptan 1.00 g WAKO V-65B

Aqueous Initiator:

[0167]

TABLE-US-00004 4.97 g Water 0.99 g WAKO VA-044

Isocyanate:

[0168]

TABLE-US-00005 12.71 g 30% partially blocked Desmodur I

Polyamine:

[0169]

TABLE-US-00006 6.23 g 10% Heavy Polyamine XE solution

Stabilization:

[0170]

TABLE-US-00007 2.95 g Lutensit A-BO 3.00 g Strodex PK-90 3.84 g Silfoam SE 47 10.97 g Rohagit SD 15 1.63 g Sodium hydroxide solution (50%)

[0171] In a beaker, water as well as the protective colloid were presented and heated to 40° C. while stirring. The oily phase was separately melted and pre-mixed and then introduced into the water phase while stirring. Subsequently, the emulsion was sheared for 5 min with a rotor-stator-homogenizer. The warm emulsion was transferred to a flask, tempered at 40° C., constantly stirred via a propeller stirrer and thereby, the reaction mixture was flushed with nitrogen. After exchanging the atmosphere for nitrogen, the reaction vessel was sealed with a pressure compensation and heated to 60° C. while stirring. Held at 60° C. for 20 min, then heated to 65° C., again held for 20 min and finally heated to 70° C. and held for 60 min. After this time, an aqueous solution of the aqueous initiator was added to the resulting dispersion under protective gas and again stirred for 60 min.

[0172] The partially blocked polyisocyanate was dropped into this suspension and stirred in. Subsequently, the polyamine was added drop by drop and the temperature was raised to 80° C. After 2 h reaction time, the dispersion was cooled to room temperature, mixed with emulsifiers, defoamer as well as thickening agent and adjusted to pH 8.5 with sodium hydroxide solution. A dispersion with about 34% solids content was obtained.

EXAMPLE-2

Partial Blocking of Isocyanate Groups

[0173] 40.00 g isopropyl acetate and 12.00 g (44.98 mmol) isophorone diisocyanate (IPDI) were presented in a round-bottom flask under nitrogen atmosphere. While stirring, 10.80 g (10.80 mmol) Jeffamine M1000 were added and mixed until a homogeneous solution was formed. The mixture was heated to 50° C. and after reaching a constant NCO content was subsequently freed from the solvent under vacuum distillation.

Preparation of the Core-Shell Particles

Water Phase:

[0174]

TABLE-US-00008 488.93 g Water 71.17 g Polyvinyl alcohol solution (12.5 wt.-%, 88% saponified, medium molar weight 128000 g/mol)

Oily Phase:

[0175]

TABLE-US-00009 279.39 g Parafol 18-97 39.89 g Methylmethacrylate 17.66 g Laromer TMPTA 0.46 g Lauryl mercaptan 0.92 g WAKO V-65B

Aqueous Initiator:

[0176]

TABLE-US-00010 4.57 g Water 0.96 g WAKO VA-044

Isocyanate:

[0177]

TABLE-US-00011 20.38 g 10% partially functionalized Desmodur I

Polyamine:

[0178]

TABLE-US-00012 3.67 g 10% Heavy Polyamine XE solution

Stabilization:

[0179]

TABLE-US-00013 49.78 g Plextol R272 3.93 g Lutensit A-BO 3.15 g Strodex PK-90 3.54 g Silfoam SE 47 10.10 g Rohagit SD 15 1.50 g Sodium hydroxide solution (50%)

[0180] The sample was prepared analogously to Example 1. Additionally, a binding agent was added to the dispersion. A dispersion with about 40% solids content was obtained.

EXAMPLE-3

[0181] Preparation of the Dispersion with Decreased Ratio of Crosslinking Agent in the Layer Close to the Core

Water Phase:

[0182]

TABLE-US-00014 439.64 g Water 78.65 g Polyvinyl alcohol solution (12.5 wt.-%, 88% saponified, medium molar weight 128000 g/mol)

Oily Phase:

[0183]

TABLE-US-00015 195.53 g Parafol 18-97 35.63 g Methylmethacrylate 11.50 g Laromer TMPTA 0.41 g Lauryl mercaptan 0.83 g WAKO V-65B

Aqueous Initiator:

[0184]

TABLE-US-00016 4111 g Water 0.86 g WAKO VA-044

Isocyanate:

[0185]

TABLE-US-00017 8.77 g Desmodur I

Polyamine:

[0186]

TABLE-US-00018 6.74 g 10% Heavy Polyamine XE solution

Stabilization:

[0187]

TABLE-US-00019 199.06 g Plextol R272 2.32 g Lutensit A-BO 2.34 g Strodex PK-90 3.18 g Silfoam SE 47 9.08 g Rohagit SD 15 1.35 g Sodium hydroxide solution (50%)

[0188] The sample was prepared analogously to Example 1. A dispersion with about 36% solids content was obtained.

[0189] The permeability of the core-shell particles was determined via the loss of latent heat by means of differential scanning calorimetry (DSC). For this purpose, a latent heat storage material was covered and the dispersion was finished on a textile fabric in dilution.

[0190] A part of the textile was dried at 20° C. for 24 h, while another part was dried at 150° C. for 3 min. The difference in the measured melting enthalpy between air-dried and heat-dried sample yields the tightness. For the reproducibility of the influence of the multiple layers that lead to the overall design of the shell, this DSC method was carried out for the same sample at different points of time of the method. For instance, the permeability was determined e.g. after formation of the polyacrylate layer close to the core and then again after positioning the polyurethane layer far from the core.

TABLE-US-00020 Remaining latent heat Remaining latent heat on textile - layer close on textile - only layer to the core and layer far Sample close to the core from the core Example 1 91.9% 90.3% Example 2 87.5% 93.7% Example 3 64.5% 63.8%

[0191] The results show that the permeability is given by the layer close to the core and is not or only slightly influenced by the layer far from the core. The layer far from the core is primarily responsible for the functionalization.

EXAMPLE-4

[0192] Example 4 was carried out—as described in Example 1—whereas the partially blocked isocyanate was varied as follows.

Functionalization with Cationic Emulsifying Groups

[0193] 75.00 g isopropyl acetate and 12.00 g (53.981 mmol) isophorone diisocyanate (IPDI) were presented in a round-bottom flask under nitrogen atmosphere. While stirring, 0.962 g (10.796 mmol) N,N-dimethyl amino ethanol as well as 0.008 g (0.0071 mmol) 1,4-diazabicyclo[2.2.2]octane (DABCO) were added and mixed until a homogeneous solution was formed. The mixture was heated to 50° C. and subsequently freed from the solvent under vacuum distillation.

[0194] The exact composition is shown in Table 1.

EXAMPLE-5

[0195] Example 5 was carried out, as described in Example 1, whereas the oily phase was pre-mixed without acrylate crosslinker. The exact composition is given in Table 1. Without acrylate crosslinker, a sufficient tightness of the layer close to the core cannot be ensured.

EXAMPLE-6

[0196] Example 6 was carried out—as described in Example 1—whereas the partially blocked isocyanate was varied as follows.

Functionalization with Radiation Crosslinkable Groups

[0197] 75.00 g isopropyl acetate and 12.00 g (53.981 mmol) isophorone diisocyanate (IPDI) were presented in a round-bottom flask under nitrogen atmosphere. While stirring, 2.507 g (21.592 mmol) 2-hydroxethylacrylate as well as 0.024 g (0.0213 mmol) 1,4-diazabicyclo[2.2.2]octane (DABCO) were added and mixed until a homogeneous solution was formed. The mixture was heated to 50° C. and subsequently freed from the solvent under vacuum distillation.

[0198] The exact composition is given in Table 1.

EXAMPLE-7

Preparation of the Core-Shell Particles

[0199] In a beaker, water as well as the protective colloid were presented. The oily phase was separately pre-mixed and then introduced into the water phase while stirring. Subsequently, the emulsion was sheared for 5 min with a rotor-stator-homogenizer. The emulsion was transferred to a flask, constantly stirred via a propeller stirrer and thereby, the reaction mixture was flushed with nitrogen. After exchanging the atmosphere for nitrogen, the reaction vessel was sealed with a pressure compensation and heated to 60° C. while stirring. Held at 60° C. for 20 min, then heated to 65° C., again held for 20 min and finally heated to 70° C. and held for 60 min. After this time, an aqueous solution of the aqueous initiator was added to the resulting dispersion under protective gas and again stirred for 60 min.

[0200] The polyisocyanate was dropped into this suspension and stirred in. Subsequently, the polyamine was added drop by drop and the temperature was raised to 80° C. After 2 h reaction time, the dispersion was cooled to room temperature, mixed with emulsifiers, defoamer as well as thickening agent and adjusted to pH 8.5 with sodium hydroxide solution.

[0201] The exact composition is given in Table 1.

Comparative Examples 1 and 2

[0202] The following comparative examples are prepared analogously to Example 1, whereas the synthesis ends before the addition of an isocyanate component, since the comparative particles are single-walled core-shell particles. The compositions of the comparative examples are shown in Table 1.

[0203] In a beaker, water as well as the protective colloid were presented and heated to 40° C. while stirring. The oily phase was separately melted and pre-mixed and then introduced into the water phase while stirring. Subsequently, the emulsion was sheared for 5 min with a rotor-stator-homogenizer. The warm emulsion was transferred to a flask, tempered at 40° C., constantly stirred with a propeller stirrer and flushed with nitrogen. After exchanging the atmosphere for nitrogen, the reaction vessel was sealed with a pressure compensation and heated to 60° C. while stirring. Held at 60° C. for 20 min, then heated to 65° C., again held for 20 min and finally heated to 70° C. and held for 60 min. After this time, an aqueous solution of the aqueous initiator was added to the resulting dispersion under protective gas and again stirred for 60 min. After this time, the dispersion was cooled to room temperature, mixed with emulsifiers, defoamer as well as thickening agent and adjusted to pH 8.5 with sodium hydroxide solution.

[0204] The obtained dispersions were analogously tested for their permeability behavior (see Table 2).

TABLE-US-00021 TABLE 1 Composition of Examples 4-7 according to the invention and comparative examples 1 and 2 Comparative Comparative example 1 Example 4 example 2 Example 5 Example 6 Example 7 Polyvinyl alcohol 66.80 65.43 66.23 66.94 64.84 73.49 solution distilled water 442.09 432.87 438.26 443.00 450.96 495.19 WAKO V-65B 0.83 0.92 0.82 0.83 1.34 1.36 Monomer 1 32.48.sup.a 32.26.sup.a 32.20.sup.a 47.49.sup.a 31.94.sup.a 35.68.sup.a Lauryl mercaptan 0.42 0.50 0.41 0.41 0.45 0.51 Core material 264.90.sup.b 259.34.sup.b 262.61.sup.b 253.48.sup.b 257.24.sup.b 280.73.sup.c Laromer TMPTA 14.52 14.15 14.39 0.00 14.10 16.50 Monomer 2 3.25.sup.d 0.00 0.62.sup.e 0.00 0.00 0.00 distilled water 4.14 4.05 4.10 4.09 6.45 7.31 WAKO VA-044 0.87 0.85 0.86 0.93 0.89 1.01 Isocyanate 0.00 9.33.sup.f 0.00 9.55.sup.g 10.40.sup.h 9.75.sup.g distilled water 0.00 0.00 0.00 0.00 2.15 2.44 10% Heavy Polyamine 0.00 2.96 0.00 3.21 3.85 4.37 XE solution PLEXTOL R 272 149.82 146.73 148.52 150.13 135.88 49.57 Emulsifier 1 3.56.sup.i 9.86.sup.j 9.98.sup.j 3.57.sup.i 3.46.sup.i 3.92.sup.i Emulsifier 2 2.83.sup.k 4.81.sup.l 4.87.sup.l 2.84.sup.k 2.75.sup.k 3.12.sup.k SILFOAM SE 47 3.00 2.94 2.98 3.01 3.11 3.52 Thickening agent 9.13.sup.m 5.29.sup.n 5.36.sup.n 9.15.sup.m 8.87.sup.m 10.05.sup.m Expedient 1 1.37.sup.o 5.29.sup.p 5.36.sup.p 1.37.sup.o 1.33.sup.o 1.50.sup.o Expedient 2 0.00 2.41.sup.q 2.43.sup.q 0.00 0.00 0.00 .sup.amethylmethacrylate .sup.bParafol 18-97 .sup.c1:10 mixture of Exxsol D100 ULA and C.I. Pigment Black 7 .sup.dVisiomer MPEG 750 MA .sup.eN,N-dimethylaminoethylmethacrylate .sup.fDesmodur I partially blocked with 10 mol % dimethylaminoethanol .sup.gDesmodur I .sup.hDesmodur I partially blocked with 20 mol % 2-hydroxyethylacrylate .sup.iLutensit A-BO .sup.jDisponil A 3065 .sup.kStrodex PK-90 .sup.lArquad 2.10-50 .sup.mRohagit SD 15 .sup.nBYK 7420 ES .sup.oSodium hydroxide solution 50% .sup.phexylene diglycol .sup.qDISPERBYK 192

TABLE-US-00022 TABLE 2 Type of functionalization and permeability of the core-shell particles according to the invention and the comparative particles Remaining latent Remaining latent heat on textile - heat on textile - layer close to the Solids content only layer close core and layer far of the Example Functionalization to the core from the core dispersion [%] Example 1 double wall with blocked 91.90% 90.30% 34% isocyanate groups Example 2 double wall with non-ionic 87.50% 93.70% 40% emulsifying groups Example 3 double wall decreased 64.50% 63.8% 36% acrylate crosslinker Comparative non-ionic emulsifying 45.35% / 40% example 1 groups Example 4 double wall with cationic 89.30% 89.00% 40% emulsifying groups Comparative Cationic emulsifying 64.37% / 40% example 2 groups Example 5 double wall without  0.00% 0.00% 40% acrylate crosslinker Example 6 double wall with 86.30% 87.20% 39% radiation-curing groups Example 7 double wall with / / 13% encapsulation of black dye

[0205] The following items are subject-matter of the present invention [0206] 1. Core-shell particles comprising [0207] (a) a core comprising at least one lipophilic compound and [0208] (b) a shell comprising at least one layer close to the core and one layer far from the core. [0209] 2. The core-shell particles of item 1, wherein the layer far from the core is disposed on the layer close to the core. [0210] 3. The core-shell particles of item 1 or 2, wherein the layer close to the core surrounds the core. [0211] 4. The core-shell particles of one of the preceding items, wherein the core is solid at room temperature (20° C.). [0212] 5. The core-shell particles of one of items 1-3, wherein the core is liquid, preferably present as solution, emulsion or suspension, or is solid, preferably present as powder, at room temperature (20° C.). [0213] 6. The core-shell particles of one of the preceding items, wherein the lipophilic compound has a water solubility of <10 g/l, preferably <5 g/l, more preferably <3 g/l at 20° C. [0214] 7. The core-shell particles of one of the preceding items, wherein the lipophilic compound is selected from pigments, dyes, fragrances, cosmetics, flame retardants, latent heat storage materials, biocides, catalysts, adhesives, adhesive components, hydrophobing agents, polymer building blocks, isocyanates, oils, silicone oils, waxes or mixtures thereof. [0215] 8. The core-shell particles according to item 7, wherein the latent heat storage material is selected from [0216] saturated or unsaturated, linear, branched or cyclic hydrocarbon, preferably saturated or unsaturated, linear, branched or cyclic C.sub.10-C.sub.40-hydrocarbon, more preferably linear or cyclic C.sub.10-C.sub.40-alkane and aromatic C.sub.6-C.sub.20 hydrocarbon, most preferably n-hexadecane, n-heptadecane, n-octadecane, n-nonadecane, n-eicosane, cyclohexane, cyclooctane, cyclodecane, benzene, naphthalene, biphenyl, [0217] saturated or unsaturated C.sub.6-C.sub.30-fatty acid, saturated or unsaturated C6-C30-fatty alcohol and saturated or unsaturated C.sub.6-C.sub.30-fatty acid-C.sub.1-C.sub.10-alkyl ester, preferably lauric, stearic, oleic or behenic acid, lauryl, stearyl or oleyl alcohol, propyl palmitate, methyl stearate or methyl palmitate, and [0218] mixtures thereof. [0219] 9. The core-shell particles of item 7, wherein the dye is selected from reactive dye, such as e.g. C.I. Reactive Red 2, disperse dye, such as e.g. C.I. Disperse Yellow 42, acid dye, such as e.g. C.I. Acid Blue 1, or basic dye, such as e.g. C. Basic Violet 3, and mixtures thereof. [0220] 10. The core-shell particles of item 7, wherein the pigments are selected from organic or inorganic pigments, particularly color pigments, magnetic pigments, and mixtures thereof. [0221] 11. The core-shell particles of item 7, wherein the fragrances are selected from synthetic or natural fragrances. [0222] 12. The core-shell particles of item 7, wherein the flame retardants are halogenated flame retardants, preferably tetrabromobisphenol A (TBA), bromopolystyrene, chlorinated paraffins and dibromoneopentylglycol (DBNPG), phosphoric flame retardants, preferably organic phosphoric acid ester or cyclic phosphate derivatives, or mixtures thereof. [0223] 13. The core-shell particles of item 7, wherein the biocides are selected from pesticides, fungicides, herbicides, insecticides, algicides, molluscicides, acaricides, rodenticides, bactericides, antibiotics, antiseptics, antibacterial, antiviral, antifungal, antiparasitic biocides and mixtures thereof. [0224] 14. The core-shell particles of item 7, wherein the cosmetics are selected from anti-wrinkle agents, radical quenchers, self-tanning agents and/or massage oils. [0225] 15. The core-shell particles of one of the preceding items, wherein the layer close to the core is obtainable by polymerization of at least one monomer with at least one ethylenically unsaturated group. [0226] 16. The core-shell particles of item 15, wherein the monomer with at least one ethylenically unsaturated group does not have a nucleophilic group with active hydrogen atom, particularly no NCO-reactive hydrogen. [0227] 17. The core-shell particles of item 15 or 16, wherein the layer close to the core is obtainable by radical polymerization. [0228] 18. Core-shell particle of one of items 15-17, wherein the ethylenically unsaturated group is a vinyl, vinyl ether, acryl, C1-6-alkyl acryl, allyl and/or allyl ether group. [0229] 19. The core-shell particles of one of items 15-18, wherein the monomer with at least one ethylenically unsaturated group has the structure:

##STR00004##

with

##STR00005##

B=—R.sup.5-R.sup.6
R.sup.1=—C.sub.1-C.sub.6-alkyl or —H, preferably —H or —CH.sub.3,
R.sup.2=linear or branched C.sub.1-C.sub.24-alkyl,
R.sup.3=linear or branched C.sub.1-C.sub.24-alkylene,

##STR00006##

R.sup.7=polyester, particularly obtainable by reaction of C.sub.1-C.sub.6-alkyldiols and C.sub.1-C.sub.6-alkyldicarboxyilic acids, such as e.g. diester, e.g. malonic acid ester, oxalic acid ester, succinic acid ester, glutaric acid ester or adipic acid ester, and
n=0-20 [0230] 20. The core-shell particles of one of items 15-19, wherein the molar ratio of monomers with one ethylenically unsaturated group to monomers with several ethylenically unsaturated groups is 2 to 40, preferably 4 to 30. [0231] 21. The core-shell particles of one of the preceding items, wherein the layer far from the core contains at least one urethane, allophanate, carbodiimide, isocyanurate, biuret, uretdione, urea, iminooxadiazinedione or uretonimine group. [0232] 22. The core-shell particles of one of the preceding items, wherein the layer far from the core is an addition product of at least one polyisocyanate and at least one compound comprising at least two groups with NCO-reactive hydrogen atom, preferably hydroxy, amino, carboxylic acid, urethane and/or urea groups. [0233] 23. The core-shell particles of item 22, wherein the polyisocyanate is aromatic, acyclic or aliphatic, preferably selected from methylene diphenyl isocyanate (MDI), polymeric MDI, toluylene diisocyanate (TDI), triphenylmethane-4,4′,4″-triisocyanate, 2,4,6-triisocyanatetoluene, isophorone diisocyanate (IPDI), 4,4′-methylenebis(cyclohexyl isocyanate) (H12MDI), methyl-2,4-cyclohexanediisocyanate, 1,3,5-triisocyanatecyclohexane, 1,3,5-trimethylisocyanatecyclohexane, trimethylene diisocyanate, 1,4,8-triisocyanateoctane, 1,3,6-triisocyanatehexane, hexamethylene diisocyanate, xylene diisocyanate (XDI), biuret-containing and isocyanurate-containing polyisocyanates. [0234] 24. The core-shell particles of item 22 or 23, wherein the NCO groups of the polyisocyanate are partially blocked. [0235] 25. The core-shell particles of item 23, wherein 0.1 to 80%, preferably 1 to 50%, more preferably 1 to 30% of the NCO groups of the polyisocyanate are blocked. [0236] 26. The core-shell particles of one of items 22-25, wherein the compound comprising at least two groups with NCO-reactive hydrogen atom is selected from polyols, polyester polyols, polyether polyols, polyureas, amino- and/or hydroxy-functionalized homo- or copolymers, polyamines and hydroxy-functionalized amines. [0237] 27. The core-shell particles of one of items 22-26, wherein the molar ratio of NCO groups to groups with NCO-reactive hydrogen atom lies between 1 and 100, preferably 2 and 100, more preferably 5 and 100 and even more preferably 5 and 80. [0238] 28. The core-shell particles of one of the preceding items, wherein the layer far from the core has at least one functional group, preferably an anionic, cationic or non-ionic group. [0239] 29. The core-shell particles of item 28, wherein the anionic group comprises at least one carboxylate, phosphate, phosphonate, sulfate or sulfonate group and preferably has the formula (I):

-L-X   formula (I)

wherein [0240] X is SO.sub.3.sup.−, SO.sub.4.sup.−, COO.sup.−, PO.sub.4.sup.2− or PO.sub.3.sup.2−, and [0241] L is linear or branched, saturated or unsaturated C.sub.1-C.sub.10 alkylene, which is optionally substituted with —OH. [0242] 30. The core-shell particles of item 28, wherein the cationic functional group comprises at least one quaternary ammonium ion or an ammonium salt and preferably has the formula (II):

-L-Y   formula (II) [0243] wherein [0244] Y is NHR.sub.8R.sub.9.sup.+ or NR.sub.8R.sub.9R.sub.10.sup.+, [0245] R.sub.8, R.sub.9 and R.sub.10 are each independently of each other H or linear or branched, saturated or unsaturated, C.sub.1-C.sub.10-alkyl, which is optionally substituted with OH and/or COOH, and [0246] L is as defined above. [0247] 31. The core-shell particles of item 28, wherein the non-ionic functional group comprises a polyalkylene oxide, preferably polyethylene oxide and/or polypropylene oxide. [0248] 32. The core-shell particles of one of items 28-31, wherein the functional group is bound to the layer far from the core via a urethane group. [0249] 33. The core-shell particles of one of items 27-31, wherein 0-30%, preferably 0 to 20%, more preferably 0.1 to 20% of the NCO groups in the polyisocyanate are converted with a compound comprising at least one functional group. [0250] 34. Composition, comprising at least one core-shell particle according to items 1-33. [0251] 35. The composition of item 34, wherein the composition comprises water. [0252] 36. The composition of item 34 or 35, wherein the composition further contains at least one surface-active reagent, particularly surfactant, a binding agent, a defoamer, a protective colloid and/or a thickening agent. [0253] 37. The composition of item 36, wherein the binding agent is a polymer with a glass transition temperature in the range of −45 to +45° C., particularly a polymer on the basis of (meth)acrylic acid ester, styrene, isoprene, butadiene, vinyl acetate and/or isocyanate. [0254] 38. The composition of one of items 34-37, wherein the defoamer is a mineral oil, a silicic acid or a silicone-containing defoamer. [0255] 39. The composition of one of items 34-38, wherein the core-shell particles according to items 1-33 make up 10 to 55 wt.-%, preferably 15 to 45 wt.-%, particularly preferred 20 to 37.5 wt.-% based on the total mass of the composition. [0256] 40. Method for preparing a core-shell particle of one of items 1-33 or a composition of one of items 34-39, comprising the steps: [0257] (i) providing at least one lipophilic compound, optionally slurried in a carrier oil, [0258] (ii) mixing the at least one lipophilic compound and optionally the carrier oil with [0259] at least one monomer with at least one ethylenically unsaturated group, [0260] water, [0261] at least one polymerization initiator, [0262] at least one protective colloid, [0263] optionally at least one surface-active reagent, [0264] optionally at least one chain regulator, [0265] under formation of an emulsion, wherein the water forms the continuous phase. [0266] (iii) treating the emulsion obtained in (ii) at elevated temperature while stirring, [0267] (iv) adding at least one, optionally partially blocked, polyisocyanate and at least one compound comprising at least two groups with NCO-reactive hydrogen atom and optionally adding at least one compound comprising at least one functional group and an NCO-reactive hydrogen atom, [0268] (v) optionally treating the mixture obtained in (iv) at elevated temperature, [0269] (vi) optionally adding at least one binding agent, defoamer, surface-active reagent and/or a thickening agent and [0270] (vii) optionally at least partially removing the water. [0271] 41. The method of item 40, wherein the disperse phase has a diameter D.sub.50 of 0.1 to 100 μm, preferably 0.5 to 80 μm and more preferably 1 to 75 μm. [0272] 42. The method of item 40 or 41, wherein the protective colloid is selected from water-soluble polymer, particularly polyvinyl alcohol, cellulose derivatives, particularly hydroxyalkyl cellulose or carboxyalkyl cellulose, gum arabic, polyacrylic acid, polyacrylamides, polyvinylpyrrolidone and/or maleic acid anhydride copolymers. [0273] 43. The method of one of items 40-42, wherein the surface-active reagent is selected from anionic, cationic or non-ionic surfactants. [0274] 44. The method of one of items 40-43, wherein the polymerization initiator is a radical initiator, particularly a peroxide, an azo compound, a persulfate, a hydroperoxide and/or a redox initiator, or mixtures thereof. [0275] 45. The method of one of items 40-44, wherein the chain regulator is a sulfurous compound, particularly lauryl mercaptan or ethylhexylthioglycolate. [0276] 46. The method of one of items 40-45, wherein the solubilizer is mono-, di- or triglyceride, mineral oil, silicone oil, castor oil and/or isopropyl myristate. [0277] 47. The method of one of items 40-46, wherein step (iii) takes place at temperatures of 25 to 100° C., preferably 50 to 100° C. [0278] 48. The method of one of items 40-47, wherein step (iv) takes place at temperatures of 25 to 100° C., preferably 50 to 100° C. [0279] 49. The method of one of items 40-48, wherein step (v) is preferably carried out for 0.25 to 4 hours, preferably at temperatures of 25 to 100° C., preferably 30 to 90° C. [0280] 50. Core-shell particles obtainable by a method according to items 40-49. [0281] 51. Use of the core-shell particles of one of items 1-33 or 50 or the composition of one of items 34-39 for the functionalization of materials, particularly fibers, textile fabrics, construction materials, plastics, plastic foams, paint and varnish. [0282] 52. Method for the finishing of materials, particularly of textiles, comprising the steps [0283] (a) providing the core-shell particles of one of items 1-33 or 50 or the composition of one of items 34-39, [0284] (b) applying the core-shell particles or the composition to a material; and [0285] (c) thermally treating the material. [0286] 53. Materials, particularly fibers or textile materials, comprising core-shell particles of one of items 1-33 or 50 or the composition of one of items 34-39.