EP3810673A1

EP3810673A1 - Functional multi-walled core-shell particles

Info

Publication number: EP3810673A1
Application number: EP19731758.9A
Authority: EP
Inventors: Jonas HEPP; Dirk Sielemann; Gunther Duschek
Original assignee: Rudolf GmbH
Current assignee: Rudolf GmbH
Priority date: 2018-06-25
Filing date: 2019-06-24
Publication date: 2021-04-28
Also published as: TWI821320B; CN112313259B; US20210245132A1; WO2020002202A1; CN112313259A; EP3587467A1; TW202016164A

Abstract

The present invention relates to core-shell particles comprising a core that includes at least one lipophilic compound and a shell that includes at least a layer close to the core and a layer remote from the core. The invention further relates to the production of such core-shell particles and to the use thereof, in particular for finishing fibers and textiles.

Description

Functional multi-walled core-shell particles

The present invention relates to core-shell particles comprising a core which comprises at least one lipophilic compound and a shell which comprises at least one layer close to the core and one layer remote from the core. The invention further relates to the production of such core-shell particles and their use, in particular for finishing fibers and textiles.

The microencapsulation of lipophilic compounds is well known: The mostly liquid or solid compounds are surrounded in the smallest portions with a shell and thus immobilized. The formation of the shell is usually generated by coacervation, interfacial reactions or in situ polymerization techniques. For this purpose, the compound to be encapsulated is usually dispersed in a liquid medium and the shell is formed at the interface between the compound and the medium. So far, special attention has been paid to melamine-formaldehyde microcapsules. As described above, a dispersion of medium and compound to be encapsulated is first produced, to which a melamine-formaldehyde prepolymer is added. The prepolymer hardens at the interface and forms a solid, impermeable shell with mechanically acceptable properties. Since formaldehyde is known to be released from the condensates, melamine-formaldehyde microcapsules are becoming less and less important for health reasons.

EP 1 246 693 suggests adding melamine during the hardening phase of the melamine-formaldehyde resin shell in order to reduce the subsequent release of formaldehyde. From DE 2 242 910 it is known that a polyurea shell can be produced by an interface reaction of polyisocyanates with polyamines. EP 1 029 018 describes the formation of capsule walls by polymerizing acrylates. Attempts have been made to further functionalize the shell.

On the basis of the systems described above, functionalization is either not possible or negatively influences the shell morphology, e.g. by forming pores, channels, etc.

It is known from WO 2012/075293 that when the polar monomer N, N-dimethylaminoethyl methacrylate is polymerized, hydrogel structures are formed. When swelling, channels and pores are created that promote the diffusion of the active substance of the core.

No. 8,747,999 describes a core-shell particle, the shell of which is produced by simultaneous reaction of a melamine-formaldehyde resin with a diallyldimethylammonium chloride copolymer. The shell thus carries functional groups in the form of cationic units and reactive methylol functions. However, the shell cannot be functionalized to any degree, since this inevitably leads to a disturbance in the shell structure.

EP 2 043 773 discloses the subsequent functionalization of a core-shell particle by coating with a polyelectrolyte.

Furthermore, microencapsulations are described in the prior art, in which more than two shells are formed around the core. WO 2013/182855 discloses a core-shell particle with two polyurea shells arranged one above the other as a shell. The double encapsulation allows the permeability to be reduced. However, applying the second polyurea shell to the first polyurea shell is complicated and requires additional chemicals.

No. 8,329,233 describes core shell particles which have a melamine-formaldehyde shell, which in turn is coated with a polyacrylate shell. The release of formaldehyde is to be prevented by the outer polyacrylate shell. The potential danger of

Formaldehyde release cannot be excluded.

EP 1 513 610 discloses a core-shell particle with a double wall structure with the aim of reducing the permeability. The sleeves made of polyurethane and polyurea are cross-linked, which can lead to defects in the respective sleeves.

No. 7,025,912 describes a core-shell particle with a double-wall structure, the inner shell of which consists of polyurea and the outer shell of which is based on ethylenically unsaturated monomers. In the

Polyurea shells are embedded in ethylenically unsaturated surfactants, which serve as anchor points for the second shell. The use of the surfactants can lead to disturbances, e.g. Pores or channels that come in the polyurea shell. In addition, the inner polyurea shell is not sufficiently compatible with the core material.

In view of the prior art, it was an object of the present invention to encapsulate a lipophilic compound. The shell of the capsule should be inert to the lipophilic compound. Furthermore, the properties of the shell, for example the permeability, mechanical strength, functionality, etc., should be variable and reproducible. In the following, functionality is understood in particular to mean the modification of the shell with functional, in particular functional chemical, groups. Surprisingly, it has been found that the object is achieved by the core-shell particle according to the invention, which comprises (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 remote from the core.

The aggregate state of the core can be gaseous, solid or liquid, the core is preferably solid at room temperature (20 ° C.) and can be in the form of a powder, for example. In another preferred embodiment, the core is liquid at room temperature (20 ° C.) and can also be in the form of a solution, emulsion or suspension at this temperature. In a preferred embodiment, the core comprises at least 80% by weight, more preferably at least 90 to 99% by weight, of the at least one lipophilic compound (based on the total mass of the core). In a preferred embodiment, the core consists of at least one lipophilic compound. In a preferred embodiment, the lipophilic compound has a water solubility of <10 g / l, more preferably <5 g / l, even more preferably <3 g / l at 20 ° C.

Preferred lipophilic compounds, which can optionally be suspended in a carrier oil, are selected from pigments, dyes, fragrances, cosmetics, flame retardants, latent heat storage materials, biocides, catalysts, adhesives, adhesive components, hydrophobizing agents, polymer building blocks, isocyanates, oils, silicone oils, waxes or mixtures thereof. Suitable carrier oils are, for example, mono-, di- or triglyceride, mineral oil, silicone oil, castor oil and isopropyl myristate, or mixtures thereof. Latent heat storage materials refer to substances that have a phase transition. The phase transition should take place in the range of the respective application temperature; the latent heat storage material used is preferably a substance which has a solid / liquid phase transition in the temperature range from -20 to 120 ° C. Latent heat storage materials for clothing materials typically have a phase transition between 15 and 35 ° C.

Suitable latent heat storage materials are preferably selected from · saturated or unsaturated, linear, branched, or cyclic hydrocarbon, preferably saturated or unsaturated, linear, branched, or cyclic Cio-C ₄ o- hydrocarbon, more preferably linear or cyclic C ₀ - C ₄₀ alkane and aromatic C ₆ -C ₂ o hydrocarbon, most preferably n-hexadecane, n-heptadecane, n-octadecane, n-nonadecane, n-eicosane, cyclohexane, cyclooctane, cyclodecane, benzene, naphthalene, biphenyl,

• saturated or unsaturated C ₆ -C 3 ₀ fatty acid, saturated or unsaturated C ₆ -C 3 ₀ fatty alcohol and saturated or unsaturated C ₆ -C ₃ o fatty acid Ci-Cio-alkyl-ester, preferably lauric, stearic, Oleic or behenic acid, lauryl, stearyl or oleyl alcohol, propyl palmitate, methyl stearate or methyl palmitate, and

• Mixtures of these. Dyes can be selected from reactive dyes such as Cl Reactive Red 2, disperse dyes such as Cl Disperse Yellow 42, acid dyes such as Cl Acid Blue 1, or basic dyes such as Cl Basic Violet 3 and mixtures thereof. Pigments are coloring substances that are practically insoluble in the application medium, e.g. oils. Preferred pigments are either inorganic or organic pigments. Pigments can also be classified according to their optical properties (specific color) and their technical properties (corrosion protection, magnetism). In the latter case, color pigments, magnetic pigments and mixtures thereof are preferred.

Perfumes according to the present invention can be synthetic or natural in nature. Natural fragrances include e.g. oily flower and / or fruit bark extracts or essential oils. Synthetic fragrances include, for example, esters, ethers or aldehydes.

The flame retardants used are preferably halogenated flame retardants, more preferably tetrabromobisphenol A (TBA), bromopolystyrene, chlorinated paraffins and dibromoneopentyl glycol (DBNPG), phosphate-containing flame retardants, more preferably organic

Phosphoric acid esters or cyclic phosphate derivatives, or mixtures thereof.

Biocides according to the present invention are preferably selected from pesticides, fungicides, herbicides, insecticides, algicides, molluscicides,

Acaricides, rodenticides, bactericides, antibiotics, antiseptics, antibacterial, antiviral, antifungal, antiparasitic biocides and mixtures thereof. Cosmetics are preferably selected from anti-wrinkle agents, free radical scavengers, self-tanners and / or massage oils.

L /, L / '- dimethylaminoethanol, N, N'-dimethylcyclohexylamine, tin (II) -2-ethylhexanoate, dibutyltin dilaurate and mixtures thereof can be used as catalysts. Adhesives and adhesive components include, for example, one-component and two-component systems, for example based on lipophilic isocyanates, polyols, polyamines, carbodiimides, organotin compounds, acrylates and / or epoxides.

Suitable oils preferably include natural or synthetic oils. Aliphates, such as saturated, unsaturated and / or cyclic hydrocarbons, aromatic hydrocarbons, such as e.g. Benzene, xylene, naphthalene and / or toluene, vegetable oils such as e.g. Soybean oil, olive oil and / or rapeseed oil, silicone oils, and mixtures thereof.

Suitable waxes include, for example, polyolefin waxes such as e.g. Polyethylene wax, carnauba wax, polyvinyl ether wax, and mixtures thereof.

In a preferred embodiment, the shell comprises a layer close to the core and a layer remote from the core. In a preferred embodiment, the shell essentially consists of a layer close to the core and a layer remote from the core. In a preferred embodiment, the shell consists of a layer close to the core and a layer remote from the core and optionally auxiliaries.

In a preferred embodiment, the layer remote from the core and / or the layer close to the core, in particular the layer remote from the core and the layer close to the core, is covalently crosslinked.

In a preferred embodiment, the layer close to the core directly surrounds the core.

In a preferred embodiment, the layer remote from the core is arranged on the layer close to the core, ie between the layer remote from the core and In particular, no additional covalently cross-linked layer is arranged in the layer close to the core.

In a preferred embodiment, the - possibly covalently cross-linked - layer close to the core and the - optionally covalently cross-linked - layer remote from the core are not covalently bonded to one another.

The layer remote from the core and / or close to the core is / is preferably a polymer, in particular a crosslinked polymer, for example based on a polyolefin, polyacrylate, polyurethane, which may also contain one or more allophanate, carbodiimide, isocyanurate, biuret, uretdione -, Urea, iminooxadiazinedione and / or uretonimine groups can contain, polyallophanate, polycarbodiimide, polyisocyanurate, polybiurets, polyuretdione, polyurea, polyiminooxadiazinedione, polyuretonimine, epoxy resin, vinyl polymer, allyl polymer, in particular or based on a polyacrylate.

The layer close to the core is preferably based on a polymer of at least one ethylenically unsaturated monomer, in particular a crosslinked polyacrylate polymer. The core-distant layer is preferably based on a polyurethane, which may also contain one or more allophanate, carbodiimide, isocyanurate, biuret, uretdione, urea, iminooxadiazinedione and / or uretonimine groups, polyallophanate, polycarbodiimide, Polyisocyanurate, polybiurets, polyuretdione, polyurea, polyiminooxadiazinedione, and / or polyuretonimine, in particular based on a crosslinked polyurethane and polyurea.

The layer close to the core is preferably inert to the core. The layer close to the core furthermore preferably contains no functional groups, in particular no functional groups which enable a covalent connection to the layer remote from the core. In a preferred embodiment, the near-core layer is obtainable by polymerizing at least one monomer with at least one ethylenically unsaturated group. The layer close to the core is particularly preferably obtainable by polymerizing at least one monomer with a monoethylenically unsaturated group and at least one monomer with a polyethylenically unsaturated group.

Preferred ethylenically unsaturated groups are vinyl, vinyl ether, acrylic, CrC ₆ alkyl acryl, allyl and / or allyl ether groups.

Suitable monomers with at least one ethylenically unsaturated group preferably do not contain a nucleophilic group with an active hydrogen atom, in particular no nucleophilic group with an NCO-reactive hydrogen atom.

The monomer having at least one ethylenically unsaturated group is preferably selected from compounds having the following structures:

B = - R ⁵ - R ⁶

R ¹ = -CrC ₆ -alkyl or -H, preferably -H or -CH ₃ ,

R ² = linear or branched Ci-C ₂₄ alkyl,

R ³ = linear or branched Ci-C2 ₄ alkylene,

R ⁷ = polyester, especially obtainable by reaction of CrC ₆ alkyldiols and C- _| -C ₆ alkyl dicarboxylic acids, such as malonic acid, oxalic acid, succinic acid, glutaric acid or adipic acid, and n = 0-20.

Preferred monomers with an ethylenically unsaturated group are Cr C ₂₄ alkyl esters of (meth) acrylic acid, CrC ₂₄ vinyl ether, CrC ₂₄ allyl ether and styrene. “Alkyl” in the sense of the present invention is a saturated, linear, cyclic or branched, hydrocarbon. Monomers with an ethylenically unsaturated group are particularly preferred methyl, ethyl, n-propyl, n-butyl, / so-butyl (sec-butyl and ferf-butyl) and / ^' so-propyl (meth) acrylate. As monomers with several, preferably 2, 3, 4 or 5, ethylenically unsaturated groups, preference is given to using diesters of diols and (meth) acrylic acid and diallyl and divinyl ethers of these diols. Monomers with several ethylenically unsaturated groups are particularly preferred selected from ethanediol diacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol methacrylate, allyl acrylate, allyl methacrylate,

Polyesters of polyols and (meth) acrylic acid and polyallyl and polyvinyl ethers of these polyols, in particular butanediol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate and pentaeritrite tetra (meth) acrylate.

The layer close to the core is preferably obtained by radical polymerization. In addition to UV initiators and redox initiators, suitable radical polymerization initiators are in particular peroxides, hydroperoxides, azo compounds, persulfates, perborates, or mixtures thereof.

The layer close to the core is preferred by radical polymerization of methyl (meth) acrylate, ethyl (meth) acrylate, A / -propyl (meth) acrylate or N-butyl (meth) acrylate and butanediol di (meth) acrylate and / or

Trimethylolpropane tri (meth) acrylate obtained. The molar ratio of monomers with one ethylenically unsaturated group to monomers with several ethylenically unsaturated groups is preferably 0 to 40, more preferably 2 to 40, even more preferably 4 to 30.

In another embodiment, the near-core layer can be obtained by polymerizing 100 mol% of monomers with an ethylenically unsaturated group. The polymer of the near-core layer preferably contains at least 55 mol%, more preferably at least 60 mol%, even more preferably at least 65 mol%, and most preferably at least 70 mol% of monomers with an ethylenically unsaturated group based on the total amount of the Monomers in the layer close to the core, for example 70 to 100 mol%.

The proportion of monomers with several ethylenically unsaturated groups in the layer close to the core is, for example, 0 to 45 mol%, preferably up to 30 mol%, such as 5 to 30 mol%, more preferably up to 20 mol%, for example 10 to 20 mol %, more preferably up to 15 mol%, for example 10 to 15 mol% and most preferably 0.01 to 30 mol%, based on the total amount of monomers in the near-core layer. In a preferred embodiment, the near-core layer is obtainable by polymerizing at least 80 mol% of monomers with one ethylenically unsaturated group and up to 20 mol% of monomers with several ethylenically unsaturated groups. The ratio of monomers with one ethylenically unsaturated group and monomers with several ethylenically unsaturated groups is determined the degree of cross-linking. The degree of crosslinking has a decisive influence, for example, on the mechanical stability and permeability of the layer. Thus, with increasing degree of crosslinking (that is, with increasing proportion of monomers with several ethylenically unsaturated groups), the mechanical stability usually increases, and at the same time the permeability decreases. The thickness of the layer close to the core also plays a role in the mechanical stability and permeability. The thicker the layer, the lower the permeability and the higher the mechanical stability.

The layer remote from the core preferably contains at least one urethane, allophanate, carbodiimide, isocyanurate, biuret, uretdione, urea, iminooxadiazinedione and / or uretonimine group, more preferably at least one urethane and / or urea group.

In a preferred embodiment, the layer remote from the core is one

Addition product of at least one polyisocyanate and at least one compound comprising at least two groups with an NCO-reactive hydrogen atom, preferably hydroxyl, amino, carboxylic acid, urethane and / or urea groups.

In a preferred embodiment, the layer remote from the core is one

Polyurethane. The polyisocyanate is preferably aromatic, alicyclic or aliphatic. The polyisocyanate is preferably selected from methylene diphenyl isocyanate (MDI), polymeric MDI, tolylene diisocyanate (TDI), triphenylmethane-4,4 ', 4 “- triisocyanate, 2,4,6-triisocyanate toluene, isophorone diisocyanate (IPDI), 4,4'-methylene bis - (cyclohexyl isocyanate) (H12MDI), methyl 2,4-cyclohexane diisocynate, 1, 3,5-triisocyanate cyclohexane, 1, 3,5-trimethyl isocyanate cyclohexane, trimethylene diisocyanate, 1, 4,8-triisocyanatoctane, 1, 3, 6 Triisocyanate hexane, hexamethylene diisocyanate, xylene diisocyanate (XD I), in particular 1,3, or 1,4-xylene diisocyanate, and derivatives thereof, such as, for example, polyisocyanates containing biurethane and isocyanurate. Some of the NCO groups of the polyisocyanate can be blocked. In the case of blocked isocyanates, the NCO groups are reacted with protective groups so that the isocyanate group does not react under normal storage conditions (for example 0 to 80 ° C.). By activating the blocked isocyanates, for example by increasing the temperature (so-called deblocking temperature, for example> 80 ° C.), the protective group can be split off, with the isocyanate groups regressing. The blocking of isocyanates is known to the person skilled in the art and is described in the literature (see DA Wieks, ZW Wieks Jr., Progress in Organic Coating 36 (1999), 148-172). Suitable blocking agents for isocyanates are, for example, malonic esters, such as, for example, dimethyl malonate, acetoacetate

Ethyl acetoacetate, β-diketones (e.g. 2,4-pentanedione) and cyanoacetates; Bisulfite (e.g. sodium bisulfite), phenol (e.g. 4-nitrophenol), pyridinol (e.g. 3-hydroxypyridine), thiophenol, mercaptopyridine (e.g. 2-mercaptopyridine), alcohol (e.g. 2-ethylhexyl alcohol), N-hydroxysuccinimide, oxime (e.g. methyl ethyl ketone oxime, 2 Butanone oxime), amide (e.g. acetanilide, caprolactam),

Imide (e.g. succinimide), imidazole, amidine, guanidine, pyrazole (e.g. 3,5-dimethylpyrazole), triazoles (e.g. 1, 2,4-triazole) or amine (e.g. piperidine, tert-butylbenzylamine). If necessary, at least one catalyst can be added for the reaction of the isocyanate groups. All catalysts known to those skilled in the art which are used in polyurethane chemistry are suitable for this. For example, organic, in particular tertiary aliphatic, cycloaliphatic or aromatic amines, and Lewis acidic organic metal compounds come into consideration. This includes N, N'

Dimethylaminoethanol, N, N'-dimethylcyclohexylamine, 1, 4- Diazabicyclo [2.2.2] octane, tin (II) -2-ethylhexanoate, dibutyltin dilaurate and mixtures thereof.

The catalyst is preferably used in amounts of 0.0001 to 10% by weight, particularly preferably in an amount of 0.001 to 5% by weight, based on the mass of the polyisocyanate.

Pyrazole, oxime and benzylamine are preferably used to block isocyanate groups, more preferably 3,5-dimethylpyrazole, 2-butanone oxime and tert-butylbenzylamine.

Preferably 0.1 to 80%, more preferably 1 to 50%, even more preferably 1 to 30% of the NCO groups of the polyisocyanate are blocked. Preferably 0.1 to 50%, more preferably 5 to 40%, even more preferably 10 to 30% of the NCO groups of the polyisocyanate are blocked.

Preferably the deblocking temperature is in the range of 80 to 180 ° C, more preferably in the range of 120 to 160 ° C.

An advantage of the reversible blocking reaction of isocyanate groups is the regeneration of a highly reactive functional group. For example, it is able to improve the connection of the core-shell particles to a substrate and thus also the abrasion and / or wash resistance.

The compound, comprising at least two groups with an NCO-reactive hydrogen atom, is preferably selected from polyol (including diol), polyester polyol, polyether polyol, polyurea, amino- and / or hydroxy-functionalized homo- or copolymer, polyamine (including diamine), hydroxy-functional amine, polyurethane and / or polycarboxylic acid. Polyether polyols are preferably based on C2-C5 alkylene oxide units, such as, for example, ethylene oxide, propylene oxide, butane oxide and / or pentane oxide units. Polyether polyols are preferably polyethylene glycol and / or polypropylene glycol.

Polyester polyols are preferably reaction products of diols (e.g. 1,4-butanediol, diethylene glycol, or 1,6-hexanediol) with dicarboxylic acids (e.g. glutaric acid, adipic acid or pimelic acid), and / or lactones (e.g. e-caprolactone).

Hydroxy-functionalized polymers are preferably based on hydroxy-functional vinyl monomers e.g. 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. Suitable polyamines have at least two primary and / or secondary amines. Polyvinylamine, diethylene triamine, pentaethylene hexamine, toluenediamine, piperazine, polyethyleneimine and mixtures thereof are preferably used. Preferred hydroxy-functional amines are ethanolamine or aminopropyl alcohol.

The compound comprising at least two groups with an NCO-reactive hydrogen atom is preferably water-soluble (> 10 g / l at 20 ° C.). Preferred is the molar ratio of NCO groups to groups with NCO reactive hydrogen, e.g. -OH, -NH2, -NHR, between 1 and 100, preferably 2 and 100, more preferably 5 and 100 and even more preferably 5 and 80.

In a preferred embodiment, the addition product of the layer remote from the core comprises about 1 to 50 mol%, more preferably about 3 to 40 mol% and even more preferably about 5 to 20 mol% of the compound, comprising at least two groups with NCO-reactive hydrogen atom, based on the amount of substance of the free isocyanate groups originally available. In a preferred embodiment, the layer remote from the core contains at least 1 mol%, preferably at least 2.5 mol%, even more preferably at least 5 mol%, of polyols and / or polyamines, based on the amount of substance of the free isocyanate originally available -Groups.

The addition product of the layer remote from the core preferably comprises about 40 to 99% by weight of polyisocyanate, more preferably 60 to 99% by weight, even more preferably 70 to 99% by weight, even more preferably 80 to 99% by weight and am most preferably about 90 to 99% by weight of polyisocyanate based on the total mass of the layer remote from the core.

In a further preferred embodiment, the layer remote from the core has at least one additional functional group, preferably an anionic, cationic or nonionic group or an ethylenically unsaturated group (for example vinyl, allyl or (meth) acrylic group). The at least one additional functional group, in particular an anionic, cationic or nonionic group, brings about improved dispersibility and dispersion stability of the core-shell particles in an aqueous environment. Core-shell particles with ethylenically unsaturated groups in the layer remote from the core can be polymerized or crosslinked by thermal treatment or treatment with energetic radiation. If necessary, auxiliaries known to the person skilled in the art, such as catalysts, initiators, photoinitiators, etc., can be used for better polymerization or crosslinking. The anionic group preferably comprises at least one carboxylate, phosphate, phosphonate, sulfate, sulfonate group. The anionic group more preferably comprises the formula (I)

-L-X

Formula (I)

in which

X is S0 ₃ , S0 ₄ , COO, P0 ₄ ² or P0 ₃ ² , in particular S0 ₃ or COO, and

L is linear or branched, saturated or unsaturated C1-C10 alkylene, which is optionally substituted by -OH.

In the case of addition products of at least one polyisocyanate and at least one compound comprising at least two groups with an NCO-reactive hydrogen atom, the functional anionic group can be introduced into the layer remote from the core by reaction of an isocyanate group of the polyisocyanate with a compound which, in addition to an anionic group, has an isocyanate-reactive hydrogen atom become. The compounds mentioned above preferably have the formula ALX, where L and X are as defined above and A is preferably OH, NH ₂ or NHR. Preferably the functional cationic group is a quaternary ammonium ion or an ammonium salt and more preferably has formula (II):

-L-Y

Formula (II)

in which

Y is NHR ₈ R ₉ ⁺ or NR ₈ R ₉ RIO ⁺ , R ₈ , Rg and Rio are each independently H or linear or branched, saturated or unsaturated, Ci-Cio-alkyl, which is optionally substituted with -OH and / or -COOH and

L is as defined above.

In the case of an addition product composed of at least one polyisocyanate and at least one compound comprising at least two groups with an NCO-reactive hydrogen atom, the cationic functional group is preferably introduced via a compound which, in addition to an isocyanate-reactive hydrogen atom, has a quaternary ammonium ion, secondary or tertiary amine. Preferred compounds are N-methyldiethanolamine and A /, A / -dimethylethanolamine. The amines can then be converted into quaternary ammonium groups or ammonium ions by alkylation or protonation. The amines are preferably methylated. Suitable methods for alkylation and corresponding alkylating agents are known to the person skilled in the art. Preferred alkylating agents are dimethyl sulfate, methyl chloride, or methyl tosylate.

Preferred nonionic functional groups include polyalkylene oxides, preferably polyethylene oxide and / or polypropylene oxide. Polyalkylene oxides with a weight average molecular weight of 200 to 2000 g / mol, more preferably 400 to 1000 g / mol, are preferably used. Preferred polyalkylene oxides are methyl-capped-polyethylene glycol (MPEG), methyl-capped-polypropylene glycol or methyl-capped-poly- (ethylene glycol / propylene glycol).

In the case of addition products of at least one polyisocyanate and at least one compound comprising at least two groups with an NCO-reactive hydrogen atom, the functional nonionic group can be reacted by reacting an isocyanate group of the polyisocyanate with a compound which has an isocyanate-reactive hydrogen atom in addition to a nonionic group the far core layer are introduced. In the case of addition products of at least one polyisocyanate and at least one compound comprising at least two groups with an NCO-reactive hydrogen atom, the functional ethylenically unsaturated group can be obtained by reacting an isocyanate group of the polyisocyanate with a compound which, in addition to at least one ethylenically unsaturated group, has an isocyanate-reactive hydrogen atom, be introduced into the layer remote from the core. Compounds which have an isocyanate-reactive hydrogen atom in addition to at least one ethylenically unsaturated group are preferred (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, allylamine, acrylamide,

Diallylamine, pentaerythritol triacrylate and polymers containing one or more such compounds as comonomers. Compounds with one or more acrylate functions are particularly preferred. In a preferred embodiment, the additional functional group is covalently bound to the layer remote from the core via a urethane group.

In the case of an addition product composed of at least one polyisocyanate and at least one compound comprising at least two groups with an NCO-reactive hydrogen atom in the layer remote from the core, up to 50%, more preferably 5-40%, even more preferably 10 to 30% of those originally available NCO groups in the polyisocyanate can be reacted with a compound comprising at least one functional group. In the case of an addition product composed of at least one polyisocyanate and at least one compound comprising at least two groups with an NCO-reactive hydrogen atom in the layer remote from the core, up to 30%, more preferably up to 20%, even more preferably 0.1 to 20% of the originally Available NCO groups in the polyisocyanate can be reacted with a compound comprising at least one functional group. The layer remote from the core and the layer close to the core can optionally be covalently bonded to one another. The layer close to the core and away from the core are preferably not covalently bonded to one another. Surface-active reagent, in particular surfactant, defoamer, protective colloid or thickener, may be arranged between the layer remote from the core and the layer close to the core. The compounds, which can be arranged mainly between the layer remote from the core and the layer close to the core, make up, for example, 0 to 70% by weight, preferably 5 to 30% by weight, more preferably 10 to 15% by weight, based on the total mass of the core away and the near-core layer.

In a particularly preferred embodiment, the core-shell particle according to the invention comprises

(a) a core comprising at least one lipophilic compound and

(b) a shell comprising a layer close to the core and a layer remote from the core

Layer.

In a particularly preferred embodiment, the core-shell particle consists of

(a) a core comprising at least one lipophilic compound,

(b) a shell comprising a layer close to the core and a layer remote from the core and

(c) optionally at least one auxiliary, in particular surface-active reagent, preferably surfactant, binder, defoamer, protective colloid or thickener.

In a particularly preferred embodiment, the core-shell particle consists of

(a) a core comprising at least one lipophilic compound and

Layer. In a particularly preferred embodiment, the core-shell particle according to the invention comprises

(a) a core comprising at least one lipophilic compound and

Layer,

the layer close to the core being obtainable by polymerizing at least one monomer having at least one ethylenically unsaturated group.

(a) a core comprising at least one lipophilic compound and

(b) a shell comprising a layer close to the core and a layer remote from the core,

the near-core layer is obtainable by polymerizing at least one monomer having at least one ethylenically unsaturated group and the distant-core layer contains at least one urethane, allophanate, carbodiimide, isocyanurate, biuret, uretdione, urea, iminooxadiazinedione or uretonimine group and is preferably a polyurethane.

The weight ratio between the near-core layer and the remote core layer is preferably 50:50 to 95: 5% by weight, more preferably 70:30 to 90:10% by weight and most preferably 80:20 to 90:10% by weight. % based on the total mass of the near-core and the far-away layer.

The weight ratio of core: shell is preferably in the range from 50:50 to 95: 5, preferably 70:30 to 90:10. The layer remote from the core is preferably permeable to the lipophilic compound. Methods for determining the permeability of the core-shell particles are known. The permeability can be determined, for example, via the loss of latent heat by means of dynamic differential scanning calorimetry (DSC) (cf. also examples).

The core-shell particles according to the invention are preferably spherical or ellipsoidal, more preferably spherical.

The mean diameter (D50) of the core-shell particles according to the invention is preferably 0.1 to 100 pm, more preferably 0.5 to 80 pm and even more preferably 1 to 75 pm (e.g. determined by laser diffraction). Another aspect of the invention relates to a composition comprising at least one core-shell particle according to the invention. The composition preferably also contains water.

In a preferred embodiment, the composition further contains at least one auxiliary, preferably at least one surface-active reagent, in particular a surfactant, a binder, a defoamer, a protective colloid and / or a thickener.

Nonionic, anionic or cationic surfactants and / or mixtures thereof can be used in particular as surface-active reagents. Preferred nonionic surfactants are e.g. Alkoxylation products of fatty acids, fatty acid esters, fatty acid amides, aliphatic alcohols and sugar derivatives. Ethoxylation products of linear or branched aliphatic alcohols having 6 to 22 carbon atoms are preferably used.

Preferred cationic surfactants are quaternary ammonium salts, such as, for example, di- (C10-C24) -alkyldimethylammonium chloride, (C10-C24) -alkyldimethylethylammonium chloride or -bromide, (C10-C24) -alkyltrimethylammonium chloride or -bromide, (C10-C24dimoniumchloride) alkylbenzylammonium chloride . Alkylmethylpoly (oxyethylene) ammonium chloride, bromide or monoalkyl sulfate, salts of primary, secondary and tertiary fatty amines with 8 to 24 carbon atoms with organic or inorganic acids, salts of ethoxylated primary and secondary fatty amines with 8 to 24 carbon atoms with organic or called inorganic acids, imidazolinium derivatives or esterquats. Di (C10-C24) alkyldimethylammonium chloride, (C10-C24) alkyltrimethylammonium chloride or bromide, salts of primary, secondary and tertiary fatty amines having 8 to 24 carbon atoms with organic or inorganic acids and esterquats are preferred.

Anionic surfactants are especially fatty alcohol sulfates such as Sodium lauryl sulfate, alkyl sulfonates such as e.g. Sodium lauryl sulfonate, alkylbenzenesulfonate, e.g. Sodium dodecylbenzenesulfonate and fatty acid salts such as e.g. Sodium stearate and phosphate esters, e.g. Phosphate esters of aliphatic alcohols.

The surface-active reagents are preferably added in an amount of 0-10% by weight, more preferably 0 to 5% by weight, even more preferably 0 to 2% by weight, based on the mass of the total composition.

Preferred protective colloids are preferably water-soluble polymers, for example polyvinyl alcohol, cellulose derivatives, in particular hydroxyalkyl cellulose or carboxyalkyl cellulose, gum arabic, polyacrylic acid, polyacrylamide, polyvinyl pyrrolidone and / or maleic anhydride copolymers, polyvinyl alcohol is particularly preferred.

The protective colloid is preferably present in amounts of 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, even more preferably 0.5 to 5% by weight, based on the mass of the total composition. Preferred binders are polymers with a glass transition temperature in the range from -45 to +45 ° C., particularly selected from polymers based on (meth) acrylic acid ester, styrene, isoprene, butadiene, vinyl acetate and / or isocyanate. The binder is preferably in amounts of 0.01 to 20% by weight, more preferably 0.01 to 5% by weight, based on the mass of the

Overall composition.

Preferred defoamers are selected from mineral oil, silicic acid, silicone-containing compounds, such as e.g. Organosilicon compounds. The defoamer is preferably present in amounts of 0.01 to 10% by weight, more preferably 0.01 to 2% by weight, based on the mass of the total composition.

The composition according to the invention preferably comprises 10 to 55% by weight, more preferably 15 to 45% by weight, even more preferably 20 to

37.5% by weight of the core-shell particles according to the invention, based on the total mass of the composition.

Another aspect of the present invention is a method for producing the core-shell particle or the composition according to the invention. The process includes the steps:

(i) providing at least one lipophilic compound, optionally suspended 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, with the formation of an emulsion in which the water forms the continuous phase.

(iii) treating the emulsion obtained in (ii) at elevated temperature with stirring,

(iv) adding at least one, optionally partially blocked, polyisocyanate and at least one compound comprising at least two groups having an 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 binder, defoamer, surface-active reagent and / or a thickener, and

(vii) optionally at least partially removing the water.

If the lipophilic compound is present as a solid at room temperature, step (i) is preferably carried out at temperatures above room temperature, particularly preferably at temperatures above the melting point of the lipophilic compound (s). Under these conditions, an emulsion can form, in particular an oil-in-water emulsion, in which the water forms the continuous phase and the lipophilic compound (s) together with at least part of the monomer forms the disperse phase. The protective colloid stabilizes the emulsion. The stabilization of the emulsion can be further improved by adding surface-active reagents become. Protective colloids and surface-active reagents are as defined above and are preferably used in the corresponding amounts.

Preferred polymerization initiators are radical initiators, in particular a peroxide, an azo compound, a persulfate

Hydroperoxide and / or a redox initiator or mixtures thereof. The decomposition temperature of the polymerization initiators is preferably above the melting point of the lipophilic compound, in particular up to 50 ° C. above the melting point of the lipophilic compound. Suitable initiators are azo compounds, such as, for example, 2,2'-azobis- (2-amidinopropane) dihydrochloride, 2,2'-azobis- (A /, A / -dimethylene) isobutyramidine-dihydrochloride, 2- (carbamoylazo) isobutyronitrile, 4 , 4'-azobis (4-cyanovaleric acid), 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, and 2,2 ^, -azobis (2,4-dimethylvaleronitrile).

Suitable peroxide compounds are, for example, acetylacetone peroxide, methyl ethyl ketone peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-amyl perpivalate, tert-butyl perpivalate, tert-butyl perneohexanoate, tert-butyl perisobutyrate, tert-butyl per-2-ethylhexanoate, tert-butyl peranoate .-Butyl permaleate, tert-butyl perbenzoate, tert-butyl per-3,5,5-trimethylhexanoate and tert-amyl perneodecanoate, and

Sodium peroxodisulfate or potassium peroxodisulfate.

Particularly preferred initiators are 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride and 2,2'-azobis (2,4-dimethylvaleronitrile), whose 10-hour half-life in the temperature range from 30 to 100 ° C. The initiator can be used as a solid or solution. The polymerization initiators are usually used in amounts of 0.01 to 5% by weight, preferably 0.1 to 3.5% by weight, based on the total mass of the monomers having at least one ethylenically unsaturated group. The chain length of the polymers obtainable from monomers with at least one ethylenically unsaturated group can be controlled via chain regulators. Such chain regulators are known to the person skilled in the art. Preferred chain regulators are sulfur-containing compounds, in particular thiols, in particular lauryl mercaptan or ethylhexyl thioglycolate. The chain regulator is typically used in amounts of 0 to 4% by weight, more preferably 0.01 to 3% by weight, based on the total mass of the monomers with at least one ethylenically unsaturated group. After step (ii), the mixture is further emulsified under shear forces, in particular using a homogenizer, for example Ultra-Turrax® or Dispax®. The average droplet size (D50) of the disperse phase determined by means of light radiation is preferably from 0.1 to 100 pm, more preferably 0.5 to 80 pm, even more preferably 1 to 75 pm.

The emulsion obtained in step (ii) is then treated in step (iii) at elevated temperature, preferably at 25 to 100 ° C, more preferably at 50 to 100 ° C, with stirring. Treatment step (iii) usually lasts 0.5 to 8 hours, preferably 1 to 8 hours, more preferably 3 to 4 hours. After step (iii), 90 to 100% of the monomers are preferably reacted with at least one ethylenically unsaturated group.

Step (ii) and step (iii) are preferably carried out under a protective gas atmosphere, in particular under nitrogen or argon.

The radical polymerization causes a polymer to form in situ at the interface between the disperse phase and the continuous phase. This preferably results in spherical or ellipsoidal particles from cores which are surrounded by the layer close to the core. The particles so obtained have preferably a diameter D50 of 0.1 to 100 miti, preferably 0.5 to 80 mhh, more preferably 1 to 75 miti.

In step (iv), at least one - optionally partially blocked - polyisocyanate and at least one compound comprising at least two groups having an NCO-reactive hydrogen atom are added to the particles from step (iii) dispersed in the continuous phase. If appropriate, at least one compound comprising at least one functional group and an NCO-reactive hydrogen atom is added in this step. The latter compound is added in particular if a functional layer remote from the core is to be obtained. Alternatively, the polyisocyanate may already contain at least one functional group. Step (iv) usually takes place at temperatures of 25 to 100 ° C., preferably 50 to 100 ° C.

In step (iv), the optionally partially blocked polyisocyanate orients itself to the layer close to the core surrounding the core. Subsequent addition of the compound comprising at least two groups with an NCO-reactive hydrogen atom forms a layer remote from the core on the layer close to the core.

In step (v), the mixture obtained in step (iv) is optionally thermally treated at elevated temperature. Step (v) - if carried out - is preferably carried out at temperatures from 25 to 100 ° C., preferably 30 to 90 ° C. The reaction time is preferably 0.25 to 4 hours. Under these

Conditions are preferably 90 to 100%, more preferably 95 to 100% of all NCO groups implemented.

In a preferred embodiment, there is no chemical reaction between the layer close to the core and the layer remote from the core, which may lead to leads to a covalent connection of the near-core and distant layers.

After the reaction in step (iv) or (v), auxiliaries such as binders, defoamers, surface-active reagents and / or thickeners can optionally be added.

After step (iv) or step (v), a composition according to the invention comprising the core-shell particles according to the invention and water is obtained. The composition obtained forms a stable dispersion. The core-shell particles therein have a diameter D50 of 0.1 to 100 miti, preferably 0.5 to 80 miti, more preferably 1 to 75 miti. After step (vi) it may be possible to equalize the particle size distribution via filtration steps.

The core-shell particles can optionally be isolated in step (vii) by the processes known to the person skilled in the art by at least partially removing the water. Preferred processes are centrifugation, filtration, distillation and / or spray drying. Isolated core-shell particles can, for example, be incorporated into a preparation as a slurry or powder. In another aspect, the present invention is directed to core-shell particles obtainable by the method described above.

The core-shell particles and compositions of the invention can be used in a variety of technical fields. For example, they can be used to functionalize fabrics, in particular fibers, textile fabrics, paints, varnishes, building materials, Plastics and / or plastic foams are used. One aspect of the present invention is therefore the use of the core-shell particles according to the invention or the composition according to the invention for the functionalization of flat structures, in particular fibers, textile flat fabrics, building materials, plastics or plastic foams, for example polyurethane, polystyrene, latex and melamine resin foams, Paints and varnishes.

Textiles are to be understood in particular as fibers or textile fabrics, such as textile fabrics, nonwovens (for example nonwovens or filters). For the functionalization of textile fibers, the core-shell particles can be added to a melt or in the form of an aqueous dispersion of the fiber matrix and used in a spinning process, for example in a melt spinning process or a wet spinning process.

“Fibers” mean natural fibers as well as synthetic fibers. "Natural fibers" preferably contain cotton, wool and / or silk. “Synthetic fibers” or “synthetic fibers” are produced synthetically from natural and / or synthetic polymers and preferably contain polyester, polyolefin, for example preferably polyethylene or polypropylene, more preferably polypropylene, polyamide, polyaramide, such as Kevlar® and Nomex®, polyacrylonitrile, Spandex and / or viscose. Textiles are to be understood in particular as fibers or textile fabrics. A "textile" is made of several fibers and is preferably linear or flat. "Line-shaped textile" is understood to mean, for example, a yarn, a thread or a rope. "Flat textiles" are preferably nonwovens, felts, fabrics, knitted fabrics and braids. Textiles can contain natural fibers and synthetic fibers or mixtures thereof. Another object of the present invention is a method for finishing fabrics, in particular textiles, comprising the steps

(a) providing the core-shell particles or compositions according to the invention,

(b) applying the core-shell particles or compositions according to the invention to a fabric; and

(c) thermal treatment of the fabric. The application of the core-shell particles or the composition e.g. by impregnating the textile, in particular the textile fabric, in step (b), there are generally overlaps of 0.1 to 3% by weight, preferably 1 to 8% by weight, particularly preferably 1 to 6.5% by weight. % Solids based on the weight of the textile to be treated. For this purpose, an aqueous composition is usually prepared in the desired concentration. The concentration of the composition is chosen so that the desired order results in each case. Further preparation agents can be added to the composition. Additional preparation agents include chemicals for crease-free finishing (e.g. methylol compounds from

Dihydroxyethylene urea or methylol melamine ether with different degrees of methylolation), flame retardants or softeners.

The composition is applied to the fabric, in particular the textile fabric, using conventional methods known to those skilled in the art, for example by forced application, exhaust process, spraying, impregnation, splashing, printing, coating, for example by transfer coating or rotary printing, or padding. In a preferred embodiment, the composition according to the invention is applied to the foulard by soaking the fabric and then squeezing it off. The drying and thermal treatment of the fabric obtained in step (b) is preferably carried out in step (c) at temperatures between 130 to 170 ° C. The treatment is preferably carried out in the stenter dryer. At the specified temperatures, the blocking groups, if present, also split off and evaporate. The resulting reactive isocyanate group reacts with isocyanate-reactive hydrogen atoms of the fabric and / or the other components, so that the core-shell particles are covalently bound to the fabric. The thermal treatment of the fabric is preferably carried out in 0.5 to 10 minutes, particularly preferably in 1 to 5 minutes. The duration of the thermal treatment also depends on the temperatures used.

The present invention therefore also relates to fabrics, in particular fibers or textile fabrics comprising the core-shell particles according to the invention or the composition according to the invention.

The core-shell particles or the composition according to the present invention can also be used in building materials, for fixing polymeric moldings and / or in polymeric coating compositions. The core-shell particles according to the invention are preferably used as a functional additive in mineral coating compositions such as plaster or in wall paints. The core-shell particles according to the invention are particularly suitable for the functionalization of polymer moldings and polymeric coating compositions made of thermoplastic and thermosetting plastics, the core-shell particles of which are not destroyed during processing. Examples of thermoplastic and thermosetting plastics are epoxy resins, urea resins,

Melamine resins, polyurethane and silicone resins, but also varnishes.

It has been found that the core-shell particles according to the invention can be functionalized easily and variably without the primary properties of the core-shell particles, such as e.g. To influence permeability and mechanical stability. According to the invention, the permeability and mechanical stability of the particles are variably adjusted via the layer close to the core. The layer close to the core is preferably made of a material that is inert to the core. The layer remote from the core can be variably functionalized.

Since there are preferably no interactions, in particular no covalent interactions, between the near-core layer and the remote core layer, the non-core layer does not influence the property profile of the near-core layer. The core-shell particles according to the invention and the method according to the invention also enable a modular system in which the cores coated with the layer close to the core are provided in stock and can then be modified as desired with different functional groups via the layer remote from the core without the Change the properties of the core (primary particle) surrounded by the layer close to the core.

The present invention is explained in more detail by means of examples, the invention being not restricted to these examples. used material

Embodiment - 1st

Partial blocking of isocyanate groups

40.00 g of isopropyl acetate and 10.00 g (44.98 mmol) of isophorone diisocyanate (IPDI) were placed in a round bottom flask under a nitrogen atmosphere. 2.60 g (27.05 mmol) of 3,5-dimethylpyrazole were added with stirring and mixed until a homogeneous solution was obtained. The mixture was heated to 40 ° C. and, after reaching a constant NCO content, the solvent was then removed under vacuum distillation.

Production of the core-shell particles water phase:

530.75 g water

80.20 g polyvinyl alcohol solution (12.5% by weight, 88% saponified, average molecular weight 128000 g / mol) Oil phase:

286.22 g Parafol 18-97

37.50 g methyl methacrylate

16.55 g Laromer TMPTA

0.49 g lauryl mercaptan

1.00 g WAKO V-65B

Aqueous initiator:

4.97 g water

0.99 g WAKO VA-044

isocyanate:

12.71 g 30% partially blocked Desmodur I

polyamine:

6.23 g 10% heavy polyamine XE solution Stabilization:

2.95 g Lutensit A-BO

3.00 g Strodex PK-90

3.84 g Silfoam SE 47

10.97 g of Rohagit SD 15

1.63 g sodium hydroxide solution (50%)

Water and the protective colloid were placed in a beaker and heated to 40 ° C. with stirring. The oil phase was melted and premixed separately and then introduced into the water phase with stirring. The emulsion was then sheared for 5 minutes using a rotor-stator homogenizer. The warm emulsion was transferred to a flask, temperature-controlled at 40 ° C., constantly stirred using a propeller stirrer and the reaction mixture was flushed with nitrogen. After replacing the atmosphere with nitrogen, the reaction vessel was closed with a pressure equalization and heated to 60 ° C. with stirring. Maintained 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 the mixture was stirred again for 60 minutes. The partially blocked polyisocyanate was added dropwise to this suspension and stirred in. The polyamine was then added dropwise and the temperature increased to 80 ° C. After a reaction time of 2 h, the dispersion was cooled to room temperature, mixed with emulsifiers, defoamers and thickeners and adjusted to pH 8.5 with sodium hydroxide solution. A dispersion with a solids content of approximately 34% was obtained.

Embodiment - 2nd

Partial blocking of isocyanate groups

40.00 g of isopropyl acetate and 12.00 g (44.98 mmol) of isophorone diisocyanate (IPDI) were placed in a round bottom flask under a nitrogen atmosphere. With stirring, 10.80 g (10.80 mmol) of Jeffamine M1000 were added and mixed until a homogeneous solution was obtained. The mixture was heated to 50 ° C. and, after reaching a constant NCO content, the solvent was then removed under vacuum distillation. Production of the core-shell particles

Water phase:

488.93 g water

71, 17 g of polyvinyl alcohol solution (12.5% by weight, 88% saponified, average molecular weight 128000 g / mol)

Oil phase:

279.39 g Parafol 18-97

39.89 g methyl methacrylate

17.66 g Laromer TMPTA

0.46 g lauryl mercaptan

0.92 g WAKO V-65B

Aqueous initiator:

4.57 g water

0.96 g WAKO VA-044

isocyanate:

20.38 g 10% partially functionalized Desmodur I polyamine:

3.67 g 10% heavy polyamine XE solution

Stabilization:

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 of Rohagit SD 15

1.50 g sodium hydroxide solution (50%) The sample was produced analogously to Example 1. In addition, a binder was added to the dispersion. A dispersion with a solids content of approximately 40% was obtained. Embodiment - 3rd

Preparation of the dispersion with a reduced crosslinker content in the near-core water phase layer:

439.64 g water

78.65 g polyvinyl alcohol solution (12.5% by weight, 88% saponified, average molecular weight 128000 g / mol)

Oil phase:

195.53 g Parafol 18-97

35.63 g methyl methacrylate

11.50 g Laromer TMPTA

0.41 g lauryl mercaptan

0.83 g WAKO V-65B

Aqueous initiator:

4.11 g water

0.86 g WAKO VA-044

isocyanate:

8.77 g Desmodur I

polyamine:

6.74 g 10% heavy polyamine XE solution Stabilization:

199.06 g Plextol R272

2.32 g Lutensit A-BO

2.34 g Strodex PK-90

3.18 g of Silfoam SE 47

9.08 g of Rohagit SD 15

1.35 g sodium hydroxide solution (50%)

The sample was produced analogously to Example 1. A dispersion with a solids content of approximately 36% was obtained.

The permeability of the core-shell particles was determined via the loss of latent heat by means of dynamic differential calorimetry (English differential scanning calorimetry - DSC). For this purpose, a latent heat storage material was wrapped and the dispersion was diluted on a textile fabric.

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 enthalpy of fusion between air-dried and heat-dried sample gives the tightness. In order to understand the influence of the multiple layers that lead to the overall structure of the shell, this DSC method was carried out for the same sample at different times in the process. For example, the permeability was determined after the formation of the polyacrylate layer close to the core and then again after the polyurethane layer remote from the core had been put on.

The results show that the permeability is determined by the layer close to the core and is not or only slightly influenced by the layer remote from the core. The core remote layer is primarily responsible for the functionalization.

Exemplary embodiment - 4 Exemplary embodiment 4 - as described in exemplary embodiment 1 - was carried out, the partially blocked isocyanate being varied as follows.

Functionalization with Cationically Emulsifying Groups 75.00 g of isopropyl acetate and 12.00 g (53.981 mmol) of isophorone diisocyanate (IPDI) were placed in a round bottom flask under a nitrogen atmosphere. 0.962 g (10.796 mmol) of N, N-dimethylaminoethanol and 0.008 g (0.0071 mmol) of 1,4-diazabicyclo [2.2.2] octane (DABCO) were added with stirring and mixed until a homogeneous solution was obtained. The mixture was heated to 50 ° C. and then freed from the solvent under vacuum distillation.

The exact composition is given in Table 1. Embodiment - 5th

Exemplary embodiment 5 was carried out as described in exemplary embodiment 1, the oil phase being premixed without an acrylate crosslinker. The exact composition is given in Table 1. Sufficient tightness of the layer close to the core cannot be guaranteed without acrylate crosslinker.

Embodiment - 6th

Exemplary embodiment 6 was carried out as described in exemplary embodiment 1, the partially blocked isocyanate being varied as follows. Functionalization with radiation-crosslinkable groups

75.00 g of isopropyl acetate and 12.00 g (53.981 mmol) of isophorone diisocyanate (IPDI) were placed in a round bottom flask under a nitrogen atmosphere. With stirring, 2.507 g (21.592 mmol) of 2-hydroxyethyl acrylate and 0.024 g (0.0213 mmol) of 1,4-diazabicyclo [2.2.2] octane (DABCO) were added and mixed until a homogeneous solution was obtained. The mixture was heated to 50 ° C. and then freed from the solvent under vacuum distillation. The exact composition is given in Table 1. Embodiment - 7th

Production of the core-shell particles Water and the protective colloid were placed in a beaker. The oil phase was separately premixed and then introduced into the water phase with stirring. The emulsion was then sheared for 5 minutes using a rotor-stator homogenizer. The emulsion was transferred to a flask, constantly stirred with a propeller stirrer, and the reaction mixture was flushed with nitrogen. After replacing the atmosphere with nitrogen, the reaction vessel was closed with a pressure equalization and heated to 60 ° C. with stirring. Maintained 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 the mixture was stirred again for 60 minutes.

The polyisocyanate was added dropwise to this suspension and stirred in. The polyamine was then added dropwise and the temperature increased to 80 ° C. After a reaction time of 2 h, the dispersion was cooled to room temperature, mixed with emulsifiers, defoamers and thickeners and adjusted to pH 8.5 with sodium hydroxide solution.

The exact composition is given in Table 1.

Comparative Examples 1 and 2

The following comparative examples are produced analogously to example 1, the synthesis ending before the addition of an isocyanate component, since the comparative particles are single-walled core-shell particles is. The compositions of the comparative examples are shown in Table 1.

Water and the protective colloid were placed in a beaker and heated to 40 ° C. with stirring. The oil phase was melted and premixed separately and then introduced into the water phase with stirring. The emulsion was then sheared for 5 minutes using a rotor-stator homogenizer. The warm emulsion was transferred to a flask, temperature-controlled at 40 ° C., constantly stirred with a propeller stirrer and flushed with nitrogen. After replacing the atmosphere with nitrogen, the reaction vessel was closed with a pressure equalization and heated to 60 ° C. with stirring. Maintained 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 the mixture was stirred again for 60 minutes. After this time, the dispersion was cooled to room temperature, mixed with emulsifiers, defoamers and thickeners and adjusted to pH 8.5 with sodium hydroxide solution.

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

Table 1: Composition of Examples 4-7 according to the invention and of Comparative Examples 1 and 2

-P _*

with 10 mol% dimethyaminoethanol

Methyl methacrylate Strodex PK-90 hexylene diglycol

partially blocked Desmodur I

b Parafol 18-97 ⁹ Desmodur I Arquad 2.10-50 q DISPERBYK 192 c 1:10 mixture of Exxsol D100 ULA with 20 mol% 2-hydroxyethyl acrylate

Rohagit SD 15

and C.l. Pigment Black 7 partially blocked Desmodur I

d Visiomer MPEG 750 MA Lutensit A-BO BYK 7420 ES

A /, A / -dimethylaminoethyl methacrylate Disponil A 3065 sodium hydroxide solution 50%

Table 2: Type of functionalization and permeability of the core-shell particles according to the invention and the comparison particles

The following points are the subject of the present invention

1. comprising core-shell particles

(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 remote from the core.

2. Core-shell particles according to item 1, the layer remote from the core being arranged on the layer close to the core. 3. Core-shell particles according to item 1 or 2, the layer close to the core surrounding the core.

4. Core-shell particles according to one of the preceding points, the core being solid at room temperature (20 ° C.).

5. Core-shell particles according to one of the items 1-3, the core being liquid at room temperature (20 ° C.), preferably in the form of a solution, emulsion or suspension, or solid, preferably in the form of a powder. 6. Core-shell particles according to one of the preceding points, the lipophilic compound having a water solubility of <10 g / l, preferably <5 g / l, more preferably <3 g / l at 20 ° C.

7. core-shell particles according to one of the preceding points, the lipophilic compound being selected from pigments, dyes,

Fragrances, cosmetics, flame retardants,

Latent heat storage materials, biocides, catalysts, adhesives, adhesive components, water repellents, polymer building blocks, isocyanates, oils, silicone oils, waxes or mixtures thereof. 8. Core-shell particles according to item 7, the latent heat storage material being selected from

Saturated or unsaturated, linear, branched or cyclic hydrocarbon, preferably saturated or unsaturated, linear, branched or cyclic Ci ₀ -C ₄₀ -

Hydrocarbon, more preferably linear or cyclic Ci ₀ - C ₄ o-alkane and aromatic C6-C20 hydrocarbon, most preferably n-hexadecane, n-heptadecane, n-octadecane, n-nonadecane, n-eicosane, cyclohexane, cyclooctane, cyclodecane , Benzene, naphthalene, biphenyl,

• saturated or unsaturated C ₆ -C ₃ o fatty acid, saturated or unsaturated C ₆ -C ₃ o fatty alcohol and saturated or unsaturated C ₆ -C ₃₀ fatty acid Ci-Cio-alkyl ester, preferably lauric, stearic , Oleic or behenic acid, lauryl, stearyl or oleyl alcohol, propyl palmitate, methyl stearate or methyl palmitate, and

• Mixtures of these.

9. Core-shell particles according to item 7, the dye being selected from reactive dye, such as e.g. C.I. Reactive Red 2, disperse dye, e.g. C.I. Disperse Yellow 42, acid dye, such as e.g. C.I. Acid Blue 1, or basic dye, e.g. C.I. Basic Violet 3, and mixtures thereof. 10. Core-shell particles according to item 7, the pigments being selected from organic or inorganic pigments, in particular color pigments, magnetic pigments, and mixtures thereof.

11. Core-shell particles according to item 7, the fragrances being selected from synthetic or natural fragrances. Core-shell particles according to item 7, the flame retardants being halogenated flame retardants, preferably tetrabromobisphenol A (TBA), bromopolystyrene, chlorinated paraffins and dibromoneopentylglycol (DBNPG), phosphate-containing flame retardants, preferably organic phosphoric acid esters or cyclic phosphate derivatives, or mixtures thereof. Core-shell particles according to item 7, the biocides being selected from pesticides, fungicides, herbicides, insecticides, algicides, molluscicides, acaricides, rodenticides, bactericides, antibiotics,

Antiseptics, antibacterial, antiviral, antifungal, antiparasitic biocides and mixtures thereof. Core-shell particles according to item 7, the cosmetics being selected from anti-wrinkle agents, free radical scavengers, self-tanning agents and massage oils. Core-shell particles according to one of the preceding points, the layer close to the core being obtainable by polymerizing at least one monomer having at least one ethylenically unsaturated group. Core-shell particles according to item 15, wherein the monomer with at least one ethylenically unsaturated group has no nucleophilic group with an active hydrogen atom, in particular no NCO-reactive hydrogen. Core-shell particles according to item 15 or 16, the layer close to the core being obtainable by radical polymerization. Core-shell particles according to one of items 15-17, where the ethylenically unsaturated group is a vinyl, vinyl ether, acrylic, Ci ₆ -

Alkylacryl, allyl and / or allyl ether group. Core-shell particles according to one of items 15-18, the monomer having at least one ethylenically unsaturated group having the structure:

With

B - R ⁵ - R ⁶

R ¹ = -CrC ₆ -alkyl or -H, preferably -H or -CH ₃ ,

R ² = linear or branched CrC ₂₄ alkyl,

R ³ = linear or branched CrC ₂₄ alkylene,

R ⁷ = polyester, in particular obtainable by reaction of C1-C6 alkyl diols and Ci-C ₆ alkyldicarboxylic acids, such as diesters, eg malonic, Oxalsäureester, Bernsteinsäureester, glutarate or adipate and

n = 0-20 core-shell particles according to one of the items 15-19, the molar ratio of monomers with one ethylenically unsaturated group to monomers with several ethylenically unsaturated groups being 2 to 40, preferably 4 to 30. Core-shell particles according to one of the preceding points, wherein the core-remote layer contains at least one urethane, allophanate, carbodiimide, isocyanurate, biuret, uretdione, urea, iminooxadiazinedione or uretonimine group. Core-shell particles according to one of the preceding points, the layer remote from the core being an addition product of at least one polyisocyanate and at least one compound comprising at least two groups having an NCO-reactive hydrogen atom, preferably hydroxy,

Amino, carboxylic acid, urethane and / or urea groups. 23 core-shell particles according to item 22, wherein the polyisocyanate is aromatic, alicyclic or aliphatic preferably selected from methylene diphenyl isocyanate (MDI), polymeric MDI, tolylene diisocyanate (TDI), ^{triphenylmethane-4,4,,} "-triisocyanate 4, 2 , 4,6-triisocyanatetoluene,

Isophorone diisocyanate (IPDI), 4,4'-methylenebis (cyclohexyl isocyanate) (H12MDI), methyl 2,4-cyclohexane diisocyanate, 1, 3,5-

Triisocyanate cyclohexane, 1, 3,5-trimethyl isocyanate cyclohexane,

T rimethylene diisocyanate, 1, 4,8-triisocyanatoctane, 1, 3,6-triisocyanate hexane, hexamethylene diisocyanate, xylene diisocyanate (XDI), biurethane and isocyanurate polyisocyanates.

24. Core-shell particles according to item 22 or 23, the NCO groups of the polyisocyanate being partially blocked.

25. Core-shell particles according to item 23, 0.1 to 80%, preferably 1 to 50%, more preferably 1 to 30% of the NCO groups of the polyisocyanate being blocked. 26. Core-shell particles according to one of the items 22-25, the

Compound comprising at least two groups with an NCO-reactive hydrogen atom is selected from polyols, polyester polyols, polyether polyols, polyureas, amino- and / or hydroxy-functionalized homo- or copolymers, polyamines and hydroxy-functional amines.

27. Core-shell particles according to one of the items 22-26, the molar ratio of NCO groups to groups having an NCO-reactive hydrogen atom between 1 and 100, preferably 2 and 100, more preferably 5 and 100 and even more preferably 5 and 80 lies. 28. Core-shell particles according to one of the preceding points, the layer remote from the core having at least one functional group, preferably an anionic, cationic or non-ionic group. 29. Core-shell particles according to item 28, the anionic group comprising at least one carboxylate, phosphate, phosphonate, sulfate or sulfonate group and preferably having the formula (I):

-L-X

Formula (I)

in which

X is S0 ₃ , S0 ₄ , COO, P0 ₄ ² or P0 ₃ ² , and

L is linear or branched, saturated or unsaturated C1-C-10 alkylene, which is optionally substituted with -OH.

30. Core-shell particles according to 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)

in which

Y is NHR ₈ Rg ⁺ or NR ₈ RgRio ⁺ ,

R ₈ , Rg and R _{10 are} each independently H or linear or branched, saturated or unsaturated, C1-C1 o-alkyl, which is optionally substituted by OH and / or COOH and

L is as defined above.

31. Core-shell particles according to item 28, the nonionic functional group being a polyalkylene oxide, preferably polyethylene oxide and / or

Polypropylene oxide. Core-shell particles according to one of the items 28-31, the functional group being bound to the layer remote from the core via a urethane group. Core-shell particles according to 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 reacted with a compound comprising at least one functional group , Composition comprising at least one core-shell particle according to one of items 1-33. Composition according to item 34, the composition comprising water. Composition according to item 34 or 35, wherein the composition further contains at least one surface-active reagent, in particular surfactant, a binder, a defoamer, a protective colloid and / or a thickener. Composition according to item 36, wherein the binder is a polymer with a glass transition temperature in the range from -45 to +45 ° C, in particular a polymer based on (meth) acrylic acid ester, styrene, isoprene, butadiene, vinyl acetate, and / or isocyanate. Composition according to one of items 34-37, the

Defoamer is a mineral oil, a silica or a silicone-containing defoamer. Composition according to one of items 34-38, the core-shell particles according to items 1-33 10 to 55% by weight, preferably 15 to 45% by weight, particularly preferably 20 to 37.5% by weight based on the total mass of the composition. A method for producing a core-shell particle according to one of items 1-33 or a composition according to one of items 34-39, comprising the steps:

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,

- if necessary, at least one chain regulator,

to form an emulsion in which the water forms the continuous phase.

(v) optionally treating the mixture obtained in (iv) at elevated temperature, (vi) optionally adding at least one binder, defoamer, surface-active reagent and / or a thickener, and

(vii) optionally at least partially removing the water.

41. The method according to item 40, wherein the disperse phase has a diameter D ₅₀ of 0.1 to 100 μm, preferably 0.5 to 80 μm and more preferably 1 to 75 μm. 42. The method according to item 40 or 41, the protective colloid being selected from water-soluble polymer, in particular polyvinyl alcohol, cellulose derivatives, in particular hydroxyalkyl cellulose or carboxyalkyl cellulose, gum arabic, polyacrylic acid, polyacrylamides, polyvinylpyrrolidone and / or maleic anhydride copolymers.

43. The method according to any one of items 40-42, wherein the surface-active reagent is selected from anionic, cationic or non-ionic surfactants.

44. The method according to any one of items 40-43, wherein the polymerization initiator is a radical initiator, in particular a peroxide, an azo compound, a persulfate, a hydroperoxide and / or a redox initiator, or mixtures thereof.

45. The method according to any one of items 40-44, wherein the chain regulator is a sulfur-containing compound, in particular lauryl mercaptan or ethylhexyl thioglycolate. 46. The method according to any one of items 40-45, wherein the solubilizer is mono-, di- or triglyceride, mineral oil, silicone oil, castor oil and / or isopropyl myristate. 47. The method according to any one of items 40-46, wherein step (iii) in

Temperatures of 25 to 100 ° C, preferably 50 to 100 ° C, takes place.

48. The method according to any one of items 40-47, wherein step (iv) in

Temperatures of 25 to 100 ° C, preferably 50 to 100 ° C takes place.

49. The method according to any one of items 40-48, wherein step (v) is preferably carried out for 0.25 to 4 hours, preferably at temperatures from 25 to 100 ° C., preferably 30 to 90 ° C. 50. Core-shell particles obtainable by a process according to the

Points 40-49.

51. Use of the core-shell particles according to one of items 1-33 or 50 or the composition according to one of items 34-39 for the functionalization of fabrics, in particular fibers, textile fabrics, building materials, plastics or plastic foams, paints and varnishes.

52. A method for finishing fabrics, in particular textiles, comprising the steps

(a) providing the core-shell particles according to one of items 1-33 or 50 or the composition according to one of items 34-39,

(b) applying the core-shell particles or composition to a sheet; and

(c) thermal treatment of the fabric. Flat structures, in particular fibers or textile flat structures, comprising core-shell particles according to one of items 1-33 or 50 or the composition according to one of items 34-39.

Claims

Expectations

1. comprising core-shell particles

(a) a core comprising at least one lipophilic compound and

2. Core-shell particles according to claim 1, wherein the layer remote from the core is arranged on the layer close to the core.

3. core-shell particles according to one of the preceding claims, wherein the lipophilic compound is selected from pigments, dyes, fragrances, cosmetics, flame retardants,

Latent heat storage materials, biocides, catalysts, adhesives, adhesive components, water repellents, polymer building blocks, isocyanates, oils, silicone oils, waxes or mixtures thereof.

4. Core-shell particles according to one of the preceding claims, wherein the layer close to the core is obtainable by polymerizing at least one monomer with at least one ethylenically unsaturated group, preferably with the structure:

B - R ⁵ - R ⁶ R ¹ = -CrC ₆ alkyl or -H, preferably -H or -CH ₃ ,

R ² = linear or branched Ci-C ₂₄ alkyl

R = linear or branched CrC2 ₄ alkylene,

R ⁷ = polyester, in particular obtainable by reaction of CrC ₆ alkyl diols and CrC ₆ alkyl dicarboxylic acids, such as diesters, for example Malonic acid esters, oxalic acid esters, succinic acid esters, glutaric acid esters or adipic acid esters and

n = 0-20

5. Core-shell particles according to one of the preceding claims, wherein the core-remote layer contains at least one urethane, allophanate, carbodiimide, isocyanurate, biuret, uretdione, urea, iminooxadiazinedione or uretonimine group.

6. core-shell particles according to any one of the preceding claims, wherein the core-remote layer 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. core-shell particles according to claim 6, wherein the NCO groups of the polyisocyanate are partially blocked, in particular 0.1 to 80%, preferably 1 to 50%, more preferably 1 to 30% of the NCO groups of the polyisocyanate blocked are.

8. Core-shell particles according to one of the preceding claims, wherein the core-remote layer has at least one functional group, preferably an anionic, cationic or non-ionic group, which is preferably bonded to the core-remote layer via a urethane group.

9. A composition comprising at least one core-shell particle according to any one of claims 1-8.

10. The composition of claim 9, wherein the composition comprises water and optionally further at least one surfactant Reagent, in particular surfactant, contains a binder, a defoamer, a protective colloid and / or a thickener.

11. A method for producing a core-shell particle according to one of claims 1-8 or a composition according to one of claims 9 or 10, comprising the steps:

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,

- if necessary, at least one chain regulator,

to form an emulsion in which the water forms the continuous phase.

(vii) optionally at least partially removing the water.

12. core-shell particles obtainable by a process according to claim 1 1.

13. Use of the core-shell particles according to one of claims 1 -8 or 12 or the composition according to one of claims 9 or

10 for the functionalization of fabrics, in particular fibers, textile fabrics, building materials, plastics or plastic foams, paints and varnishes.

14. Process for finishing fabrics, in particular

Textiles, covering the steps

(a) providing the core-shell particles according to one of claims 1 -8 or 12 or the composition according to one of claims 9 or 10,

(b) applying the core-shell particles or composition to a

Fabric; and

(c) thermal treatment of the fabric.

15. Flat structures, in particular fibers or textile flat structures, comprising core-shell particles according to one of claims 1 -8 or 12 or the composition according to one of claims 9 or 10.