EP1794232A1

EP1794232A1 - Composition containing core-shell particles and production thereof

Info

Publication number: EP1794232A1
Application number: EP05786357A
Authority: EP
Inventors: Jochen Ebenhoch
Original assignee: Wacker Chemie AG
Current assignee: Wacker Chemie AG
Priority date: 2004-09-30
Filing date: 2005-09-29
Publication date: 2007-06-13
Also published as: DE102004047708A1; US20090197989A1; WO2006037559A1

Abstract

The invention relates to a composition containing: (A) core-shell particles consisting of an organopolysiloxane core, which have a crosslinked or uncrosslinked organopolymer shell and optionally have a crosslinked or uncrosslinked organopolymer core or mixtures thereof with any other siloxane-containing particles, and; (B) a reactive resin or a mixture consisting of different reactive resins.

Description

Core shell particle-containing composition and their

manufacturing

The invention relates to a core-shell particle-containing composition and a process for their preparation.

EP 0266513 Bl describes modified reaction resins, processes for their preparation and their use. It is limited to compositions which in addition to a reaction resin max. 2-50 wt.% Contain three-dimensionally crosslinked polyorganosiloxane rubbers having particle sizes of 0.01 to 50 microns in amounts of 2-50 wt.%, The properties of the composition described therein in terms of impact resistance and impact strength are insufficient.

The object of the invention is to improve the state of the art and to provide a composition with improved properties of impact resistance and impact resistance.

The invention relates to a composition comprising (A) core-shell particles of an organopolysiloxane core, which have a crosslinked or uncrosslinked organopolymer shell and optionally a crosslinked or uncrosslinked organopolymer core or mixtures thereof with any other siloxane-containing particles and (B) a reactive resin or a mixture of various reactive resins.

The silicone particles are preferably elastomeric particulate copolymers having a core-shell structure composed of a core a) consisting of an organosilicon polymer and an organopolymer shell c) or two shells b) and c), or a shell and an inner core, wherein the inner shell b) consists of an organosilicon polymer, wherein the copolymer is composed of a) 0.05 to 95 wt.%, Based on the total weight of the copolymer, of a core polymer of the general formulas

0-10 units of the general formula

[R ₃ Si0i / ₂ ] (1),

0 - 90 units of the general formula

^[ R ₂ ^S i ⁰ ₂ Z2 ^{] (} 2 ⁾ '

0 -100 units of the general formula

[RSiO _3/2 ] (3),

0 -50 units of the general formula

[SiO _4/2] ^<4> '

wherein the units (2) and (3) preferably together amount to at least 5% by weight, based on the silicone content,

b) 0 to 94.5% by weight, based on the total weight of the copolymer, of a polysiloxane shell of the general formulas

0-10 units of the general formula

^[ R ₃ SiO ₁₇₂ ] ⁽ D,

0 - 90 units of the general formula [R ₂ Si0 _{_2/2]} (2) '

0 -100 units of the general formula

[RSiO _3/2 ] (3),

0 -50 units of the general formula

[SiO _4/2 ] (4),

c) from 5 to 95% by weight, based on the total weight of the copolymer, of a shell or an inner core of organopolymers of mono- or polyolefinically unsaturated monomers, where R is hydrogen or identical or different monovalent SiC-bonded, optionally substituted C 1 to C

C] _8 ~ hydrocarbon radicals and the particles one

Particle size of 10 to 400 nm and a monomodal

Have particle size distribution with a polydispersity index of at most σ ₂ = 0.2.

Particulate copolymers consisting of a core a) and a shell c) are preferably composed of: a) 5 to 95% by weight, particularly preferably 20 to 80% by weight, based on the total weight of the copolymer, of a core polymer (R ₂ Si0 ₂ / ₂ ) _x . (RSiθ3 / ₂ ) _y . (SiO 4/2) z with x = 10 to 99.5 mol%, in particular 50 to 99 mol%; y = 0.5 to 95 mol%, especially

1 to 50 mol%; z = 0 to 30 mol%, especially 0 to 20 mol%; and c) 5 to 95% by weight, particularly preferably 20 to 80% by weight, based on the total weight of the copolymer, of a shell of organopolymers of monoolefinically unsaturated monomers, where R is identical or different monovalent alkyl or alkenyl radicals having 1 to 6 C atoms, aryl radicals or substituted hydrocarbon radicals. Particulate copolymers consisting of a core a), an inner shell b) and a shell c) are preferably composed of: a) 0.05 to 90% by weight, particularly preferably 0.1 to 35% by weight, based on the total weight of the copolymer

Core polymers (R'SiC> 3/2) y • (SiC> 4/2) _z ^mi ty = 50 to 100 Mo1% and z = 0 to 50 mol%, in particular 0 to 30 mol%, b) 0.5 to 94.5 wt .%, Particularly preferably 35 to 70 wt.%, Based on the total weight of the copolymer, a polydialkylsiloxane shell of (R'2S1O2 / 2) n ~ units c) 5 to 95 wt.%, Particularly preferably 30 to 70 wt. %, based on the total weight of the copolymer, of a shell of organopolymers of monoolefinically unsaturated monomers, where R 'is preferably identical or different monovalent alkyl or alkenyl radicals having 1 to 18 C atoms, preferably 1 to 6 C atoms, aryl radicals or substituted hydrocarbon radicals.

The radicals R 'are preferably alkyl radicals, such as the methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, amyl, hexyl radical; Alkenyl radicals such as the vinyl and allyl radical and butenyl radical; Aryl radicals, such as the phenyl radical; or substituted hydrocarbon radicals. Examples of these are halogenated hydrocarbon radicals, such as the chloromethyl, 3-chloropropyl, 3-bromopropyl, 3,3,3-trifluoropropyl and 5,5,5,4,4,3,3-heptafluoropentyl radical, and the chlorophenyl radical rest; Mercaptoalkyl radicals such as 2-mercaptoethyl and 3-mercaptopropyl; Cyanoalkyl radicals such as the 2-cyanoethyl and 3-cyanopropyl radicals; Aminoalkyl radicals, such as the 3-aminopropyl radical; Acyloxyalkyl radicals such as 3-acryloxypropyl and 3-methacryloxypropyl; Hydroxyalkyl radicals, such as the hydroxypropyl radical.

Particularly preferred are the radicals methyl, ethyl, propyl, phenyl, vinyl, 3-methacryloxypropyl and 3-mercaptopropyl, wherein less than 30 mol% of the radicals in the siloxane polymer are vinyl, 3-methacryloxypropyl or 3-mercaptopropyl groups.

The organosilicon shell polymer b) preferably consists of dialkylsiloxane units (R'2SiC> 2/2) 'where R' is the

Meanings have methyl or ethyl.

As monomers for the organic polymer portion c) are preferably acrylic or methacrylic esters of aliphatic alcohols having 1 to 10 carbon atoms, acrylonitrile, styrene, p-methylstyrene, α-methylstyrene, vinyl acetate, vinyl propionate, maleimide, vinyl chloride, ethylene, butadiene, isoprene and chloroprene. Particularly preferred are styrene and acrylic esters and methacrylic acid esters of aliphatic alcohols having 1 to 4 carbon atoms, for example methyl (meth) acrylate, ethyl (meth) acrylate or butyl (meth) acrylate. Both homopolymers and copolymers of said monomers are suitable as the organic polymer fraction.

The finely divided elastomeric graft copolymers have an average particle size (diameter) of 10 to 400 nm, preferably from 30 to 350 nm, measured by the transmission electron microscope. The particle size distribution is very uniform, the graft copolymers are monomodal, that is, the particles have a maximum in the

Particle size distribution and a polydispersity factor o ^~ 2 of at most 0.2, measured by the transmission electron microscope.

The core shell particles are preferably prepared according to EP 492 376 A2 (Wacker-Chemie GmbH) and examples thereof.

The core shell particles are in the composition of the invention in amounts of from 5 to 95 wt.% Based on the Total weight of the composition, preferably 10 to 90 wt.%, Particularly preferably 20 to 60 wt.%.

The total content of all particles in the composition is 5 to 95% by weight, based on the total weight of the

Composition, preferably 5 to 90 wt.% And particularly preferably 10 to 80 wt.%.

The compositions of the invention may contain one or more types of different core shell particles as described above, differing in size or construction. Preferably, the compositions contain max. 3 different types of core shell particles.

The mixtures with any other siloxane-containing particles are to be understood as those which, in addition to the core shell particles described above, also contain one or more types of organopolysiloxane particles, as described, for example, in EP 744 432 A.

Preferably, the compositions contain max. 1 type of organopolysiloxane particles, as described above, and optionally particles as described in EP 0 266 513 Bl.

The composition according to the invention, wherein the core-shell particles, a core and optionally an inner core and a shell around the core and the silicone content of the core-shell particles between preferably 5 and 95 wt.%, Preferably 10 to 90 wt.%, Particularly preferably 20 to 90% by weight.

Particularly preferred core-shell particles contain a core of at least 20% by weight of a crosslinked silicone core and a

Bowl of max. 60% by weight of a grafted-on organopolymer. Particularly preferred organopolymers are polymers based on poly (alkyl) (meth) acrylates and their copolymers with other monomer building blocks.

The compositions may contain from 0.1% by weight to 99.9% by weight of core-shell particles, preferably between 5.0% by weight and 60% by weight and more preferably between 10.0% by weight and 50% wt.%.

In the composition according to the invention, the core-shell particles have an average diameter of preferably 5 to 400 nm, preferably 50 to 400 nm, particularly preferably 80 to 350 nm.

In the composition according to the invention is the

Silicone content of the core shell particles of organopolysiloxane

0-10 units of the general formula

[R ₃ Si0i / ₂ ] (1),

0 - 90 units of the general formula

[R ₂ Si0 _{_2/2]} (2)

0 -100 units of the general formula

[RSiO _3/2 ] < ³ >'

0 -50 units of the general formula

[SiO _4/2 ] < ⁴ >'together where the units (2) and (3) preferably together amount to at least 5% by weight, based on the silicone content, in which

R is hydrogen or identical or different monovalent SiC-bonded, optionally substituted C] _ to Cχ8 ~ hydrocarbon radicals.

Examples of unsubstituted radicals R are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl -, neo-pentyl, tert-pentyl radical, hexyl radicals, such as the n-hexyl radical, heptyl radicals, such as the n-heptyl radical, octyl radicals, such as the n-octyl radical and iso-

Octyl radicals, such as the 2, 2, 4-trimethylpentyl radical, nonyl radicals, such as the n-nonyl radical, decyl radicals, such as the n-decyl radical, dodecyl radicals, such as the n-dodecyl radical, octadecyl radicals, such as the n-octadecyl radical; Alkenyl radicals such as the vinyl, allyl, n-5-hexenyl, 4-vinylcyclohexyl and 3-norbornenyl radicals; Cycloalkyl radicals such as cyclopentyl, cyclohexyl, 4-ethylcyclohexyl, cycloheptyl radicals, norbornyl radicals and methylcyclohexyl radicals; Aryl radicals such as the phenyl, biphenylyl, naphthyl, anthryl and phenanthryl radicals; Alkaryl radicals, such as o-, m-, p-tolyl radicals, xylyl radicals and ethylphenyl radicals; Aralkyl radicals, like the

Benzyl, the alpha- and ß-phenylethyl, and the Fluorenylrest.

Examples of substituted hydrocarbon radicals as radical R are halogenated hydrocarbon radicals, such as the chloromethyl, 3-chloropropyl, 3-bromopropyl, 3, 3, 3-trifluoropropyl and 5, 5, 5, 4, 4, 3, 3-heptafluoropentyl radical and the chlorophenyl, dichlorophenyl and trifluorotolyl radicals; Mercaptoalkyl radicals, such as the 2-mercaptoethyl and 3-mercaptopropyl radical; Cyanoalkyl radicals, such as the 2-cyanoethyl and 3-cyanopropyl radicals; Aminoalkyl radicals such as the 3-aminopropyl, N- (2-aminoethyl) -3-aminopropyl and N- (2-aminoethyl) -3-amino- (2-methyl) propyl radical; Aminoaryl radicals, such as the aminophenyl radical; quaternary ammonium radicals; Acryloxyalkyl radicals such as 3-acryloxypropyl and 3-methacryloxypropyl; Hydroxyalkyl radicals, such as hydroxypropyl; phosphonic; Phosphonate radicals and sulfonate radicals, such as the 2-diethoxyphosphonatoethyl or the 3-sulfonato-propyl radical, dihydroxypropyl radical, hydroxyphenyl radical.

The radical R is preferably unsubstituted and substituted C 1 -C 4 -alkyl radicals, hydrogen and the

Phenyl, in particular the methyl, phenyl, vinyl, allyl, methacryloxypropyl, 3-chloropropyl, 3-mercaptopropyl, 3-aminopropyl and the (2-aminoethyl) -3-aminopropyl radical, hydrogen and quaternary ammonium radicals and the

Dihydroxypropyl, hydroxyphenyl and hydroxypropyl.

Suitable reaction resins according to the invention are all polymeric or oligomeric organic compounds which are provided with a sufficient number of suitable reactive groups for a curing reaction. It is irrelevant for the purpose of the invention, which crosslinking or

Hardening mechanism in a specific case expires. Therefore, as starting materials for the preparation of the modified reaction resins according to the invention are generally suitable all reactive resins that can be processed into thermosets, regardless of the particular crosslinking mechanism that takes place in the curing of the respective reaction resin.

In principle, the reaction resins which can be used as starting materials can be divided into three groups according to the type of crosslinking by addition, condensation or polymerization.

From the first group of the polyaddition networked

Reaction resins are preferably selected from one or more epoxy resins, urethane resins and / or air-drying alkyd resins as the starting material. Epoxy and urethane resins are generally by addition of stoichiometric amounts of a hydroxyl, amino, carboxyl or carboxylic anhydride groups containing Hardener crosslinked, wherein the curing reaction takes place by addition of the oxirane or isocyanate groups of the resin to the corresponding groups of the curing agent. In the case of epoxy resins, the so-called catalytic hardening by polyaddition of the oxirane groups themselves is also possible. Air-drying alkyd resins crosslink by autoxidation with atmospheric oxygen. Also addition-curing silicone resins are known, preferably those with the proviso that no further free silanes are included.

Examples of the second group of polycondensation-crosslinked reaction resins are condensation products of aldehydes, e.g. Formaldehyde, with amine group-containing aliphatic or aromatic compounds, e.g. Urea or melamine, or with aromatic compounds such as phenol, resorcinol, cresol, xylene, etc., furthermore furan resins, saturated polyester resins and condensation-curing silicone resins. Curing is usually carried out by increasing the temperature with elimination of water, low molecular weight alcohols or other low molecular weight compounds. Preference is given as starting material for the inventively modified

Reaction resins one or more phenolic resins, resorcinol resins and / or cresol resins, both resoles and novolacs, urea, formaldehyde and melamine formaldehyde precondensates, furan resins and saturated polyester resins and / or silicone resins selected.

From the third group of crosslinked by polymerization reaction resins are one or more homo- or copolymers of acrylic acid and / or methacrylic acid or its esters, further unsaturated polyester resins, vinyl ester resins and / or

Maleimide resins are preferred as starting resins for the invention modified reactive resins. These resins have polymerizable double bonds, through the polymerization or copolymerization, the three-dimensional crosslinking is effected. As starters serve to form free Radical-capable compounds, for example peroxides, peroxo compounds or azo-containing compounds. An initiation of the crosslinking reaction by high-energy radiation, such as UV or electron radiation, is possible.

Not only the abovementioned reaction resins, but also all others which are suitable for the production of thermosetting plastics, can be modified in the manner proposed according to the invention and can be obtained according to

Crosslinking and Hardening Thermosets with significantly improved resistance to breakage and impact, while leaving other essential properties, such as strength, heat distortion resistance and chemical resistance, which are characteristic of the thermosets, essentially unaffected. It does not matter if the reaction resins are solid or liquid at room temperature. The molecular weight of the reaction resins is practically irrelevant.

Compounds which are often used as hardener components for reactive resins, e.g. Phenolic resins or anhydride hardeners can also be considered as reactive resins.

Preference may be given as reactive resins in the composition according to the invention: epoxy resins, such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, novolak epoxy resins, epoxy resin containing biphenyl units, aliphatic or cycloaliphatic epoxy resins, such as 3,4-epoxycyclohexylmethyl-3 , 4-epoxycyclohexanecarboxylate. All epoxy resins may deviate more or less from the monomeric structure, depending on the degree of condensation in the preparation. Furthermore, acrylate resins can be used for the compositions according to the invention. Examples of preferred acrylate resins are triethylene glycol dimethacrylate, urethane dimethacrylate, Glycidyl. Also, phenolic resins, urethane resins, silicone resins, the latter preferably those with the proviso that no further free silanes are included.

The compositions according to the invention can be prepared, for example, by dispersion of isolated core-shell particles in the reactive resin. In this case, for example, the reactive resin is introduced and the core-shell particles mixed at temperatures between 20 ⁰ C and 250 ⁰ C, all known dispersing methods can be used. The

Use of shear energy in the dispersion is advantageous here. The quality of the dispersion can be checked after curing of the Raktivharzes example, by electron microscopy methods.

Another object of the invention is a process for preparing a composition according to the invention, wherein in an organic solution of the core-shell particles and optionally further siloxane-containing particles at least one reactive resin is added and the solvent is removed.

Preferably, the solution of the core-shell particles is prepared according to EP 100 32 820.

However, it can also be prepared by preparing a solution of the core shell particles with a solvent. Preferred are, for example, aliphatic or aromatic hydrocarbons, such as hexane, styrene, benzene, toluene, xylene, aliphatic or aromatic lactones, lactams, ketones, ketals, acetals, alcohols, thiols, amines, amides, esters, sulfones, but also low molecular weight polyorganosiloxanes, such as Hexamethyldisiloxane, octamethyltrisiloxane or cyclooctamethyltetrasiloxane. Particularly preferred are toluene, xylene, butyl acetate, ethyl acetate, methyl isobutyl ketone, methyl ethyl ketone, butyl methyl ether and hexamethyldisiloxane. Particular preference is also given to mixtures of these compounds.

It is also possible to subsequently modify the core shell particles chemically or physically after the preparation of the solution in the solvents mentioned. For example, after the preparation of the solution, polymer-analogous reactions, crosslinking, hydrolysis or other reactions can be carried out. Also, the attachment or incorporation of organic, organometallic or inorganic molecules, such as. Catalysts, cocatalysts or dyes are possible.

The mixture of solution and resin can be carried out in any order, if several types of core Schalepartikeln are present, preferably, the mixing process takes place at least 20 ⁰ C and up to the maximum boiling temperature of the solvent.

Optionally, additional solvent can be added after mixing. This may be advantageous when other interfering components, such as e.g. Water should be expelled.

Thereafter, it is possible to react the reactive resin with the core shell particles, for example by simply heating, irradiating or by adding auxiliaries which facilitate a reaction. As a result, the core shell particles are modified with the reactive resin or the reactive resin is modified with the core shell particles, which may be advantageous. Thereafter, the solvent is removed in one or more stages; For example, the solvent can be removed by membrane filtration, by molecular sieves, by freezing, by washing or extraction, or by drying. Preferably, the solvent is removed by drying, wherein the drying can take place at low temperatures in vacuo or at elevated temperatures with or without a vacuum. Preferably, the drying is carried out at higher temperatures, which is also known as distillation. The

Removal of the solvent may also be carried out by a combination of several different methods which are used sequentially.

Preferably, the solvent is removed by distillation in one or more steps. Optionally, it may be necessary to add a stabilizer for the reactive resin prior to distillation to prevent or at least suppress premature polymerization or crosslinking reaction.

It may be advantageous not to completely remove the solvent if the solvent itself is a reactive resin.

Examples:

example 1 Ia) 500 g of an aqueous dispersion of 100 nm core Schalepartikeln consisting of a silicone core and a grafted Acrylatcopolymerhülle, and a narrow particle size distribution and a solids content of 30 wt.% Is precipitated with 500 g of a 5% NaCl solution at room temperature. The precipitated core-shell material is pressed and treated for the preparation of an organosol with 850 g of toluene and dissolved for 24 hours at 60 ⁰ C with constant movement. The solution is cooled, filtered and the solids content determined (12.7 wt.%). Thereafter, this solution is mixed with 250 g of a cycloaliphatic epoxy resin and the solvent distilled off at slightly reduced pressure. This gave a flowable, viscous opalescent composition containing 34 wt% core-shell particles.

Ib) As in Example Ia, however, core shell particles having a mean diameter of 380 nm were used. The amount of cycloaliphatic epoxy resin was adjusted to result in a composition containing 10 wt.% Core shell particles in the resin.

Example 2

As in Example Ia, however, the aqueous dispersion of core-shell particles before precipitation with an aqueous

Dispersion mixed with silicone elastomer particles, which had a diameter of about 100 nm. The precipitated material contained 40% by weight silicone elastomer particles and 60% by weight core-shell particles. Thereafter, the same procedure was followed as in Example Ia. Instead of 250g epoxy, however, 350g

Triethylene glycol dimethacrylate used. A composition was obtained which contained 25% by weight of particles. Example 3

500 g of an aqueous dispersion of highly crosslinked, resinous, functional silicone particles was grafted with a copolymer of styrene, acrylic acid and methyl methacrylate and had an average particle size of 40 nm at a solids content of 18% by weight. There were 250g

Ethyl acetate added and heated to boiling temperature. Thereafter, 500 g of a 10% magnesium chloride solution was added over 30 minutes, and the mixture was cooled. The organic phase was separated and the solids content determined (28 wt.%). Thereafter, 150 g of a mixture of a bisphenol A diglycidylether and bisphenol F diglycidylether were added. Thereafter, the solvent was removed by distillation at boiling temperature. One received one

A composition containing 37% by weight of core shell particles dispersed in the resin mixture.

Example 4

As in Example 3, but a total of 3 aqueous dispersions of core Schalepartikeln with a solids content of 25-35 wt.% Was used, each having an average particle size of 50 nm, 150nm and 400nm and each separately with the extractant methyl isobutyl ketone were extracted. Each of 24-28% organosols were mixed together and mixed with an aromatic epoxy resin. The solvent was removed by distillation under reduced pressure to give a composition having 30 wt.% Core shell particles in 3 particle populations of different particle size.

Example 5 625 g of an organosol of core Schalepartikeln having an average particle size of lOOnm and a solids content of 30 wt.%, Dissolved in butyl methyl ether and prepared by the method of Example 3 was at room temperature with 375g of a commercially available composition (Albidur, Fa. Hanse-Chemie ) And a further amount of epoxy resin and stirred for 24 h at 40 ⁰ C until the mixture was homogeneous. Thereafter, the solvent was distilled off at 80 ⁰ C and slightly reduced pressure. This gave a composition with 30 wt.% Particle content and two different particle populations, of which one population had a particle size between 0.3 and 3 microns with a broad particle size distribution.

Example 6

An aqueous dispersion of core shell particles having an elastomeric silicone core and a grafted acrylate copolymer shell and an inner core of one

Acrylate copolymer and a particle size of 350 nm and a bimodal particle size distribution was precipitated by addition of a mixture of 60 wt.% Methanol and 40 wt.% Acetone. The precipitate was filtered off, washed and dried. 200 g of solid were obtained. Then 300g one at

Room temperature solid epoxy resin and heated to 12O ⁰ C, wherein the resin melted and became fluid. The solid consisting of the reversibly agglomerated core Schalepartikeln was added and dispersed first for 6 hours at 120 ⁰ C, then 2h at 140 ⁰ C with the aid of high shear forces, which was then filtered at 14O ⁰ C was. Upon cooling, a solid, homogeneous composition containing 40 wt% core-shell particles was obtained which was substantially in agglomerate-free form. Example 7

As Example 6, but instead of the solid epoxy resin, a liquid urethane resin was used. One received one

A composition containing 22% by weight of core shell particles dispersed in the urethane resin.

Example 8

As in Example 6, an aqueous dispersion of functional core Schalepartikeln was presented, but still had no Organopolymerhülle, but only an inner core and a particle size of 250nm and a broader particle size distribution, but not precipitated as a solid, but with 700g toluene, 40g methyl methacrylate and 500g of a 10% solution of magnesium sulfate, which also contained some acetic acid. After stirring for 24 hours, the aqueous phase was separated and the organic solution filtered and washed several times with water to remove the detergent from the dispersion. 800 g of an organosol having a solids content of 20% by weight were obtained. The organosol was added with a small amount of a polymerization initiator. Thereafter, the mixture was stirred at 90 ^° C. for 24 h. An acrylate resin mixture consisting of 3 components and a stabilizer was added which suppresses the polymerization of the acrylate resins. The residual solvent was then removed by distillation to give a composition of 35 wt% core-shell particles dispersed in an acrylate resin mixture.

Claims

claims

A composition comprising (A) core-shell particles of an organopolysiloxane core which have a crosslinked or uncrosslinked organopolymer shell and optionally a crosslinked or uncrosslinked organopolymer core or mixtures thereof with any other siloxane-containing particles and (B) a reactive resin or a mixture of different reactive resins.

2. Composition according to claim 1, characterized in that the core-shell particles have an average diameter of 5 to 400 nm.

3. The composition of claim 1 or 2, characterized in that in the core Schalepartikeln having a core and optionally an inner core and a shell around the core, wherein the silicone content of the core Schalepartikel is between 20 and 95 wt.% ,

4. The composition according to one or more of claims 1, 2 and 3, characterized in that the silicone content of organopolysiloxane

0-10 units of the general formula

[R ₃ SiO ₁₇₂ ] (1),

0 - 90 units of the general formula

[R ₂ SiO ₂₇₂ ] (2),

0 -100 units of the general formula

[RSiO ₃₇₂ ] (3), 0 -50 units of the general formula

wherein the units (2) and (3) optionally together at least 5 wt.% Based on the silicone content, wherein

R represents hydrogen atoms or identical or different monovalent SiC-bonded, optionally substituted C] _ to C] _g hydrocarbon radicals.

5. Composition according to one or more of claims 1 -

4, characterized in that in the core shell particles, the shell and / or the inner core consist of a grafted organopolymer, which is composed of one or more radically polymerizable monomers.

6. Composition according to one or more of claims 1 -

5, characterized in that (B) a reactive resin or a reactive resin mixture of various reactive resins from the

Group selected from epoxy resins, phenolic resins, urethane resins, acrylate resins, silicone resins.

7. A method for producing a composition according to one or more of claims 1-6, characterized in that in an organic solution of the core-shell particles and optionally further siloxane-containing particles at least one reactive resin is added and the solvent is removed.