EP1572768A2 - Core and shell particle for modifying impact resistance of a mouldable poly(meth)acrylate material - Google Patents

Core and shell particle for modifying impact resistance of a mouldable poly(meth)acrylate material

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Publication number
EP1572768A2
EP1572768A2 EP03769412A EP03769412A EP1572768A2 EP 1572768 A2 EP1572768 A2 EP 1572768A2 EP 03769412 A EP03769412 A EP 03769412A EP 03769412 A EP03769412 A EP 03769412A EP 1572768 A2 EP1572768 A2 EP 1572768A2
Authority
EP
European Patent Office
Prior art keywords
weight
core
shell
alkyl
carbon atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP03769412A
Other languages
German (de)
French (fr)
Inventor
Klaus Schultes
Reiner Müller
Andreas Spiess
Klaus Albrecht
Werner Höss
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Roehm GmbH Darmstadt
Original Assignee
Roehm GmbH Darmstadt
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Filing date
Publication date
Application filed by Roehm GmbH Darmstadt filed Critical Roehm GmbH Darmstadt
Publication of EP1572768A2 publication Critical patent/EP1572768A2/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/06—Copolymers with vinyl aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/005—Homopolymers or copolymers obtained by polymerisation of macromolecular compounds terminated by a carbon-to-carbon double bond
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2998—Coated including synthetic resin or polymer

Definitions

  • the present invention relates to core-shell particles, processes for producing core-shell particles, molding compositions containing core-shell particles and their use.
  • the present invention relates to core-shell particles which can be used for impact modification of poly (meth) acrylate molding compositions. It has long been known that the notched impact strength of molding compositions, in particular poly (meth) acrylate molding compositions, can be improved by adding a suitable amount of so-called impact modifiers to the molding composition.
  • the use of core-shell particles with one or two shells has become established in technology. These generally have an elastomeric phase, in the case of a core-shell particle with one shell usually the core and, in the case of a core-shell particle with two shells, usually the first shell grafted onto the core being the elastomeric phase.
  • US Pat. No. 3,793,402 discloses impact-resistant molding compositions, in particular based on poly (meth) acrylate, which contain 90 to 4% by weight of a multi-stage core-shell particle with a hard core, an elastomeric first shell and a hard one have second shell.
  • Typical main components of the core and the second shell are alkyl methacrylate with 1 to 4 carbon atoms in the alkyl radical, in particular methyl methacrylate.
  • the first shell is essentially composed of butadiene, substituted butadienes and / or alkyl acrylates with 1 to 8 carbon atoms in the alkyl radical.
  • copolymerizable monomer units such as, for example, copolymerizable, monoethylenically unsaturated monomer units.
  • copolymerizable monomer units such as, for example, copolymerizable, monoethylenically unsaturated monomer units.
  • the total diameter of the core-shell particles is in the range from 100 to 300 nm.
  • German patent application DE 41 21 652 A1 describes impact modifiers for thermoplastics, such as polymethyl methacrylate, consisting of an at least three-phase emulsion polymer containing
  • a hard core made of a crosslinked homo- or copolymer of ethylenically unsaturated, free-radically polymerizable monomers
  • a molding compound (example 3) which is mentioned in this publication has an Izod impact strength at room temperature of 6.2 kJ / m 2 , at -10 ° C of 4.7 kJ / m 2 and at -20 ° C of 3.7 kJ / m 2 .
  • the Vicat softening temperature of the molding compound is 97 ° C.
  • German patent application DE 41 36 993 A1 discloses impact-modified molding compositions which contain 10 to 96% by weight of a polymer based on polymethyl methacrylate and 4 to 90% by weight of a multi-stage core-shell-shell particle, the preparation of the Core and the second shell, a monomer mixture is used which essentially contains methyl methacrylate.
  • the monomer mixture for the first shell comprises 60 to 89.99% by weight of acrylic acid alkyl esters with 1 to 20 carbon atoms in the alkyl radical and / or cycloalkylacrylates with 5 to 8 carbon atoms in the cycloalkyl radical and 10 to 39.99% by weight of phenyl acrylic acid.
  • alkyl esters with 1 to 4 carbon atoms in the alkyl radical and optionally further constituents are included in the alkyl esters with 1 to 4 carbon atoms in the alkyl radical and optionally further constituents.
  • the average particle diameter of the core-shell-shell particles is in the range from 50 nm to 1000 nm, in particular in the range from 150 nm to 400 nm.
  • European patent EP 0 828 772 B1 describes the impact modification of poly (meth) acrylates by means of multi-stage core-shell particles, which consist of a core, a first shell and optionally a second shell, and of vinylically unsaturated compounds with at least two identical reactive double bonds are free.
  • the core contains a first (meth) acrylic polymer.
  • the first shell has a polymer with a low glass transition temperature, which contains 0 to 25% by weight, in particular 5 to 26% by weight, of a styrenic monomer and 75 to 100% by weight of a (meth) acrylic monomer which contains a homopolymer forms a glass transition temperature between -75 ° C and -5 ° C.
  • the optionally present second shell contains a second (meth) acrylic polymer which corresponds to the first (meth) acrylic polymer or can be different from him.
  • the total diameter of the core-shell particles is in the range from 250 nm to 320 nm.
  • suspension polymers are also occasionally used to modify the impact strength of molding compositions.
  • the rubber grafted with, for example, polymethyl methacrylate is present in the matrix of the molding composition, for example polymethyl methacrylate, relatively finely distributed.
  • the elastomeric phase consists of a mostly crosslinked copolymer with a low glass transition temperature below 25 ° C., which usually has alkyl acrylate units with 1 to 8 carbon atoms in the alkyl radical, in particular butyl acrylate units, as the main component.
  • polybutadiene or polybutadiene copolymers are also used as the tough phase.
  • the molding composition should have an Izod impact strength at 23 ° C., preferably greater than 6.0 kJ / m 2 , an elastic modulus preferably greater than 1450 MPa, a melt viscosity preferably greater than 2000 Pa s and advantageously less than 4500 Pa s, a Vicat temperature preferably greater than 93 ° C and a strand expansion preferably in the range of 0 to 20%.
  • the present invention provides impact modifiers for molding compositions, in particular for poly (meth) acrylate molding compositions, which enable the notched impact strength of molding compositions to be improved, in particular at low temperatures, without simultaneously the noticeable deterioration of the other properties of the molding composition which are important for the application, in particular the modulus of elasticity, the melt viscosity, the Vicat temperature and the strand expansion.
  • the molding compositions should have an Izod impact strength at 23 ° C., preferably greater than 6.0 kJ / m 2 , an elastic modulus preferably greater than 1450 MPa, a melt viscosity preferably greater than 2000 Pa s. And advantageously less than 4500 Pa s, a Vicat temperature preferably greater than 93 ° C. and a strand expansion preferably in the range from 0 to 20%.
  • the present invention was also based on the object Specify areas of application and possible uses of the impact modifier according to the invention.
  • a core-shell particle which consists of a core, a first shell and optionally a second shell, wherein: i) the core, based on its total weight, at least 75.0% by weight (meth) repeating acrylate units; ii) the first shell has a glass transition temperature below 30 ° C; iü) the optionally present second shell, based on its total weight, comprises at least 75.0% by weight of (meth) acrylate repeat units; iv) the first shell, based on its total weight, comprises the following components:
  • styrene repeat units of the general formula (I) where the radicals R 1 to R 5 are each independently hydrogen, a halogen, a C- ⁇ - 6 alkyl group or a C 2 - 6 - alkenyl group call and the radical R 6 is hydrogen or an alkyl group having 1 to 6 carbon atoms, wherein the weight percentages of E) and F) add up to 100.0% by weight, v) the radius of the core-shell particle, including any second shell, measured by the Coulter method, in the range of greater than 160.0 up to 240.0 nm,
  • Molding compositions which are particularly suitable according to the invention have a notched impact strength according to Izod at 23 ° C., preferably greater than 6.0 kJ / m 2 , an elastic modulus preferably greater than 1450 MPa, a melt viscosity preferably greater than 2000 Pa s and advantageously less than 4500 Pa s, a Vicat Temperature preferably greater than 93 ° C and a strand expansion preferably in the range of 0 to 20%.
  • a number of important advantages can be achieved by using the core-shell particles according to the invention. These include:
  • molding compositions with significantly improved notched impact strength values are expediently molding compositions with an Izod impact strength according to ISO 180 greater than 3.7 kJ / m 2 at -20 ° C, accessible.
  • the core-shell particles according to the invention can be produced in a simple manner, on an industrial scale and inexpensively.
  • the impact-modified molding compositions according to the invention are distinguished by a significantly improved property profile at low temperatures, in particular at -20 ° C. This makes them ideal for applications at low temperatures, especially at temperatures below 0 ° C.
  • the present invention relates to core-shell particles which have a core, a first shell and optionally a second shell.
  • the core-shell particles according to the invention can optionally comprise further shells, although for the purposes of the present invention those core-shell particles which consist of a core, a first shell and preferably a second shell have proven particularly useful.
  • the term “core-shell particles” is best known from the prior art and, in the context of the present invention, denotes polymers which can be obtained by multi-stage emulsion polymerization. This method has long been known in the prior art and is carried out and explained, for example, in Houben-Weyl, Volume E20, Part 2 (1987), p. 1150 ff. The person skilled in the art can also obtain further valuable information from the publications US Pat. No. 3,793,402, DE 41 21 652 A1, DE 41 36 993 A1, EP 828 772 A1, the disclosure of which is hereby expressly incorporated by reference.
  • the core based on its total weight, has at least 75% by weight of (meth) acrylate repeating units.
  • (meth) acrylates denotes acrylates, methacrylates and mixtures of the two. They thus comprise compounds which have at least one group of the following formula
  • R denotes hydrogen or a methyl radical.
  • They include, in particular, alkyl acrylates and / or alkyl methacrylates.
  • the core preferably comprises, based in each case on its total weight, A) 50.0 to 99.9% by weight, suitably 60.0 to 99.9% by weight, preferably 75.0 to 99.9% by weight , particularly preferably 80.0 to 99.0% by weight, in particular 85.0 to 99.0% by weight, alkyl methacrylate repeating units with 1 to 20, preferably 1 to 12, in particular 1 to 8 carbon atoms in the alkyl radical,
  • the compounds A), B), C) and D) are of course different from one another, in particular the compounds A) and B) do not comprise any crosslinking monomers C).
  • the radicals R 1 to R 5 each independently denote hydrogen, a halogen, in particular fluorine, chlorine or bromine, or an alkyl group having 1 to 6 carbon atoms, preferably hydrogen.
  • the radical R 6 denotes hydrogen or an alkyl group with 1 to 6 carbon atoms, preferably hydrogen.
  • Particularly suitable alkyl groups with 1 to 6 carbon atoms are methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl groups and Cyclopentyl and cyclohexyl groups.
  • Styrene repeat units of the general formula (I) thus comprise recurring structural units which can be obtained by polymerizing monomers of the general formula (Ia).
  • Suitable monomers of the general formula (Ia) include, in particular, styrene, substituted styrenes with an alkyl substituent in the side chain, such as, for example, methylstyrene and ⁇ -ethylstyrene, substituted styrenes with an alkyl substituent on the ring, such as, for example, vinyl toluo! and p-methylstyrene, halogenated styrenes such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes.
  • alkyl methacrylate repeating units (A) mentioned above are taken to mean repeating structural units which can be obtained by polymerizing esters of methacrylic acid.
  • Suitable esters of methacrylic acid include in particular methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-octyl methacrylate, non-ethylhexyl methacrylate, 2-ethylhexyl methacrylate, tert-butylheptyl methacrylate, 3-iso-propylheptyl methacrylate, decyl methacrylate, undecyl methacrylate, 5-
  • the core based on its total weight, contains at least 50% by weight, suitably at least 60% by weight, preferably at least 75% by weight, in particular at least 85% by weight, of methyl methacrylate repeating units ,
  • alkyl acrylate repeating units (B) are understood to mean recurring structural units which can be obtained by polymerizing esters of acrylic acid.
  • Suitable esters of acrylic acid include in particular methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-octyl acrylate, ethyl hexyl acrylate, 2-methyl acrylate, 2-ethyl acrylate, 2-methyl acrylate, 2-ethyl acrylate, 2-ethyl acrylate, 2-ethyl acrylate, 2-ethyl acrylate, 2-ethyl acrylate, -tert Butylheptylacrylat, 3-iso-propyl
  • crosslinking repeat units (C) are taken to mean recurring structural units which can be obtained by polymerizing crosslinking monomers.
  • Suitable crosslinking monomers include in particular all the compounds which are able to bring about crosslinking under the present polymerization conditions. These include in particular
  • R is hydrogen or methyl and n denotes a positive integer greater than or equal to 2, preferably between 3 and 20, in particular Di ( meth) acrylates of propanediol, butanediol, hexanediol, octanediol, nonanediol, decanediol and eicosanediol;
  • R is hydrogen or methyl and n is a positive integer between 1 and 14, in particular di (meth) acrylates of ethylene glycol, diethylene glycol, triethylene glycols, tetraethylene glycols, dodecaethylene glycols, tetradecaethylene glycols, propylene glycols, dipropyl glycols and tetradecapropylene glycols.
  • Glycerol di (meth) acrylate 2,2'- bis [p- ( ⁇ -methacryloxy- ⁇ -hydroxypropoxy) phenylpropane] or bis-GMA, biphenol-A-dimethacrylate, neopentyl glycol di (meth) acrylate, 2,2'-di (4- methacryloxypolyethoxyphenyl) propane with 2 to 10 ethoxy groups per molecule and 1, 2-bis (3-methacryloxy-2-hydroxypropoxy) butane.
  • Trifunctional or polyfunctional (meth) acrylates in particular trimethylolpropane tri (meth) acrylates and pentaerythritol tetra (meth) acrylate.
  • aromatic crosslinkers in particular 1,2-divinylbenzene, 1,3-divinylbenzene and 1,4-divinylbenzene.
  • the proportions by weight of constituents A) to D) of the core are preferably selected such that the core has a glass transition temperature Tg of at least 10 ° C., preferably of at least 30 ° C.
  • the glass transition temperature Tg of the polymer can be determined in a known manner by means of differential scanning calorimetry (DSC). Furthermore, the glass transition temperature Tg can also be calculated approximately in advance using the Fox equation. According to Fox T. G., Bull. Am. Physics Soc. 1, 3, page 123 (1956) applies:
  • the first shell of the core-shell particles according to the invention has a glass transition temperature of less than 30 ° C., preferably less than 10 ° C., in particular in the range from 0 to -75 ° C.
  • the glass transition temperature Tg of the polymer can be determined by means of differential scanning calorimetry (DSC) and / or can be calculated approximately in advance using the Fox equation.
  • the first shell based on its total weight, contains the following components:
  • the first shell comprises
  • E-1) 90.0 to 97.9% by weight alkyl acrylate repeat units with 3 to 8 carbon atoms in the alkyl radical and / or alkyl methacrylate repeat units with 7 to 14 carbon atoms in the alkyl radical, in particular butyl acrylate and / or dodecyl methacrylate repeat units, and
  • the compounds E-1), E-2) and F) are of course different from one another, in particular the compounds E-1) do not comprise any crosslinking monomers E-2).
  • the second shell if present, includes, based on it
  • G 50.0 to 100.0% by weight, advantageously 60.0 to 100.0% by weight, particularly preferably 75.0 to 100.0% by weight, in particular 85.0 to 99.5% by weight .-%, alkyl methacrylate repeating units with 1 to 20, preferably 1 to 12, in particular 1 to 8, carbon atoms in the alkyl radical,
  • alkyl acrylate repeat units with 1 to 20, preferably 1 to 12, in particular 1 to 8, carbon atoms in the alkyl radical,
  • the second shell contains, based on its total weight, at least 50% by weight, expediently at least 60% by weight, preferably at least 75% by weight, in particular at least 85% by weight of methyl methacrylate. repeating units.
  • the constituents of the second shell are advantageously selected in such a way that the second shell has a glass transition temperature Tg of at least 10 ° C., preferably of at least 30 ° C.
  • the glass transition temperature Tg of the polymer can be determined by means of differential scanning calorimetry (DSC) and / or can be calculated approximately in advance using the Fox equation.
  • the total radius of the core-shell particle, including the optionally present second shell is in the range from greater than 160 to 240 nm, preferably in the range from 170 to 220 nm, in particular in the range from 175 to 210 nm. The total radius is determined according to the Coulter Procedure determined.
  • the first shell 20.0 to 75.0% by weight, preferably 30.0 to 60.0
  • % By weight, expediently 35.0 to 55.0% by weight, in particular 40.0 to 50% by weight, and iii) the second shell 0.0 to 50.0% by weight, preferably 5, 0 to 40.0
  • % By weight, expediently 10.0 to 30.0% by weight, in particular 15.0 to 25.0% by weight, the weight percentages preferably adding up to 100.0% by weight.
  • the core-shell particles according to the invention can be produced in a manner known per se, for example by means of multi-stage emulsion polymerization. It is expediently carried out by a process in which water and emulsifier are initially introduced.
  • the template preferably contains 90.00 to 99.99 parts by weight of water and 0.01 to 10.00 parts by weight of emulsifier Advantageously add parts by weight to 100.00 parts by weight.
  • the monomers for the core are then added to this template step by step in the following order b) in the desired ratios and up to a conversion of at least 85.0% by weight, preferably at least 90.0% by weight, advantageously at least 95 , 0% by weight, in particular at least 99% by weight, in each case based on their total weight, polymerized, c) the monomers for the first shell are added in the desired ratios and up to a conversion of at least 85.0% by weight , preferably at least 90.0% by weight, expediently at least 95.0% by weight, in particular at least 99% by weight, in each case based on their total weight, polymerized, d) optionally the monomers for the second shell in the desired ratios added and up to a conversion of at least 85.0% by weight, preferably at least 90.0% by weight, advantageously at least 95.0% by weight, in particular at least 99% by weight, in each case based on their total weight, polymerized.
  • polymers refer to compounds which have at least ten times the molecular weight in comparison with the respective starting compound A) to I), the so-called monomer.
  • the progress of the polymerization reaction in each step can be monitored in a known manner, for example gravimetrically or by means of gas chromatography.
  • the polymerization in steps b) to d) is preferably carried out at a temperature in the range from 0 to 120 ° C., preferably in the range from 30 to 100 ° C.
  • Suitable organic initiators are, for example, hydroperoxides, such as tert-butyl hydroperoxide or cumene hydroperoxide.
  • Suitable inorganic initiators are hydrogen peroxide and the alkali metal and ammonium salts of peroxodisulfuric acid, especially sodium and potassium peroxodisulfate.
  • Suitable redox initiator systems are, for example, combinations of tertiary amines with peroxides or sodium disulfite and alkali metal and the ammonium salts of peroxodisulfuric acid, in particular sodium and potassium peroxodisulfate, or particularly preferably peroxides.
  • the initiators mentioned can be used either individually or in a mixture. They are preferably used in an amount of 0.05 to 3.0% by weight, based on the total weight of the monomers in the respective stage.
  • the polymerization can also preferably be carried out with a mixture of different polymerization initiators with different half-lives in order to keep the radical stream constant during the course of the polymerization and at different polymerization temperatures.
  • the batch is preferably stabilized by means of emulsifiers and / or protective colloids. Stabilization by emulsifiers is preferred in order to obtain a low dispersion viscosity.
  • the total amount of emulsifier is preferably 0.1 to 5% by weight, in particular 0.5 to 3% by weight, based on the total weight of the monomers A) to I).
  • Particularly suitable emulsifiers are anionic or nonionic emulsifiers or mixtures thereof, in particular:
  • Alkyl sulfates preferably those with 8 to 18 carbon atoms in the alkyl radical, alkyl and alkylaryl ether sulfates with 8 to 18 carbon atoms in the alkyl radical and 1 to 50 ethylene oxide units;
  • Sulfonates preferably alkyl sulfonates with 8 to 18 carbon atoms in the alkyl radical, alkylarylsulfonates with 8 to 18 carbon atoms in the alkyl radical, esters and half esters of sulfosuccinic acid with monohydric alcohols or alkylphenols with 4 to 15 carbon atoms in the alkyl radical; optionally these alcohols or alkylphenols can also be ethoxylated with 1 to 40 ethylene oxide units;
  • Partial phosphoric acid esters and their alkali and ammonium salts preferably alkyl and alkylaryl phosphates with 8 to 20 carbon atoms in the alkyl or alkylaryl radical and 1 to 5 ethylene oxide units;
  • Alkyl polyglycol ethers preferably with 8 to 20 carbon atoms in the alkyl radical and 8 to 40 ethylene oxide units;
  • Alkylaryl polyglycol ethers preferably having 8 to 20 carbon atoms in the alkyl or alkylaryl radical and 8 to 40 ethylene oxide units;
  • Ethylene oxide / propylene oxide copolymers preferably block copolymers, advantageously with 8 to 40 ethylene oxide or propylene oxide units.
  • Mixtures of anionic emulsifier and nonionic emulsifier are preferably used according to the invention.
  • the emulsifiers can also be used in a mixture with protective colloids.
  • Suitable protective colloids include u. a. partially saponified polyvinyl acetates, polyvinyl pyrrolidones, carboxymethyl, methyl, hydroxyethyl, hydroxypropyl cellulose, starches, proteins, poly (meth) acrylic acid, poly (meth) acrylamide, polyvinylsulfonic acids, melamine formaldehyde sulfonates, naphthalene formaldehyde sulfonates, styrene-maleic acid and copolyether. If protective colloids are used, this is preferably done in an amount of 0.01 to 1.0% by weight, based on the total amount of monomers A) to I).
  • the protective colloids can be introduced or metered in before the start of the polymerization.
  • the initiator can be introduced or metered in. Furthermore, it is also possible to introduce part of the initiator and to meter in the rest.
  • the polymerization is preferably started by heating the batch to the polymerization temperature and metering in the initiator, preferably in aqueous solution.
  • the dosages of emulsifier and monomers can be carried out separately or as a mixture.
  • the procedure is such that the emulsifier and monomer are premixed in a mixer upstream of the polymerization reactor.
  • the remainder of emulsifier and the remainder of monomer are preferred were not submitted, metered in separately from one another after the start of the polymerization. Dosing is preferably started 15 to 35 minutes after the start of the polymerization.
  • the template contains a so-called "seed latex", which is preferably obtainable by polymerizing alkyl (meth) acrylates and moreover advantageously has a particle radius in the range from 3.0 to 20 0 nm.
  • seed latex preferably obtainable by polymerizing alkyl (meth) acrylates and moreover advantageously has a particle radius in the range from 3.0 to 20 0 nm.
  • These small radii can be calculated after a defined polymerisation of the seed latex, in which a shell is built up around the seed latex and the radii of the particles produced in this way were measured using the Coulter method.
  • This method for particle size determination known in the literature is based on the measurement of the electrical resistance, which changes in a characteristic manner when particles pass through a narrow measurement opening. Further details can be found, for example, in Chem. Tech. Lab. 43, 553-566 (1995).
  • the monomer components of the actual core ie the first composition
  • the polymer formed in the first stage of the process is stored in a shell-like manner around the seed latex.
  • the monomer components of the first shell material (second composition) are added to the emulsion polymer under conditions such that the formation of new particles is avoided.
  • the polymer produced in the second stage is stored in a shell-like manner around the existing core. This procedure is appropriate for each additional bowl. - to repeat.
  • the core-shell particles according to the invention are obtained by an emulsion polymerization process in which, instead of the seed latex, a long-chain, aliphatic alcohol, preferably having 12 to 20 carbon atoms, is initially emulsified.
  • a long-chain, aliphatic alcohol preferably having 12 to 20 carbon atoms
  • stearyl alcohol is used as the long-chain, aliphatic alcohol.
  • the core-shell structure is obtained analogously to the procedure described above by stepwise addition and polymerization of the corresponding monomers while avoiding the formation of new particles.
  • the person skilled in the art can obtain further details on the polymerization process from the patents DE 3343766, DE 3210891, DE 2850105, DE 2742178 and DE 3701579.
  • the chain lengths, in particular the (co) polymers of the second shell, can be adjusted by polymerizing the monomer or the monomer mixture in the presence of molecular weight regulators, such as, in particular, the mercaptans known for this, such as, for example, n-butyl mercaptan, n-dodecyl mercaptan, 2- Mercaptoethanol or 2-ethylhexylthioglycolate, pentaerythritol tetrathioglycolate; the molecular weight regulators generally in amounts of 0.05 to 5% by weight, based on the monomer mixture, preferably in amounts of 0.1 to 2% by weight and particularly preferably in amounts of 0.2 to 1% by weight be used on the monomer mixture (see, for example, H.
  • molecular weight regulators such as, in particular, the mercaptans known for this, such as, for example, n-butyl mercaptan, n-dodecyl
  • the molecular weight regulator used is preferably n-dodecyl mercaptan.
  • postpolymerization can be carried out using known methods to remove residual monomers, for example by means of initiated postpolymerization.
  • the process according to the invention is particularly suitable for the production of aqueous dispersions with a high solids content of more than 50% by weight, based on the total weight of the aqueous dispersion
  • the relative proportions of all substances are expediently chosen such that the total weight of the monomers, based on the Total weight of the aqueous dispersion, greater than 50.0% by weight, suitably greater than 51.0% by weight, preferably greater than 52.0% by weight.
  • the substances to be considered in this connection also include all other substances used, such as water, emulsifier, initiator, possibly regulators and protective colloids, etc.
  • the aqueous dispersions obtainable by the process according to the invention are characterized by a low coagulum content which, based on the total weight of the aqueous dispersion, is preferably less than 5.0% by weight, advantageously less than 3.0% by weight, in particular less than 1.5 wt%.
  • the aqueous dispersion based on its total weight, has less than 1.0% by weight, preferably less than 0.5% by weight, suitably less than 0.25% by weight , in particular 0.10 wt .-% or less, coagulate.
  • the term “coagulate” denotes water-insoluble constituents which can preferably be filtered off, preferably by filtration of the dispersion, using a filter sleeve with clamped filter fabric No. 0.90 DIN 4188.
  • the core-shell particle according to the invention can be obtained from the dispersion, for example, by spray drying, freeze coagulation, precipitation by adding electrolyte or by mechanical or thermal stress, as can be carried out according to DE 27 50 682 A1 or US 4 110 843 by means of a degassing extruder.
  • the spray drying process is the most common, although the other processes mentioned have the advantage that the water-soluble polymerization auxiliaries are at least partially separated from the polymer.
  • the core-shell particle according to the invention serves to improve the notched impact strength of hard thermoplastics which are compatible with the hard phase, preferably of poly (meth) acrylate molding compositions, in particular of polymethyl methacrylate.
  • the poly (meth) acrylate molding compositions preferably contain further polymers in order to modify the properties in a suitable manner.
  • polyacrylonitriles include in particular polyacrylonitriles, polystyrenes, polyethers, polyesters, polycarbonates and polyvinyl chlorides.
  • These polymers can be used individually or as a mixture, copolymers which can be derived from the aforementioned polymers being added to the molding compositions in the context of a very particularly preferred embodiment of the present invention.
  • These include, in particular, styrene-acrylonitrile copolymers (SAN), which are preferably added to the molding compositions in an amount of up to 45% by weight.
  • SAN styrene-acrylonitrile copolymers
  • Particularly preferred styrene-acrylonitrile copolymers can be obtained through the
  • 100 parts of the molding composition to be modified are admixed with 10 to 60 parts of the impact modifier.
  • particularly preferred molding compositions contain, in each case based on their total weight:
  • the (meth) acrylic polymer comprises, in each case based on its total weight, preferably a) 50.0 to 100.0% by weight, advantageously 60.0 to 100.0% by weight, particularly preferably 75.0 to 100, 0% by weight, in particular 85.0 to 99.5% by weight, of repeating alkyl methacrylate units with 1 to 20, preferably 1 to 12, advantageously 1 to 8, in particular 1 to 4, carbon atoms in the alkyl radical, b) 0, 0 to 40.0% by weight, preferably 0.0 to 25.0% by weight, in particular 0.1 to 15.0% by weight, of alkyl acrylate repeating units with 1 to 20, preferably 1 to 12, expediently 1 to 8, in particular 1 to 4, carbon atoms in the alkyl radical and c) 0.0 to 8.0 wt .-% styrene repeat units of the general
  • Formula (I) the percentages by weight adding up to 100.0% by weight.
  • the (meth) acrylic polymer based on its total weight, contains at least 50.0% by weight, advantageously at least 60.0% by weight, preferably at least 75.0% by weight, in particular at least 85.0% by weight methyl methacrylate repeat units.
  • the (meth) acrylic polymer preferably has a number average molecular weight in the range from 1,000 to 100,000,000 g / mol, preferably in the range from 10,000 to 1,000,000 g / mol, in particular in the range from 50,000 to 500,000 g / mol.
  • the molecular weight can be determined, for example by means of gel permeation chromatography with calibration for polystyrene.
  • the dispersion of the core-shell particle can be mixed with an aqueous dispersion of the mixing component and the mixture coagulated, the water phase separated and the coagulate melted into a molding compound.
  • a particularly uniform mixing of the two masses can be achieved.
  • the components can also be prepared and isolated separately and mixed in the form of their melts or as powders or granules and homogenized in a multi-screw extruder or on a roller mill.
  • Usual additives can be mixed in at any suitable processing stage. These include dyes, pigments, fillers, reinforcing fibers, lubricants, UV protection agents, etc.
  • the molding composition contains, based in each case on its total weight, 0.1 to 10% by weight, preferably 0.5 to 5.0% by weight, in particular 1.0 to 4, 0% by weight of a further polymer (AP) which, in comparison with the (meth) acrylic polymer, has a weight average molecular weight which is at least 10%, preferably at least 50%, in particular at least 100% higher.
  • the molecular weight can be determined, for example by means of gel permeation chromatography with calibration for polystyrene.
  • Polymers (AP) which are particularly suitable according to the invention comprise, based on their total weight, preferably a) 50.0 to 100.0% by weight, advantageously 60.0 to 100.0% by weight, particularly preferably 75.0 to 100 , 0 wt .-%, in particular 85.0 to 99.5 wt .-%, alkyl methacrylate repeating units having 1 to 20, preferably 1 to 12, advantageously 1 to 8, in particular 1 to 4, carbon atoms in the alkyl radical, b) 0 , 0 to 40.0% by weight, preferably 0.0 to 25.0% by weight, in particular 0.1 to 15.0% by weight, repeating alkyl acrylate units with 1 to 20, preferably 1 to 12, expediently 1 to 8, in particular 1 to 4, carbon atoms in the alkyl radical and c) 0.0 to 8.0% by weight of styrene repeat units of the general formula (I), the weight percentages adding up to 100.0% by weight.
  • alkyl methacrylate repeating units having 1 to 20,
  • the polymer (AP), based on its total weight, contains at least 50.0% by weight, advantageously at least 60.0% by weight, preferably at least 75.0% by weight, in particular at least 85.0% by weight methyl methacrylate repeat units.
  • the polymer (AP) preferably has a weight average molecular weight in the range from 10,000 to 100,000,000 g / mol, preferably in the range from 50,000 to 5,000,000 g / mol, advantageously in the range from 100,000 to 1,000,000 g / mol, in particular in the range from 250,000 to 600,000 g / mol.
  • the molecular weight can be, for example, by means of
  • Mixtures of the core-shell particles, in particular with polymethyl methacrylate, are particularly suitable for the production of moldings, expediently with a wall thickness of more than 1 mm, such as extruded webs of 1 to 10 mm in thickness, which can be easily punched and for example for the production of printable screens for Electrical devices are useful, or for the production of molded high-quality moldings, for. B. automotive windows. Thinner films, for example 50 ⁇ m thick, can also be produced therefrom.
  • the molded articles obtainable according to the invention stand out
  • KSZ notched impact strength KSZ (Izod 180 / 1eA) according to ISO 180 of at least 5.8 kJ / m 2 , advantageously greater than 6.0 kJ / m 2 , at 23 ° C and preferably of at least 3.7 kJ / m 2 at -20 ° C and
  • the moldings according to the invention are used as a mirror housing or spoiler of a vehicle, as a tube, as a film for sports articles, as a cover or as a component of a refrigerator.
  • a seed latex was made by emulsion polymerization of a monomer composition containing 98% by weight of ethyl acrylate and 2% by weight of allyl methacrylate. These particles, about 20 nm in diameter, were about 10% by weight in water.
  • All of the core-shell particles described below were produced by means of emulsion polymerization in accordance with the general preparation instructions below.
  • the emulsions I to III given in Table 1 were used.
  • Emulsion I was then metered in over 1 h. 10 minutes after the end of emulsion I, emulsion II was metered in over a period of about 2 hours. Then about 90 min after the end of the emulsion II, emulsion III was metered in over a period of about 1 h. 30 minutes after the end of the emulsion III was cooled to 30 ° C.
  • the dispersion was frozen for 2 d at -20 ° C., then thawed again and the coagulated dispersion was separated off using a filter cloth.
  • the solid was dried at 50 ° C. in a drying cabinet (duration: approx. 3 d).
  • the particle size of the core-shell particles was determined using a Coulter N4 device, the particles being measured in dispersion.
  • Table 1 Composition of the individual emulsions (all figures in fine)
  • Aerosol OT 75 65.88 65.88 65.88 65.88 65.88 65.88 65.88
  • Aerosol OT 75 84.71 84.71 84.71 84.71 84.71
  • Aerosol OT 75 10.59 10.59 10.59 10.59 10.59
  • Test specimens were produced from the mixed molding compositions.
  • the molding compounds and the corresponding test specimens were tested according to the following measurement methods:
  • the notched impact strength of the molding compositions according to the invention is significantly higher at -20 ° C. than that of the comparative molding compositions. All mixtures have a comparable impact strength at room temperature. Even a tough phase without styrene does not improve the
  • the good low-temperature impact strength is achieved without the other important properties of the molding compositions, in particular the
  • Modulus of elasticity [MPa] 1660 1550 1620 1650

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Abstract

The invention relates to a core and shell particle comprising a core, a first shell and eventually a second shell. Said core consists of at least 75.0 mass % (meth)acrylate repeating units with respect to the total mass thereof. The first shell has an internal glass transition temperature of 30 °C. The second shell consists of at least 75.0 mass % (meth)acrylate repeating units with respect to the total mass thereof. The first shell contains the following elements with respect to the total mass thereof: E) 92,0 to 98.0 mass % (meth)acrylate repeating units and F) 2.0 to 8.0 mass % styrene repeating units of the formula (i), wherein groups from R1 to R6 are defined in the claim and the mass percentages of E) and F) are summarised in such a way that they form 100 mass %. The radius of the core and shell particle, including the eventual second shell, which is measured using the Coulter principle ranges from 160.0 to 240.0 nm. A method for producing the core and shell particle on a mouldable material containing it and for using said core and shell particle is also disclosed.

Description

Kern-Schale-Teilchen zur Schlagzähmodifizierung von Poly(meth)acrylat-Formmassen Core-shell particles for impact modification of poly (meth) acrylate molding compounds
Die vorliegende Erfindung betrifft Kern-Schale-Teilchen, Verfahren zur Herstellung von Kern-Schale-Teilchen, Formmassen enthaltend Kern- Schale-Teilchen sowie deren Verwendung. Insbesondere bezieht sich die vorliegende Erfindung auf Kern-Schale-Teilchen, welche zur Schlagzähmodifizierung von Poly(meth)acrylat-Formmassen eingesetzt werden können. Es ist bereits seit langem bekannt, dass die Kerbschlagzähigkeit von Formmassen, insbesondere von Poly(meth)acrylat-Formmassen, verbessert werden kann, indem man der Formmasse eine geeignete Menge sogenannter Schlagzähmodifizierer zusetzt. Dabei hat sich der Einsatz von Kern-Schale-Teilchen mit einer oder zwei Schalen in der Technik durchgesetzt. Diese weisen im allgemeinen eine elastomere Phase auf, wobei bei einem Kern-Schale- Teilchen mit einer Schale meist der Kern und bei einem Kern-Schale- Teilchen mit zwei Schalen meist die auf den Kern aufgepfropfte erste Schale die elastomere Phase darstellen.The present invention relates to core-shell particles, processes for producing core-shell particles, molding compositions containing core-shell particles and their use. In particular, the present invention relates to core-shell particles which can be used for impact modification of poly (meth) acrylate molding compositions. It has long been known that the notched impact strength of molding compositions, in particular poly (meth) acrylate molding compositions, can be improved by adding a suitable amount of so-called impact modifiers to the molding composition. The use of core-shell particles with one or two shells has become established in technology. These generally have an elastomeric phase, in the case of a core-shell particle with one shell usually the core and, in the case of a core-shell particle with two shells, usually the first shell grafted onto the core being the elastomeric phase.
Beispielsweise offenbart das US-Patent US 3 793 402 schlagzähe Formmassen, insbesondere auf Poly(meth)acrylat-Basis, welche 90 bis 4 Gew.-% eines mehrstufigen Kem-Schale-Teilchens mit einem harten Kern, einer elastomeren ersten Schale und einer harten zweiten Schale aufweisen. Typische Hauptbestandteile des Kerns und der zweiten Schale sind Alkylmethacr late mit 1 bis 4 Kohlenstoffatomen im Alkylrest, insbesondere Methylmethacrylat. Die erste Schale ist im wesentlichen aus Butadien, substituierten Butadienen und/oder Alkylacrylaten mit 1 bis 8 Kohlenstoffatomen im Alkylrest aufgebaut. Sie kann jedoch auch 0 bis 49,9 Gew.-%, insbesondere 0,5 bis 30 Gew.-% copolymerisierbare Monomer-Einheiten, wie beispielsweise copolymerisierbare, monoethylenisch-ungesättigte Monomer-Einheiten, enthalten. Dabei ist gemäß US 3 793 402 die Anwesenheit von 10 bis 25 Gew.-% copolymerisierbaren, monoethylenisch-ungesättigten Monomer-Einheiten, insbesondere von Styrol, ganz besonders vorteilhaft. Der Gesamtdurchmesser der Kern-Schale-Teilchen liegt im Bereich von 100 bis 300 nm.For example, US Pat. No. 3,793,402 discloses impact-resistant molding compositions, in particular based on poly (meth) acrylate, which contain 90 to 4% by weight of a multi-stage core-shell particle with a hard core, an elastomeric first shell and a hard one have second shell. Typical main components of the core and the second shell are alkyl methacrylate with 1 to 4 carbon atoms in the alkyl radical, in particular methyl methacrylate. The first shell is essentially composed of butadiene, substituted butadienes and / or alkyl acrylates with 1 to 8 carbon atoms in the alkyl radical. However, it can also contain 0 to 49.9% by weight, in particular 0.5 to 30% by weight, of copolymerizable monomer units, such as, for example, copolymerizable, monoethylenically unsaturated monomer units. According to US Pat. No. 3,793,402, the presence of 10 to 25% by weight of copolymerizable, monoethylenically unsaturated monomer units, in particular of styrene, is very particularly advantageous. The total diameter of the core-shell particles is in the range from 100 to 300 nm.
In ähnlicher Weise beschreibt die deutsche Patentanmeldung DE 41 21 652 A1 Schlagzähmodifizierer für thermoplastische Kunststoffe, wie Polymethylmethacrylat, bestehend aus einem wenigstens dreiphasigen Emulsionspolymerisat, enthaltendSimilarly, the German patent application DE 41 21 652 A1 describes impact modifiers for thermoplastics, such as polymethyl methacrylate, consisting of an at least three-phase emulsion polymer containing
A) einen harten Kern aus einem vernetzten Homo- oder Copolymerisat von ethylenisch-ungesättigten, radikalisch polymerisierbaren Monomeren;A) a hard core made of a crosslinked homo- or copolymer of ethylenically unsaturated, free-radically polymerizable monomers;
B) einer in Gegenwart des Kernmaterials erzeugten Elastomerphase mit einer Glasübergangstempe.ratur nicht über 10°C, die aufgebaut ist aus a) einem Alkylester der Acrylsäure mit 1 bis 8 Kohlenstoffatomen im Alkylrest; b) wenigstens einem vernetzenden Comonomeren mit zwei oder mehr polymerisierbaren Doppelbindungen im Molekül; c) Arylalkylacrylat oder -methacrylat; d) einer in Gegenwart der Elastomerphase erzeugten Hartphase aus einem Homo- oder Copolymerisat von ethylenisch-ungesättigten, radikalisch polymeriserbaren Monomeren mit einer Glasübergangstemperatur von wenigstens 50 °C.B) an elastomer phase produced in the presence of the core material with a glass transition temperature not above 10 ° C., which is composed of a) an alkyl ester of acrylic acid with 1 to 8 carbon atoms in the alkyl radical; b) at least one crosslinking comonomer with two or more polymerizable double bonds in the molecule; c) aryl alkyl acrylate or methacrylate; d) a hard phase produced in the presence of the elastomer phase from a homo- or copolymer of ethylenically unsaturated, radically polymerizable monomers with a glass transition temperature of at least 50 ° C.
Eine examplahsch in dieser Druckschrift angeführte Formmasse (Beispiel 3) weist eine Izod-Kerbschlagzähigkeit bei Raumtemperatur von 6,2 kJ/m2, bei -10 °C von 4,7 kJ/m2 und bei -20 °C von 3,7 kJ/m2 auf. Die Vicat- Erweichungstemperatur der Formmasse beträgt dabei 97 °C.A molding compound (example 3) which is mentioned in this publication has an Izod impact strength at room temperature of 6.2 kJ / m 2 , at -10 ° C of 4.7 kJ / m 2 and at -20 ° C of 3.7 kJ / m 2 . The Vicat softening temperature of the molding compound is 97 ° C.
Die deutsche Patentanmeldung DE 41 36 993 A1 offenbart schlagzähmodifizierte Formmassen, welche 10 bis 96 Gew.-% eines Polymerisats auf Basis von Polymethylmethacrylat und 4 bis 90 Gew.-% eines mehrstufigen Kern-Schale-Schale-Teilchens enthalten, wobei für die Herstellung des Kerns und der zweiten Schale jeweils eine Monomermischung eingesetzt wird, die im wesentlichen Methylmethacrylat enthält. Die Monomermischung für die erste Schale umfasst 60 bis 89,99 Gew.-% Acrylsäurea kylester mit 1 bis 20 Kohlenstoffatomen im Alkylrest und/oder Cycloalkylacrylate mit 5 bis 8 Kohlenstoffatomen im Cycloalkylrest und 10 bis 39,99 Gew.-% Acrylsäure- phenyl-alkylester mit 1 bis 4 Kohlenstoffatomen im Alkylrest sowie gegebenenfalls weitere Bestandteile. Der mittlere Teilchendurchmesser der Kern-Schale-Schale-Teilchen liegt im Bereich von 50 nm bis 1000 nm, insbesondere im Bereich von 150 nm bis 400 nm.German patent application DE 41 36 993 A1 discloses impact-modified molding compositions which contain 10 to 96% by weight of a polymer based on polymethyl methacrylate and 4 to 90% by weight of a multi-stage core-shell-shell particle, the preparation of the Core and the second shell, a monomer mixture is used which essentially contains methyl methacrylate. The monomer mixture for the first shell comprises 60 to 89.99% by weight of acrylic acid alkyl esters with 1 to 20 carbon atoms in the alkyl radical and / or cycloalkylacrylates with 5 to 8 carbon atoms in the cycloalkyl radical and 10 to 39.99% by weight of phenyl acrylic acid. alkyl esters with 1 to 4 carbon atoms in the alkyl radical and optionally further constituents. The average particle diameter of the core-shell-shell particles is in the range from 50 nm to 1000 nm, in particular in the range from 150 nm to 400 nm.
Das europäische Patent EP 0 828 772 B1 beschreibt die Schlagzähmodifizierung von Poly(meth)acrylaten mittels mehrstufiger Kern-Schale-Teilchen, die aus einem Kern, einer ersten Schale und gegebenenfalls einer zweiten Schale bestehen und von vinylisch ungesättigten Verbindungen mit mindestens zwei gleich reaktiven Doppelbindungen frei sind. Dabei enthält der Kern ein erstes (Meth)acrylpolymer. Die erste Schale weist ein Polymer mit tiefer Glasübergangstemperatur auf, welches 0 bis 25 Gew.-%, insbesondere 5 bis 26 Gew.-%, eines styrolischen Monomers und 75 bis 100 Gew.-% eines (Meth)acrylmonomers, das ein Homopolymer mit einer Glasübergangstemperatur zwischen -75 °C und -5° C bildet, umfasst. Die gegebenenfalls vorhandene zweite Schale enthält ein zweites (Meth)acrylpolymer, das dem ersten (Meth)acrylpolymer entsprechen oder von ihm verschieden sein kann. Der Gesamtdurchmesser der Kern- Schale-Teilchen liegt im Bereich von 250 nm bis 320 nm.European patent EP 0 828 772 B1 describes the impact modification of poly (meth) acrylates by means of multi-stage core-shell particles, which consist of a core, a first shell and optionally a second shell, and of vinylically unsaturated compounds with at least two identical reactive double bonds are free. The core contains a first (meth) acrylic polymer. The first shell has a polymer with a low glass transition temperature, which contains 0 to 25% by weight, in particular 5 to 26% by weight, of a styrenic monomer and 75 to 100% by weight of a (meth) acrylic monomer which contains a homopolymer forms a glass transition temperature between -75 ° C and -5 ° C. The optionally present second shell contains a second (meth) acrylic polymer which corresponds to the first (meth) acrylic polymer or can be different from him. The total diameter of the core-shell particles is in the range from 250 nm to 320 nm.
Neben den Emulsionspolymerisaten werden vereinzelt auch Suspensionspolymerisate zur Schlagzähmodifizierung von Formmassen eingesetzt. Hier liegt der Kautschuk mit beispielsweise Polymethylmethacrylat gepfropft relativ fein verteilt in der Matrix der Formmasse, beispielsweise Polymethylmethacrylat, vor. Die elastomere Phase besteht aus einem meist vernetzten Copolymerisat mit niedriger Glasübergangstemperatur kleiner 25 °C, welche üblicherweise Alkylacrylat-Einheiten mit 1 bis 8 Kohlenstoffatomen im Alkylrest, insbesondere Butylacrylat-Einheiten, als Hauptkomponente aufweisen. Vereinzelt werden auch Polybutadien oder Polybutadien-Copolymere als Zähphase eingesetzt.In addition to the emulsion polymers, suspension polymers are also occasionally used to modify the impact strength of molding compositions. Here, the rubber grafted with, for example, polymethyl methacrylate is present in the matrix of the molding composition, for example polymethyl methacrylate, relatively finely distributed. The elastomeric phase consists of a mostly crosslinked copolymer with a low glass transition temperature below 25 ° C., which usually has alkyl acrylate units with 1 to 8 carbon atoms in the alkyl radical, in particular butyl acrylate units, as the main component. In some cases, polybutadiene or polybutadiene copolymers are also used as the tough phase.
Obwohl schon unter Verwendung der vorstehend beschriebenen Schlagzähmodifizierer eine deutliche Verbesserung der Kerbschlagzähigkeit erreicht werden kann, ist diese jedoch für viele Anwendungen noch nicht vollkommen befriedigend. So erfordert insbesondere die Schlagzähmodifizierung bei tiefen Temperaturen eine verhältnismäßig große Menge dieser Schlagzähmodifizierer, welches wiederum zu einer deutlichen Verschlechterung der anderen, für die Anwendung bedeutenden Eigenschaften der Formmasse, insbesondere des E-Moduls, der Schmelzviskosität, der Vicat-Temperatur und der Strangaufweitung, führt.Although a significant improvement in the notched impact strength can be achieved using the impact modifiers described above, this is still not completely satisfactory for many applications. For example, impact modification at low temperatures requires a relatively large amount of these impact modifiers, which in turn leads to a significant deterioration in the other properties of the molding material which are important for the application, in particular the modulus of elasticity, the melt viscosity, the Vicat temperature and the strand expansion ,
Von der Technik werden daher Schlagzähmodifizierer gefordert, welche bei möglichst geringen Mengen an Schlagzähmodifizierer eine hinreichende Verbesserung der Kerbschlagzähigkeit einer Formmasse, insbesondere bei tiefen Temperaturen ermöglicht, ohne dass gleichzeitig die anderen bedeutenden Eigenschaften der Formmasse, insbesondere der E-Modul, die Schmelzviskosität, die Vicat-Temperatur und die Strangaufweitung, merklich verschlechtert werden. Dabei soll die Formmasse eine Kerbschlagzähigkeit nach Izod bei 23 °C vorzugsweise größer 6,0 kJ/m2, ein E-Modul vorzugsweise größer 1450 MPa, eine Schmelzviskosität vorzugsweise größer 2000 Pa s und günstigerweise kleiner 4500 Pa s, eine Vicat-Temperatur vorzugsweise größer 93 °C sowie eine Strangaufweitung vorzugsweise im Bereich von 0 bis 20 % aufweisen.Technology is therefore demanding impact modifiers which, with the smallest possible amounts of impact modifier, enable a sufficient improvement in the notched impact strength of a molding composition, in particular at low temperatures, without at the same time the other important properties of the molding composition, in particular the modulus of elasticity, the melt viscosity, the Vicat -Temperature and the Strand expansion, deteriorate noticeably. The molding composition should have an Izod impact strength at 23 ° C., preferably greater than 6.0 kJ / m 2 , an elastic modulus preferably greater than 1450 MPa, a melt viscosity preferably greater than 2000 Pa s and advantageously less than 4500 Pa s, a Vicat temperature preferably greater than 93 ° C and a strand expansion preferably in the range of 0 to 20%.
In Anbetracht des Standes der Technik war es nun Aufgabe der vorliegenden Erfindung, Schlagzähmodifizierer für Formmassen, insbesondere für Poly(meth)acrylat-Formmassen, zur Verfügung zu stellen, welche eine Verbesserung der Kerbschlagzähigkeit von Formmassen, insbesondere bei tiefen Temperaturen, ermöglichen, ohne gleichzeitig die anderen, für die Anwendung bedeutenden Eigenschaften der Formmasse, insbesondere der E-Modul, die Schmelzviskosität, die Vicat-Temperatur und die Strangaufweitung, merklich zu verschlechtern. Dabei sollten die Formmassen eine Kerbschlagzähigkeit nach Izod bei 23 °C vorzugsweise größer 6,0 kJ/m2, ein E-Modul vorzugsweise größer 1450 MPa, eine Schmelzviskosität vorzugsweise größer 2000 Pa s.und günstigerweise kleiner 4500 Pa s, eine Vicat-Temperatur vorzugsweise größer 93 °C sowie eine Strangaufweitung vorzugsweise im Bereich von 0 bis 20 % aufweisen.In view of the prior art, it was an object of the present invention to provide impact modifiers for molding compositions, in particular for poly (meth) acrylate molding compositions, which enable the notched impact strength of molding compositions to be improved, in particular at low temperatures, without simultaneously the noticeable deterioration of the other properties of the molding composition which are important for the application, in particular the modulus of elasticity, the melt viscosity, the Vicat temperature and the strand expansion. The molding compositions should have an Izod impact strength at 23 ° C., preferably greater than 6.0 kJ / m 2 , an elastic modulus preferably greater than 1450 MPa, a melt viscosity preferably greater than 2000 Pa s. And advantageously less than 4500 Pa s, a Vicat temperature preferably greater than 93 ° C. and a strand expansion preferably in the range from 0 to 20%.
Eine Aufgabe der vorliegenden Erfindung war auch darin zu erblicken, Verfahren zur Herstellung der erfindungsgemäßen Schlagzähmodifizierer anzugeben, welche auf einfache Art und Weise, im industriellen Maßstab und kostengünstig herstellbar sind.It was also an object of the present invention to provide methods for producing the impact modifiers according to the invention which can be produced in a simple manner, on an industrial scale and at low cost.
Der vorliegenden Erfindung lag auch die Aufgabe zugrunde, Anwendungsgebiete und Verwendungsmöglichkeiten der erfindungsgemäßen Schlagzähmodifizierer anzugeben.The present invention was also based on the object Specify areas of application and possible uses of the impact modifier according to the invention.
Gelöst werden diese sowie weitere nicht explizit genannte Aufgaben, die jedoch aus den hierin einleitend diskutierten Zusammenhängen ohne weiteres ableitbar oder erschließbar sind, durch ein Kern-Schale-Teilchen mit allen Merkmalen des vorliegenden Patentanspruchs 1. Zweckmäßige Abwandlungen des erfindungsgemäßen Kern-Schale-Teilchens werden in den auf Anspruch 1 rückbezogenen Unteransprüchen unter Schutz gestellt. Der Anspruch der Verfahrenskategorie schützt eine bevorzugte Herstellungsweise des erfindungsgemäßen Kem-Schale-Teilchens. Weiterhin werden schlagzähmodifizierte Poly(meth)acrylat-Formmassen, welche erfindungsgemäße Kern-Schale-Teilchen enthalten, sowie bevorzugte Einsatzgebiete dieser Formmassen beansprucht.These and other tasks which are not explicitly mentioned, but which can easily be derived or inferred from the contexts discussed at the outset, are achieved by means of a core-shell particle with all the features of the present patent claim 1. Useful modifications of the core-shell particle according to the invention become placed under protection in the dependent claims referring back to claim 1. The claim of the process category protects a preferred production method of the core-shell particle according to the invention. Furthermore, impact-modified poly (meth) acrylate molding compositions which contain core-shell particles according to the invention and preferred areas of use of these molding compositions are claimed.
Dadurch, dass man ein Kern-Schale-Teilchen bereitstellt, welches aus einem Kern, einer ersten Schale und gegebenenfalls einer zweiten Schale besteht, wobei: i) der Kern, bezogen auf sein Gesamtgewicht, mindestens 75,0 Gew.-% (Meth)acrylat-Wiederholungseinheiten umfasst; ii) die erste Schale eine Glasübergangstemperatur kleiner 30 °C aufweist; iü) die gegebenenfalls vorhandene zweite Schale, bezogen auf ihr Gesamtgewicht, mindestens 75,0 Gew.-% (Meth)acrylat- Wiederholungseinheiten umfasst; iv) die erste Schale, bezogen auf ihr Gesamtgewicht, die nachstehenden Bestandteile umfasst:By providing a core-shell particle which consists of a core, a first shell and optionally a second shell, wherein: i) the core, based on its total weight, at least 75.0% by weight (meth) repeating acrylate units; ii) the first shell has a glass transition temperature below 30 ° C; iü) the optionally present second shell, based on its total weight, comprises at least 75.0% by weight of (meth) acrylate repeat units; iv) the first shell, based on its total weight, comprises the following components:
E) 92,0 bis 98,0 Gew.-% (Meth)acrylat-Wiederholungseinheiten undE) 92.0 to 98.0% by weight of (meth) acrylate repeating units and
F) 2,0 bis 8,0 Gew.-% styrolische Wiederholungseinheiten der allgemeinen Formel (I) wobei die Reste R1 bis R5 jeweils unabhängig voneinander Wasserstoff, ein Halogen, eine C-ι-6-Alkylgruppe oder eine C2-6- Alkenylgruppe bezeichnen und der Rest R6 Wasserstoff oder eine Alkylgruppe mit 1 bis 6 Kohlenstoffatomen ist, wobei sich die Gewichtsprozente von E) und F) zu 100,0 Gew.-% addieren, v) der Radius des Kern-Schale-Teilchens inklusive der gegebenenfalls vorhandenen zweiten Schale, gemessen nach dem Coulter-Verfahren, im Bereich von größer 160,0 bis 240,0 nm liegt,F) 2.0 to 8.0% by weight of styrene repeat units of the general formula (I) where the radicals R 1 to R 5 are each independently hydrogen, a halogen, a C-ι- 6 alkyl group or a C 2 - 6 - alkenyl group call and the radical R 6 is hydrogen or an alkyl group having 1 to 6 carbon atoms, wherein the weight percentages of E) and F) add up to 100.0% by weight, v) the radius of the core-shell particle, including any second shell, measured by the Coulter method, in the range of greater than 160.0 up to 240.0 nm,
gelingt es auf nicht ohne weiteres vorhersehbare Weise, einen Schlagzähmodifizierer für Formmassen, insbesondere für Poly(meth)acrylat-Formmassen zugänglich zu machen, welcher eine Verbesserung der Kerbschlagzähigkeit von Formmassen, insbesondere bei tiefen Temperaturen, ermöglicht, ohne gleichzeitig die anderen, für die Anwendung bedeutenden Eigenschaften der Formmasse, insbesondere der E-Modul, die Schmelzviskosität, die Vicat-Temperatur und die Strangaufweitung, merklich zu verschlechtern. Dabei weisen erfindungsgemäß besonders geeignete Formmassen eine Kerbschlagzähigkeit nach Izod bei 23 °C vorzugsweise größer 6,0 kJ/m2, ein E-Modul vorzugsweise größer 1450 MPa, eine Schmelzviskosität vorzugsweise größer 2000 Pa s und günstigerweise kleiner 4500 Pa s, eine Vicat-Temperatur vorzugsweise größer 93 °C sowie eine Strangaufweitung vorzugsweise im Bereich von 0 bis 20 % auf. Zugleich lassen sich durch Einsatz der erfindungsgemäßen Kern-Schale- Teilchen eine Reihe wichtiger Vorteile erzielen. Hierzu gehören unter anderem:It is not easily predictable to make an impact modifier for molding compositions, in particular for poly (meth) acrylate molding compositions, which enables the notched impact strength of molding compositions to be improved, in particular at low temperatures, without the others being used at the same time significant properties of the molding composition, in particular the modulus of elasticity, the melt viscosity, the Vicat temperature and the strand expansion, noticeably deteriorate. Molding compositions which are particularly suitable according to the invention have a notched impact strength according to Izod at 23 ° C., preferably greater than 6.0 kJ / m 2 , an elastic modulus preferably greater than 1450 MPa, a melt viscosity preferably greater than 2000 Pa s and advantageously less than 4500 Pa s, a Vicat Temperature preferably greater than 93 ° C and a strand expansion preferably in the range of 0 to 20%. At the same time, a number of important advantages can be achieved by using the core-shell particles according to the invention. These include:
=> Durch Verwendung der erfindungsgemäßen Kern-Schale-Teilchen werden Formmassen mit deutlich verbesserten Kerbschlägzähigkeit- Werten, insbesondere bei tiefen Temperaturen kleiner 0 °C, zweckmäßigerweise Formmassen mit einer Kerbschlagzähigkeit nach Izod gemäß ISO 180 größer 3,7 kJ/m2 bei -20 °C, zugänglich.=> By using the core-shell particles according to the invention, molding compositions with significantly improved notched impact strength values, in particular at low temperatures below 0 ° C., are expediently molding compositions with an Izod impact strength according to ISO 180 greater than 3.7 kJ / m 2 at -20 ° C, accessible.
=> Im Vergleich mit herkömmlichen Schlagzähmodifizierem reichen deutlich geringere Mengen der erfindungsgemäßen Kern-Schale- Teilchen aus, um Formmassen mit vergleichbaren Kerbschlagzähigkeiten bei tiefen Temperaturen, insbesondere bei -20 °C, zu erhalten.=> In comparison with conventional impact modifiers, significantly smaller amounts of the core-shell particles according to the invention are sufficient to obtain molding compositions with comparable notched impact strengths at low temperatures, in particular at -20 ° C.
= Die erfindungsgemäßen Kern-Schale-Teilchen können auf einfache Art und Weise, großtechnisch und kostengünstig hergestellt werden.= The core-shell particles according to the invention can be produced in a simple manner, on an industrial scale and inexpensively.
=- Die auf erfindungsgemäße Weise schlagzähmodifizierten Formmassen zeichnen sich durch ein deutlich verbessertes Eigenschaftsprofil bei tiefen Temperaturen, insbesondere bei -20 °C, aus. Dies prädestiniert sie für Anwendungen bei tiefen Temperaturen, insbesondere bei Temperaturen kleiner 0 °C.= - The impact-modified molding compositions according to the invention are distinguished by a significantly improved property profile at low temperatures, in particular at -20 ° C. This makes them ideal for applications at low temperatures, especially at temperatures below 0 ° C.
Die vorliegende Erfindung betrifft Kern-Schale-Teilchen, welche einen Kern, eine erste Schale und gegebenenfalls eine zweite Schale aufweisen. Darüber hinaus können die erfindungsgemäßen Kern-Schale- Teilchen gegebenenfalls weitere Schalen umfassen, obwohl sich für die Zwecke der vorliegenden Erfindung solche Kern-Schale-Teilchen besonders bewährt haben, welche aus einem Kern, einer ersten Schale und vorzugsweise einer zweiten Schale bestehen. Der Begriff "Kern-Schale-Teilchen" ist aus dem Stand der Technik bestens bekannt und bezeichnet im Rahmen der vorliegenden Erfindung Polymerisate, welche durch mehrstufige Emulsionspolymerisation erhältlich sind. Dieses Verfahren ist in dem Stand der Technik bereits seit langem bekannt und wird beispielsweise in Houben-Weyl, Band E20, Teil 2 (1987), S. 1150 ff. ausgeführt und erläutert. Weitere wertvolle Hinweise kann der Fachmann auch den Druckschriften US 3 793 402, DE 41 21 652 A1 , DE 41 36 993 A1 , EP 828 772 A1 entnehmen, auf deren Offenbarung hiermit explizit Bezug genommen wird.The present invention relates to core-shell particles which have a core, a first shell and optionally a second shell. In addition, the core-shell particles according to the invention can optionally comprise further shells, although for the purposes of the present invention those core-shell particles which consist of a core, a first shell and preferably a second shell have proven particularly useful. The term “core-shell particles” is best known from the prior art and, in the context of the present invention, denotes polymers which can be obtained by multi-stage emulsion polymerization. This method has long been known in the prior art and is carried out and explained, for example, in Houben-Weyl, Volume E20, Part 2 (1987), p. 1150 ff. The person skilled in the art can also obtain further valuable information from the publications US Pat. No. 3,793,402, DE 41 21 652 A1, DE 41 36 993 A1, EP 828 772 A1, the disclosure of which is hereby expressly incorporated by reference.
Im Rahmen der vorliegenden Erfindung weist der Kern, bezogen auf sein Gesamtgewicht, mindestens 75 Gew.-% (Meth)acrylat- Wiederholungseinheiten auf.In the context of the present invention, the core, based on its total weight, has at least 75% by weight of (meth) acrylate repeating units.
Dabei bezeichnen im Rahmen der vorliegenden Erfindungen die Schreibweise "(Meth)acrylate" Acrylate, Methacrylate sowie Mischungen aus beiden. Sie umfassen somit Verbindungen, welche mindestens eine Gruppe der folgenden Formel aufweisenIn the context of the present inventions, the notation “(meth) acrylates” denotes acrylates, methacrylates and mixtures of the two. They thus comprise compounds which have at least one group of the following formula
wobei R Wasserstoff oder einen Methylrest kennzeichnet. Zu ihnen gehören insbesondere Alkylacrylate und/oder Alkylmethacrylate. where R denotes hydrogen or a methyl radical. They include, in particular, alkyl acrylates and / or alkyl methacrylates.
Vorzugsweise umfasst der Kern, jeweils bezogen auf sein Gesamtgewicht, A)50,0 bis 99,9 Gew.-%, zweckmäßigerweise 60,0 bis 99,9 Gew.-%, vorzugsweise 75,0 bis 99,9 Gew.-%, besonders bevorzugt 80,0 bis 99,0 Gew.-%, insbesondere 85,0 bis 99,0 Gew.- %, Alkylmethacrylat- Wiederholungseinheiten mit 1 bis 20, vorzugsweise 1 bis 12, insbesondere 1 bis 8, Kohlenstoffatomen im Alkylrest,The core preferably comprises, based in each case on its total weight, A) 50.0 to 99.9% by weight, suitably 60.0 to 99.9% by weight, preferably 75.0 to 99.9% by weight , particularly preferably 80.0 to 99.0% by weight, in particular 85.0 to 99.0% by weight, alkyl methacrylate repeating units with 1 to 20, preferably 1 to 12, in particular 1 to 8 carbon atoms in the alkyl radical,
B) 0,0 bis 40,0 Gew.-%, vorzugsweise 0,0 bis 24,9 Gew.-%, zweckmäßigerweise 1 ,0 bis 29,9 Gew.-% insbesondere 1 ,0 bis 14,9 Gew.- %, Alkylacrylat-Wiederholungseinheiten mit 1 bis 20, vorzugsweise 1 bis 12, besonders bevorzugt 1 bis 8, insbesondere 1 bis 4, Kohlenstoffatomen im Alkylrest, C) 0,1 bis 2,0 Gew.-% vernetzende Wiederholungseinheiten und D)0,0 bis 8,0 Gew.-% styrolische Wiederholungseinheiten der allgemeinen Formel (I)B) 0.0 to 40.0% by weight, preferably 0.0 to 24.9% by weight, suitably 1.0 to 29.9% by weight, in particular 1.0 to 14.9% by weight %, Alkyl acrylate repeat units with 1 to 20, preferably 1 to 12, particularly preferably 1 to 8, in particular 1 to 4, carbon atoms in the alkyl radical, C) 0.1 to 2.0% by weight of crosslinking repeat units and D) 0, 0 to 8.0% by weight of styrene repeat units of the general formula (I)
wobei sich die angegebenen Gewichtsprozente vorzugsweise zu 100,0 Gew.-% ergänzen.the stated percentages by weight preferably adding up to 100.0% by weight.
Dabei sind die Verbindungen A), B), C) und D) natürlich voneinander verschieden, insbesondere umfassen die Verbindungen A) und B) keine vernetzenden Monomere C).The compounds A), B), C) and D) are of course different from one another, in particular the compounds A) and B) do not comprise any crosslinking monomers C).
Die Reste R1 bis R5 bezeichnen jeweils unabhängig voneinander Wasserstoff, ein Halogen, insbesondere Fluor, Chlor oder Brom, oder eine Alkylgruppe mit 1 bis 6 Kohlenstoff atomen, vorzugsweise Wasserstoff. Der Rest R6 kennzeichnet Wasserstoff oder eine Alkylgruppe mit 1 bis 6 Kohlenstoff atomen, vorzugsweise Wasserstoff. Besonders geeignete Alkylgruppen mit 1 bis 6 Kohlestoffatomen sind Methyl-, Ethyl-, n-Propyl-, iso-Propyl-, n-Butyl-, sec-Butyl-, tert.-Butyl-, n-Pentyl-, n-Hexylgruppen sowie Cyclopentyl- und Cyclohexylgruppen. Somit umfassen styrolische Wiederholungseinheiten der allgemeinen Formel (I) wiederkehrende Struktureinheiten, welche durch Polymerisation von Monomeren der allgemeinen Formel (la) erhältlich sind.The radicals R 1 to R 5 each independently denote hydrogen, a halogen, in particular fluorine, chlorine or bromine, or an alkyl group having 1 to 6 carbon atoms, preferably hydrogen. The radical R 6 denotes hydrogen or an alkyl group with 1 to 6 carbon atoms, preferably hydrogen. Particularly suitable alkyl groups with 1 to 6 carbon atoms are methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl groups and Cyclopentyl and cyclohexyl groups. Styrene repeat units of the general formula (I) thus comprise recurring structural units which can be obtained by polymerizing monomers of the general formula (Ia).
Geeignete Monomere der allgemeinen Formel (la) umfassen insbesondere Styrol, substituierte Styrole mit einem Alkylsubstituenten in der Seitenkette, wie beispielsweise -Methylstyrol und α-Ethylstyrol, substituierte Styrole mit einem Alkylsubstituenten an dem Ring, wie beispielsweise Vinyltoluo! und p-Methylstyrol, halogenierte Styrole, wie beispielsweise Monochlorstyrole, Dichlorstyrole, Tribromstyrole und Tetrabromstyrole.Suitable monomers of the general formula (Ia) include, in particular, styrene, substituted styrenes with an alkyl substituent in the side chain, such as, for example, methylstyrene and α-ethylstyrene, substituted styrenes with an alkyl substituent on the ring, such as, for example, vinyl toluo! and p-methylstyrene, halogenated styrenes such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes.
Unter den oben erwähnten Alkylmethacrylat-Wiederholungseinheiten (A) werden wiederkehrende Struktureinheiten verstanden, welche durch Polymerisation von Estern der Methacrylsäure erhältlich sind. Geeignete Ester der Methacrylsäure umfassen insbesondere Methylmethacrylat, Ethylmethacrylat, Propylmethacrylat, Isopropylmethacrylat, n- Butylmethacrylat, sec-Butylmethacrylat, tert-Butylmethacrylat, Pentylmethacrylat, Hexylmethacrylat, Heptylmethacrylat, Octylmethacrylat, 2-Octylmethacrylat, Ethylhexylmethacrylat, Nonylmethacrylat, 2-Methyl- octylmethacrylat, 2-tert.-Butylheptylmethacrylat, 3-iso- Propylheptylmethacrylat, Decylmethacrylat, Undecylmethacrylat, 5- Methylundecylmethacrylat, Dodecylmethacrylat, 2- Methyldodecylmethacrylat, Tridecylmethacrylat, 5- Methyltridecylmethacrylat, Tetradecylmethacrylat, Pentadecylmethacrylat, Hexadecylmethacrylat, 2-Methylhexadecylmethacrylat, Heptadecylmethacrylat, 5-iso-Propylheptadecylmethacrylat, 5- Ethyloctadecylmethaciγlat, Octadecylmethacrylat, Nonadecylmethacrylat, Eicosylmethacrylat, Cycloalkylmethacrylate, wie beispielsweise Cyclopentylmethacrylat, Cyclohexylmethacrylat, 3-Vinyl-2-butyl- cyclohexylmethacrylat, Cycloheptylmethacrylat, Cyclooctylmethacrylat, Bornylmethacrylat und Isobomylmethacrylat.The alkyl methacrylate repeating units (A) mentioned above are taken to mean repeating structural units which can be obtained by polymerizing esters of methacrylic acid. Suitable esters of methacrylic acid include in particular methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-octyl methacrylate, non-ethylhexyl methacrylate, 2-ethylhexyl methacrylate, tert-butylheptyl methacrylate, 3-iso-propylheptyl methacrylate, decyl methacrylate, undecyl methacrylate, 5-methylundecyl methacrylate, dodecyl methacrylate, 2-methyldodecyl methacrylate, tridecyl methacrylate, 5-methyltridecyl methacrylate, tetradecyl methacrylate, pentadecyl methacrylate Hexadecyl, 2-Methylhexadecylmethacrylat, heptadecyl methacrylate, 5-iso-Propylheptadecylmethacrylat, 5- Ethyloctadecylmethaciγlat, octadecyl methacrylate, nonadecyl methacrylate, eicosyl methacrylate, cycloalkyl methacrylates, such as cyclopentyl, cyclohexyl, 3-vinyl-2-butyl cyclohexyl methacrylate, Cycloheptylmethacrylat, Cyclooctylmethacrylat, bornyl methacrylate and isobornyl methacrylate.
Gemäß einer besonders bevorzugten Ausführungsform der vorliegenden Erfindung enthält der Kern, bezogen auf sein Gesamtgewicht, mindestens 50 Gew.-%, zweckmäßigerweise mindestens 60 Gew.-%, vorzugsweise mindestens 75 Gew.-%, insbesondere mindestens 85 Gew.-% Methylmethacrylat-Wiederholungseinheiten.According to a particularly preferred embodiment of the present invention, the core, based on its total weight, contains at least 50% by weight, suitably at least 60% by weight, preferably at least 75% by weight, in particular at least 85% by weight, of methyl methacrylate repeating units ,
Unter den oben erwähnten Alkylacrylat-Wiederholungseinheiten (B) werden wiederkehrende Struktureinheiten verstanden, welche durch Polymerisation von Estern der Acrylsäure erhältlich sind. Geeignete Ester der Acrylsäure umfassen insbesondere Methylacrylat, Ethylacrylat, Propylacrylat, Isopropylacrylat, n-Butylacrylat, sec-Butylacrylat, tert- Butylacrylat, Pentylacrylat, Hexylacrylat, Heptylacrylat, Octylacrylat, 2- Octylacrylat, Ethyl hexylacrylat, Nonylacrylat, 2-Methyl-octylacrylat, 2-tert- Butylheptylacrylat, 3-iso-Propylheptylacrylat, Decylacrylat, Undecylacrylat, 5-Methylundecylacrylat, Dodecylacrylat, 2-Methyldodecylacrylat, Tridecylacrylat, 5-Methyltridecylacrylat, Tetradecylacrylat, Pentadecylacrylat, Hexadecylacrylat, 2-Methylhexadecylacrylat, Heptadecylacrylat, 5-iso-Propylheptadecylacrylat, 5-Ethyloctadecylacrylat, Octadecylacrylat, Nonadecylacrylat, Eicosylacrylat, Cycloalkylacrylate, wie beispielsweise Cyclopentylacrylat, Cyclohexylacrylat, 3-Vinyl-2-butyl- cyclohexylacrylat, Cycloheptylacrylat, Cyclooctylacrylat, Bomylacrylat und Isobornylacrylat. Unter den oben erwähnten vernetzenden-Wiederholungseinheiten (C) werden wiederkehrende Struktureinheiten verstanden, welche durch Polymerisation von vernetzenden Monomeren erhältlich sind. Geeignete vernetzende Monomere umfassen insbesondere alle die Verbindungen, welche in der Lage sind, unter den vorliegenden Polymerisationsbedingungen eine Vernetzung herbeizuführen. Hierzu gehören insbesondereThe above-mentioned alkyl acrylate repeating units (B) are understood to mean recurring structural units which can be obtained by polymerizing esters of acrylic acid. Suitable esters of acrylic acid include in particular methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-octyl acrylate, ethyl hexyl acrylate, 2-methyl acrylate, 2-ethyl acrylate, 2-methyl acrylate, 2-ethyl acrylate, 2-ethyl acrylate, 2-ethyl acrylate, 2-ethyl acrylate, -tert Butylheptylacrylat, 3-iso-propylheptyl, decyl, undecyl, 5-Methylundecylacrylat, dodecyl acrylate, 2-Methyldodecylacrylat, tridecyl, 5-Methyltridecylacrylat, tetradecyl, pentadecyl, hexadecyl, 2-Methylhexadecylacrylat, Heptadecylacrylat, 5-iso-Propylheptadecylacrylat, 5 Ethyl octadecyl acrylate, octadecyl acrylate, nonadecyl acrylate, eicosyl acrylate, cycloalkyl acrylates, such as, for example, cyclopentyl acrylate, cyclohexyl acrylate, 3-vinyl-2-butylcyclohexyl acrylate, cycloheptyl acrylate, cyclooctyl acrylate, and cyclooctyl acrylate. The above-mentioned crosslinking repeat units (C) are taken to mean recurring structural units which can be obtained by polymerizing crosslinking monomers. Suitable crosslinking monomers include in particular all the compounds which are able to bring about crosslinking under the present polymerization conditions. These include in particular
(a) Difunktionelle (Meth)acrylate, vorzugsweise Verbindungen der allgemeinen Formel:(a) difunctional (meth) acrylates, preferably compounds of the general formula:
R RR R
I II I
H2C=C— CO— O— (CH2)n— O— CO— C=CH2 worin R Wasserstoff oder Methyl ist und n eine positive ganze Zahl größer gleich 2, vorzugsweise zwischen 3 und 20 bezeichnet, insbesondere Di(meth)acrylate des Propandiols, Butandiols, Hexandiols, Octandiols, Nonandiols, Decandiols und des Eicosandiols;H 2 C = C - CO - O - (CH 2 ) n - O - CO - C = CH 2 where R is hydrogen or methyl and n denotes a positive integer greater than or equal to 2, preferably between 3 and 20, in particular Di ( meth) acrylates of propanediol, butanediol, hexanediol, octanediol, nonanediol, decanediol and eicosanediol;
Verbindungen der allgemeinen Formel:Compounds of the general formula:
worin R Wasserstoff oder Methyl ist und n eine positive ganze Zahl zwischen 1 und 14 bedeutet, insbesondere Di(meth)acrylate des Ethylenglycols, Diethylenglycols, Triethylenglycols, Tetraethylenglycols, Dodecaethylenglycols, Tetradecaethylenglycols, Propylenglycols, Dipropylglycols und des Tetradecapropylenglycols. where R is hydrogen or methyl and n is a positive integer between 1 and 14, in particular di (meth) acrylates of ethylene glycol, diethylene glycol, triethylene glycols, tetraethylene glycols, dodecaethylene glycols, tetradecaethylene glycols, propylene glycols, dipropyl glycols and tetradecapropylene glycols.
Glycerindi(meth)acrylat, 2,2'- Bis[p-(γ-methacryloxy-ß-hydroxypropoxy)- phenylpropan] oder Bis-GMA, Biphenol-A-dimethacrylat, Neopentylglycoldi(meth)acrylat, 2,2'-Di(4- methacryloxypolyethoxyphenyl)propan mit 2 bis 10 Ethoxygruppen pro Molekül und 1 ,2-Bis(3-methacryloxy-2- hydroxypropoxy)butan.Glycerol di (meth) acrylate, 2,2'- bis [p- (γ-methacryloxy-β-hydroxypropoxy) phenylpropane] or bis-GMA, biphenol-A-dimethacrylate, neopentyl glycol di (meth) acrylate, 2,2'-di (4- methacryloxypolyethoxyphenyl) propane with 2 to 10 ethoxy groups per molecule and 1, 2-bis (3-methacryloxy-2-hydroxypropoxy) butane.
(b) Tri- oder polyfunktionelle (Meth)acrylate, insbesondere Trimethylolpropantri(meth)acrylate und Pentaerythritpltetra(meth)acrylat.(b) Trifunctional or polyfunctional (meth) acrylates, in particular trimethylolpropane tri (meth) acrylates and pentaerythritol tetra (meth) acrylate.
(c) Pfropfvernetzer mit mindestens zwei unterschiedlich reaktiven C-C- Doppelbindungen, insbesondere Allylmethacrylat und Allylacrylat;(c) graft crosslinking agent with at least two differently reactive C-C double bonds, in particular allyl methacrylate and allyl acrylate;
(d) aromatische Vernetzer, insbesondere 1 ,2-Divinylbenzol, 1 ,3- Divinylbenzol und 1 ,4-Divinylbenzol.(d) aromatic crosslinkers, in particular 1,2-divinylbenzene, 1,3-divinylbenzene and 1,4-divinylbenzene.
Vorzugsweise erfolgt die Auswahl der Gewichtsanteile der Bestandteile A) bis D) des Kerns derart, dass der Kern eine Glasübergangstemperatur Tg von mindestens 10 °C, vorzugsweise von mindestens 30 °C, aufweist. Dabei kann die Glasübergangstemperatur Tg des Polymerisates in bekannter Weise mittels Differential Scanning Calorimetry (DSC) ermittelt werden. Weiterhin kann die Glasübergangstemperatur Tg auch mittels der Fox-Gleichung näherungsweise voraus berechnet werden. Nach Fox T. G., Bull. Am. Physics Soc. 1, 3, Seite 123 (1956) gilt:The proportions by weight of constituents A) to D) of the core are preferably selected such that the core has a glass transition temperature Tg of at least 10 ° C., preferably of at least 30 ° C. The glass transition temperature Tg of the polymer can be determined in a known manner by means of differential scanning calorimetry (DSC). Furthermore, the glass transition temperature Tg can also be calculated approximately in advance using the Fox equation. According to Fox T. G., Bull. Am. Physics Soc. 1, 3, page 123 (1956) applies:
χ„χ "
• + - - + ... + -• + - - + ... + -
Tg Tgx Tg2 Tgn Tg Tg x Tg 2 Tg n
wobei xn für den Massebruch (Gew.-%/100) des Monomeren n steht und Tgn die Glasübergangstemperatur in Kelvin des Homopolymeren des Monomeren n bezeichnet. Weitere hilfreiche Hinweise kann der Fachmann dem Polymer Handbook 2nd Edition, J. Wiley & Sons, New York (1975) entnehmen, welche Tg-Werte für die geläufigsten Homopolymerisate angibt. Die erste Schale der erfindungsgemäßen Kern-Schale-Teilchen weist eine Glasübergangstemperatur kleiner 30° C, vorzugsweise kleiner 10 °C, insbesondere im Bereich von 0 bis -75 °C, auf. Dabei kann die Glasübergangstemperatur Tg des Polymerisates, wie vorstehend bereits erwähnt mittels Differential Scanning Calorimetry (DSC) ermittelt und/oder mittels der Fox-Gleichung näherungsweise voraus berechnet werden.where x n is the mass fraction (wt .-% / 100), n of the monomer and Tg n is the glass transition temperature in Kelvin of the homopolymer of the monomer n denotes. Other helpful hints can the expert Polymer Handbook 2 nd Edition see, J. Wiley & Sons, New York (1975), which gives Tg values for the most common homopolymers. The first shell of the core-shell particles according to the invention has a glass transition temperature of less than 30 ° C., preferably less than 10 ° C., in particular in the range from 0 to -75 ° C. As already mentioned above, the glass transition temperature Tg of the polymer can be determined by means of differential scanning calorimetry (DSC) and / or can be calculated approximately in advance using the Fox equation.
Die erste Schale umfasst, bezogen auf ihr Gesamtgewicht, die nachstehenden Bestandteile:The first shell, based on its total weight, contains the following components:
E) 92,0 bis 98,0 Gew.-% (Meth)acrylat-Wiederholungseinheiten undE) 92.0 to 98.0% by weight of (meth) acrylate repeating units and
F) 2,0 bis 8,0 Gew.-% styrolische Wiederholungseinheiten der allgemeinen Formel (I), wobei sich die Gewichtsprozente zu 100 Gew.-% addieren.F) 2.0 to 8.0% by weight of styrene repeat units of the general formula (I), the percentages by weight adding up to 100% by weight.
Im Rahmen einer ganz besonders bevorzugten Ausführungsform der vorliegenden Erfindung umfasst die erste SchaleIn the context of a very particularly preferred embodiment of the present invention, the first shell comprises
E-1) 90,0 bis 97,9 Gew.-% Alkylacrylat-Wiederholungseinheiten mit 3 bis 8 Kohlenstoffatomen im Alkylrest und/oder Alkylmethacrylat- Wiederhoiungseinheiten mit 7 bis 14 Kohlenstoffatomen im Alkylrest, insbesondere Butylacrylat- und/oderDodecylmethacrylat- Wiederholungseinheiten, undE-1) 90.0 to 97.9% by weight alkyl acrylate repeat units with 3 to 8 carbon atoms in the alkyl radical and / or alkyl methacrylate repeat units with 7 to 14 carbon atoms in the alkyl radical, in particular butyl acrylate and / or dodecyl methacrylate repeat units, and
E-2) 0,1 bis 2,0 Gew.-% vernetzende Wiederholungseinheiten,E-2) 0.1 to 2.0% by weight of crosslinking repeat units,
F) 2,0 bis 8,0 Gew.-% styrolische Wiederholungseinheiten der allgemeinen Formel (I), wobei sich die Gewichtsteile vorzugsweise zu 100,0 Gew.-Teilen addieren.F) 2.0 to 8.0% by weight of styrene repeat units of the general formula (I), the parts by weight preferably adding up to 100.0 parts by weight.
Dabei sind die Verbindungen E-1), E-2) und F) natürlich voneinander verschieden, insbesondere umfassen die Verbindungen E-1) keine vernetzenden Monomere E-2). Die gegebenenfalls vorhandene zweite Schale umfasst, bezogen auf ihrThe compounds E-1), E-2) and F) are of course different from one another, in particular the compounds E-1) do not comprise any crosslinking monomers E-2). The second shell, if present, includes, based on it
Gesamtgewicht, mindestens 75 Gew.-% (Meth)acrylat-Total weight, at least 75% by weight of (meth) acrylate
Wiederholungseinheiten. Sie enthält vorzugsweiseRepeating units. It preferably contains
G)50,0 bis 100,0 Gew.-%, zweckmäßigerweise 60,0 bis 100,0 Gew.-%, besonders bevorzugt 75,0 bis 100,0 Gew.-%, insbesondere 85,0 bis 99,5 Gew.-%, Alkylmethacrylat-Wiederholungseinheiten mit 1 bis 20, vorzugsweise 1 bis 12, insbesondere 1 bis 8, Kohlenstoffatomen im Alkylrest,G) 50.0 to 100.0% by weight, advantageously 60.0 to 100.0% by weight, particularly preferably 75.0 to 100.0% by weight, in particular 85.0 to 99.5% by weight .-%, alkyl methacrylate repeating units with 1 to 20, preferably 1 to 12, in particular 1 to 8, carbon atoms in the alkyl radical,
H)0,0 bis 40,0 Gew.-%, vorzugsweise 0,0 bis 25,0 Gew.-%, insbesondere 0,1 bis 15,0 Gew.- %, Alkylacrylat-Wiederholungseinheiten mit 1 bis 20, vorzugsweise 1 bis 12, insbesondere 1 bis 8, Kohlenstoffatomen im Alkylrest,H) 0.0 to 40.0% by weight, preferably 0.0 to 25.0% by weight, in particular 0.1 to 15.0% by weight, alkyl acrylate repeat units with 1 to 20, preferably 1 to 12, in particular 1 to 8, carbon atoms in the alkyl radical,
I) 0,0 bis 10,0 Gew.-%, vorzugsweise 0,0 bis 8,0 Gew.-% styrolische Wiederholungseinheiten der allgemeinen Formel (I), wobei dich die angegebenen Gewichtsprozente vorzugsweise zu 100,0I) 0.0 to 10.0% by weight, preferably 0.0 to 8.0% by weight, of styrene repeat units of the general formula (I), the percentages by weight preferably being 100.0
Gew.-% addieren.Add% by weight.
Gemäß einer besonders bevorzugten Ausführungsform der vorliegenden Erfindung enthält die zweite Schale, bezogen auf ihr Gesamtgewicht, mindestens 50 Gew.-%, zweckmäßigerweise mindestens 60 Gew.-%, vorzugsweise mindestens 75 Gew.-%, insbesondere mindestens 85 Gew.- % Methylmethacrylat-Wiederholungseinheiten.According to a particularly preferred embodiment of the present invention, the second shell contains, based on its total weight, at least 50% by weight, expediently at least 60% by weight, preferably at least 75% by weight, in particular at least 85% by weight of methyl methacrylate. repeating units.
Weiterhin erfolgt die Auswahl der Bestandteile der zweiten Schale günstigerweise derart, dass die zweite Schale eine Glasübergangstemperatur Tg von mindestens 10 °C, vorzugsweise von mindestens 30 °C, aufweist. Dabei kann die Glasübergangstemperatur Tg des Polymerisates, wie vorstehend bereits erwähnt mittels Differential Scanning Calorimetry (DSC) ermittelt und/oder mittels der Fox-Gleichung näherungsweise voraus berechnet werden. Der Gesamtradius des Kern-Schale-Teilchens inklusive der gegebenenfalls vorhandenen zweiten Schale liegt im Bereich von größer 160 bis 240 nm, vorzugsweise im Bereich von 170 bis 220 nm, insbesondere im Bereich von 175 bis 210 nm. Dabei wird der Gesamtradius gemäß dem Coulter-Verfahren bestimmt. Dieses in der Literatur bekannte Verfahren zur Partikelgrößen-Bestimmung beruht auf der Messung des elektrischen Wiederstands, der sich beim Durchtritt von Teilchen durch eine enge Messöffnung in charakteristischer Weise ändert. Weitere Details können beispielsweise Nachr. Chem. Tech. Lab. 43, 553- 566 (1995) entnommen werden.Furthermore, the constituents of the second shell are advantageously selected in such a way that the second shell has a glass transition temperature Tg of at least 10 ° C., preferably of at least 30 ° C. As already mentioned above, the glass transition temperature Tg of the polymer can be determined by means of differential scanning calorimetry (DSC) and / or can be calculated approximately in advance using the Fox equation. The total radius of the core-shell particle, including the optionally present second shell, is in the range from greater than 160 to 240 nm, preferably in the range from 170 to 220 nm, in particular in the range from 175 to 210 nm. The total radius is determined according to the Coulter Procedure determined. This method for particle size determination, which is known in the literature, is based on the measurement of the electrical resistance, which changes in a characteristic manner when particles pass through a narrow measurement opening. Further details can be found, for example, in Chem. Tech. Lab. 43, 553-566 (1995).
Weiterhin hat es sich für die Zwecke der vorliegenden Erfindung als ganz besonders günstig erwiesen, dass, jeweils bezogen auf seinFurthermore, for the purposes of the present invention, it has proven to be particularly favorable that, in each case, based on
Gesamtgewicht, i) der Kern 5,0 bis 50,0 Gew.-%, vorzugsweise 15,0 bis 50,0 Gew.-%, zweckmäßigerweise 25,0 bis 45,0 Gew.-%, insbesondere 30,0 bis 40,0Total weight, i) the core 5.0 to 50.0% by weight, preferably 15.0 to 50.0% by weight, advantageously 25.0 to 45.0% by weight, in particular 30.0 to 40 , 0
Gew.-%, ii) die erste Schale 20,0 bis 75,0 Gew.-%, vorzugsweise 30,0 bis 60,0% By weight, ii) the first shell 20.0 to 75.0% by weight, preferably 30.0 to 60.0
Gew.-%, zweckmäßigerweise 35,0 bis 55,0 Gew.-%, insbesondere 40,0 bis 50 Gew.-%, und iii)die zweite Schale 0,0 bis 50,0 Gew.-%, vorzugsweise 5,0 bis 40,0% By weight, expediently 35.0 to 55.0% by weight, in particular 40.0 to 50% by weight, and iii) the second shell 0.0 to 50.0% by weight, preferably 5, 0 to 40.0
Gew.-%, zweckmäßigerweise 10,0 bis 30,0 Gew.-%, insbesondere 15,0 bis 25,0 Gew.-%, ausmacht, wobei sich die Gewichtsprozente vorzugsweise zu 100,0 Gew.- % addieren.% By weight, expediently 10.0 to 30.0% by weight, in particular 15.0 to 25.0% by weight, the weight percentages preferably adding up to 100.0% by weight.
Die Herstellung der erfindungsgemäßen Kern-Schale-Teilchen kann auf an sich bekannte Weise, beispielsweise mittels mehrstufiger Emulsionspolymerisation erfolgen. Zweckmäßigerweise erfolgt sie durch ein Verfahren, bei welchem man Wasser und Emulgator vorlegt. Dabei enthält die Vorlage vorzugsweise 90,00 bis 99,99 Gew.-Teile Wasser und 0,01 bis 10,00 Gew.-Teile Emulgator, wobei sich die angegebenen Gewichtsteile günstigerweise zu 100,00 Gewichtsteilen addieren.The core-shell particles according to the invention can be produced in a manner known per se, for example by means of multi-stage emulsion polymerization. It is expediently carried out by a process in which water and emulsifier are initially introduced. The template preferably contains 90.00 to 99.99 parts by weight of water and 0.01 to 10.00 parts by weight of emulsifier Advantageously add parts by weight to 100.00 parts by weight.
Zu dieser Vorlage werden dann schrittweise in der folgenden Reihenfolge b) die Monomere für den Kern in den gewünschten Verhältnissen zugegeben und bis zu einem Umsatz von mindestens 85,0 Gew.-%, vorzugsweise mindestens 90,0 Gew.-%, zweckmäßigerweise mindestens 95,0 Gew.-%, insbesondere mindestens 99 Gew.-%, jeweils bezogen auf ihr Gesamtgewicht, polymerisiert, c) die Monomere für die erste Schale in den gewünschten Verhältnissen zugegeben und bis zu einem Umsatz von mindestens 85,0 Gew.-%, vorzugsweise mindestens 90,0 Gew.-%, zweckmäßigerweise mindestens 95,0 Gew.-%, insbesondere mindestens 99 Gew.-%, jeweils bezogen auf ihr Gesamtgewicht, polymerisiert, d) gegebenenfalls die Monomere für die zweite Schale in den gewünschten Verhältnissen zugegeben und bis zu einem Umsatz von mindestens 85,0 Gew.-%, vorzugsweise mindestens 90,0 Gew.-%, zweckmäßigerweise mindestens 95,0 Gew.-%, insbesondere mindestens 99 Gew.-%, jeweils bezogen auf ihr Gesamtgewicht, polymerisiert.The monomers for the core are then added to this template step by step in the following order b) in the desired ratios and up to a conversion of at least 85.0% by weight, preferably at least 90.0% by weight, advantageously at least 95 , 0% by weight, in particular at least 99% by weight, in each case based on their total weight, polymerized, c) the monomers for the first shell are added in the desired ratios and up to a conversion of at least 85.0% by weight , preferably at least 90.0% by weight, expediently at least 95.0% by weight, in particular at least 99% by weight, in each case based on their total weight, polymerized, d) optionally the monomers for the second shell in the desired ratios added and up to a conversion of at least 85.0% by weight, preferably at least 90.0% by weight, advantageously at least 95.0% by weight, in particular at least 99% by weight, in each case based on their total weight, polymerized.
Dabei bezeichnen Polymere im Sinne der vorliegenden Erfindung Verbindungen, welche im Vergleich mit der jeweiligen Ausgangsverbindung A) bis I), dem sogenannten Monomer, mindestens das zehnfache Molekulargewicht aufweisen.For the purposes of the present invention, polymers refer to compounds which have at least ten times the molecular weight in comparison with the respective starting compound A) to I), the so-called monomer.
Die Verfolgung des Reaktionsfortschrittes der Polymerisation in jeden Schritt kann auf bekannte Weise, beispielsweise gravimetrisch oder mittels Gaschromatographie erfolgen.The progress of the polymerization reaction in each step can be monitored in a known manner, for example gravimetrically or by means of gas chromatography.
Gemäß der vorliegenden Erfindung wird die Polymerisation in den Schritten b) bis d) vorzugsweise bei einer Temperatur im Bereich von 0 bis 120 °C, vorzugsweise im Bereich von 30 bis 100 °C durchgeführt. Dabei haben sich Polymersiationstemperaturen im Bereich von größer 60 bis kleiner 90 °C, zweckmäßigerweise im Bereich von größer 70 bis kleiner 85 °C, vorzugsweise im Bereich von größer 75 bis kleiner 85 °C, als ganz besonders günstig erwiesen.According to the present invention, the polymerization in steps b) to d) is preferably carried out at a temperature in the range from 0 to 120 ° C., preferably in the range from 30 to 100 ° C. Polymerization temperatures in the range from greater than 60 to less than 90 ° C., expediently in the range from greater than 70 to less than 85 ° C., preferably in the range from greater than 75 to less than 85 ° C., have proven to be very particularly favorable.
Die Initiierung der Polymerisation erfolgt mit den für die Emulsionspolymerisation gebräuchlichen Initiatoren. Geeignete organische Initiatoren sind beispielsweise Hydroperoxide, wie tert.-Butyl- Hydroperoxid oder Cumolhydroperoxid. Geeignete anorganische Initiatoren sind Wasserstoffperoxid sowie die Alkalimetall- und die Ammoniumsalze der Peroxodischwefelsäure, insbesondere Natrium- und Kaliumperoxodisulfat. Geeignete Redox-Initiatorsysteme sind beispielsweise Kombinationen von tertiären Aminen mit Peroxiden oder Natriumdisulfit und Alkalimetall- und die Ammoniumsalze der Peroxodischwefelsäure, insbesondere Natrium- und Kaliumperoxodisulfat, oder besonders bevorzugt Peroxide. Weitere Details können der Fachliteratur, insbesondere H. Rauch-Puntigam, Th. Völker, "Acryl- und Methacrylverbindungen", Springer, Heidelberg, 1967 oder Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 1 , Seiten 386ff, J. Wiley, NewYork, 1978 entnommen werden. Im Rahmen der vorliegenden Erfindung ist der Einsatz von organischen und/oder anorganischen Initiatoren besonders bevorzugt.The polymerization is initiated using the initiators customary for emulsion polymerization. Suitable organic initiators are, for example, hydroperoxides, such as tert-butyl hydroperoxide or cumene hydroperoxide. Suitable inorganic initiators are hydrogen peroxide and the alkali metal and ammonium salts of peroxodisulfuric acid, especially sodium and potassium peroxodisulfate. Suitable redox initiator systems are, for example, combinations of tertiary amines with peroxides or sodium disulfite and alkali metal and the ammonium salts of peroxodisulfuric acid, in particular sodium and potassium peroxodisulfate, or particularly preferably peroxides. Further details can be found in the specialist literature, in particular H. Rauch-Puntigam, Th. Völker, "Acryl- und Methacrylverbindungen", Springer, Heidelberg, 1967 or Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 1, pages 386ff, J. Wiley, NewYork, 1978. In the context of the present invention, the use of organic and / or inorganic initiators is particularly preferred.
Die genannten Initiatoren können sowohl einzeln als auch in Mischung verwendet werden. Sie werden vorzugsweise in einer Menge von 0,05 bis 3,0 Gew.-%, bezogen auf das Gesamtgewicht der Monomere der jeweiligen Stufe, eingesetzt. Man kann auch bevorzugt die Polymerisation mit einem Gemisch verschiedener Polymerisationsinitiatoren unterschiedlicher Halbwertzeit durchführen, um den Radikalstrom im Verlauf der Polymerisation sowie bei verschiedenen Polymerisationstemperaturen konstant zu halten. Die Stabilisierung des Ansatzes erfolgt vorzugsweise mittels Emulgatoren und/oder Schutzkolloiden. Bevorzugt wird die Stabilisierung durch Emulgatoren, um eine niedrige Dispersionsviskosität zu erhalten. Die Gesamtmenge an Emulgator beträgt vorzugsweise 0,1 bis 5 Gew.-%, insbesondere 0,5 bis 3 Gew.-%, bezogen auf das Gesamtgewicht der Monomere A) bis I). Besonders geeignete Emulgatoren sind anionische oder nichtionische Emulgatoren oder deren Mischungen, insbesondere:The initiators mentioned can be used either individually or in a mixture. They are preferably used in an amount of 0.05 to 3.0% by weight, based on the total weight of the monomers in the respective stage. The polymerization can also preferably be carried out with a mixture of different polymerization initiators with different half-lives in order to keep the radical stream constant during the course of the polymerization and at different polymerization temperatures. The batch is preferably stabilized by means of emulsifiers and / or protective colloids. Stabilization by emulsifiers is preferred in order to obtain a low dispersion viscosity. The total amount of emulsifier is preferably 0.1 to 5% by weight, in particular 0.5 to 3% by weight, based on the total weight of the monomers A) to I). Particularly suitable emulsifiers are anionic or nonionic emulsifiers or mixtures thereof, in particular:
* Alkylsulfate, vorzugsweise solche mit 8 bis 18 Kohlenstoffatomen im Alkylrest, Alkyl- und Alkylarylethersulfate mit 8 bis 18 Kohlenstoffatomen im Alkylrest und 1 bis 50 Ethylenoxideinheiten;* Alkyl sulfates, preferably those with 8 to 18 carbon atoms in the alkyl radical, alkyl and alkylaryl ether sulfates with 8 to 18 carbon atoms in the alkyl radical and 1 to 50 ethylene oxide units;
* Sulfonate, vorzugsweise Alkylsulfonate mit 8 bis 18 Kohlenstoffatomen im Alkylrest, Alkylarylsulfonate mit 8 bis 18 Kohlenstoffatomen im Alkylrest, Ester und Halbester der Sulfobemsteinsäure mit einwertigen Alkoholen oder Alkylphenolen mit 4 bis 15 Kohlenstoffatomen im Alkylrest; gegebenenfalls können diese Alkohole oder Alkylphenole auch mit 1 bis 40 Ethylenoxideinheiten ethoxyliert sein;* Sulfonates, preferably alkyl sulfonates with 8 to 18 carbon atoms in the alkyl radical, alkylarylsulfonates with 8 to 18 carbon atoms in the alkyl radical, esters and half esters of sulfosuccinic acid with monohydric alcohols or alkylphenols with 4 to 15 carbon atoms in the alkyl radical; optionally these alcohols or alkylphenols can also be ethoxylated with 1 to 40 ethylene oxide units;
* Phosphorsäureteilester und deren Alkali- und Ammoniumsalze, vorzugsweise Alkyl- und Alkyiarylphosphate mit 8 bis 20 Kohlenstoff atomen im Alkyl- bzw. Alkylarylrest und 1 bis 5 Ethylenoxideinheiten;* Partial phosphoric acid esters and their alkali and ammonium salts, preferably alkyl and alkylaryl phosphates with 8 to 20 carbon atoms in the alkyl or alkylaryl radical and 1 to 5 ethylene oxide units;
* Alkylpolyglykolether, vorzugsweise mit 8 bis 20 Kohlenstoffatomen im Alkylrest und 8 bis 40 Ethylenoxideinheiten;* Alkyl polyglycol ethers, preferably with 8 to 20 carbon atoms in the alkyl radical and 8 to 40 ethylene oxide units;
* Alkylarylpolyglykolether, vorzugsweise mit 8 bis 20 Kohlenstoffatomen im Alkyl- bzw. Alkylarylrest und 8 bis 40 Ethylenoxideinheiten;* Alkylaryl polyglycol ethers, preferably having 8 to 20 carbon atoms in the alkyl or alkylaryl radical and 8 to 40 ethylene oxide units;
* Ethylenoxid/Propylenoxid-Copolymere, vorzugsweise Blockcopolymere, günstigerweise mit 8 bis 40 Ethylenoxid- bzw. Propylenoxideinheiten. Erfindungsgemäß bevorzugt werden Gemische aus anionischem Emulgator und nichtionischen Emulgator eingesetzt. Dabei haben sich Gemische aus einem Ester oder Halbester der Sulfobemsteinsäure mit einwertigen Alkoholen oder Alkylphenolen mit 4 bis 15 Kohlenstoffatomen im Alkylrest als anionischem Emulgator und einem Alkylpolyglykolether, bevorzugt mit 8 bis 20 Kohlenstoffatomen im Alkylrest und 8 bis 40 Ethylenoxideinheiten, als nichtionischem Emulgator in einem Gewichtsverhältnis von 8 : 1 bis 1 : 8 ganz besonders bewährt.* Ethylene oxide / propylene oxide copolymers, preferably block copolymers, advantageously with 8 to 40 ethylene oxide or propylene oxide units. Mixtures of anionic emulsifier and nonionic emulsifier are preferably used according to the invention. Mixtures of an ester or half-ester of sulfosuccinic acid with monohydric alcohols or alkylphenols with 4 to 15 carbon atoms in the alkyl radical as an anionic emulsifier and an alkyl polyglycol ether, preferably with 8 to 20 carbon atoms in the alkyl radical and 8 to 40 ethylene oxide units, as a nonionic emulsifier in a weight ratio from 8: 1 to 1: 8 especially proven.
Gegebenenfalls können die Emulgatoren auch in Mischung mit Schutzkolloiden eingesetzt werden. Geeignete Schutzkolloide umfassen u. a. teilverseifte Polyvinylacetate, Polyvinylpyrrolidone, Carboxymethyl-, Methyl-, Hydroxyethyl-, Hydroxypropyl-Cellulose, Stärken, Proteine, Poly(meth) acrylsäure, Poly(meth)acrylamid, Polyvinylsulfonsäuren, Melaminformaldehydsulfonate, Naphthalinformaldehydsulfonate, Styrol- Maleinsäure- und Vinylethermaleinsäure-Copolymere. Falls Schutzkolloide eingesetzt werden, erfolgt dies vorzugsweise in einer Menge von 0,01 bis 1 ,0 Gew.-%, bezogen auf die Gesamtmenge der Monomere A) bis I). Die Schutzkolloide können vor dem Start der Polymerisation vorgelegt oder zudosiert werden.If appropriate, the emulsifiers can also be used in a mixture with protective colloids. Suitable protective colloids include u. a. partially saponified polyvinyl acetates, polyvinyl pyrrolidones, carboxymethyl, methyl, hydroxyethyl, hydroxypropyl cellulose, starches, proteins, poly (meth) acrylic acid, poly (meth) acrylamide, polyvinylsulfonic acids, melamine formaldehyde sulfonates, naphthalene formaldehyde sulfonates, styrene-maleic acid and copolyether. If protective colloids are used, this is preferably done in an amount of 0.01 to 1.0% by weight, based on the total amount of monomers A) to I). The protective colloids can be introduced or metered in before the start of the polymerization.
Der Initiator kann vorgelegt oder zudosiert werden. Weiterhin ist es auch möglich, einen Teil des Initiators vorzulegen und den Rest zudosieren.The initiator can be introduced or metered in. Furthermore, it is also possible to introduce part of the initiator and to meter in the rest.
Bevorzugt wird die Polymerisation durch Erhitzen des Ansatzes auf die Polymerisationstemperatur und Zudosierung des Initiators, vorzugsweise in wässriger Lösung, gestartet. Die Dosierungen von Emulgator und Monomeren können separat durch geführt werden oder als Gemisch. Bei der Zudosierung von Gemischen aus Emulgator und Monomer wird so vorgegangen, dass Emulgator und Monomer in einem dem Polymerisationsreaktor vorgeschalteten Mischer vorgemischt werden. Bevorzugt wird der Rest an Emulgator und der Rest an Monomer, welche nicht vorgelegt wurden, nach dem Start der Polymerisation getrennt voneinander zudosiert. Vorzugsweise wird mit der Dosierung 15 bis 35 Minuten nach dem Start der Polymerisation begonnen.The polymerization is preferably started by heating the batch to the polymerization temperature and metering in the initiator, preferably in aqueous solution. The dosages of emulsifier and monomers can be carried out separately or as a mixture. When metering in mixtures of emulsifier and monomer, the procedure is such that the emulsifier and monomer are premixed in a mixer upstream of the polymerization reactor. The remainder of emulsifier and the remainder of monomer are preferred were not submitted, metered in separately from one another after the start of the polymerization. Dosing is preferably started 15 to 35 minutes after the start of the polymerization.
Weiterhin ist es für die Zwecke der vorliegenden Erfindung besonders vorteilhaft, dass die Vorlage ein sogenantes "Saatlatex" enthält, welches vorzugsweise durch Polymersiation von Alkyl(meth)acrylaten erhältlich ist und darüber hinaus günstigerweise einen Teilchenradius, im Bereich von 3,0 bis 20,0 nm aufweist. Diese kleinen Radien können nach einer definierten Aufpolymerisation des Saatlatex, bei der eine Schale um den Saatlatex aufgebaut wird und die Radien der so hergestellten Teilchen nach dem Coulter-Verfahren gemessen wurden, berechnet werden. Dieses in der Literatur bekannte Verfahren zur Partikelgrößen- Bestimmung beruht auf der Messung des elektrischen Wiederstands, der sich beim Durchtritt von Teilchen durch eine enge Messöffnung in charakteristischer Weise ändert. Weitere Details können beispielsweise Nachr. Chem. Tech. Lab. 43, 553-566 (1995) entnommen werden.Furthermore, it is particularly advantageous for the purposes of the present invention that the template contains a so-called "seed latex", which is preferably obtainable by polymerizing alkyl (meth) acrylates and moreover advantageously has a particle radius in the range from 3.0 to 20 0 nm. These small radii can be calculated after a defined polymerisation of the seed latex, in which a shell is built up around the seed latex and the radii of the particles produced in this way were measured using the Coulter method. This method for particle size determination known in the literature is based on the measurement of the electrical resistance, which changes in a characteristic manner when particles pass through a narrow measurement opening. Further details can be found, for example, in Chem. Tech. Lab. 43, 553-566 (1995).
Zu dem Saatlatex werden die Monomerbestandteile des eigentlichen Kerns, d. h. die erste Zusammensetzung, vorzugsweise unter solchen Bedingungen zugegeben, dass die Bildung neuer Teilchen vermieden wird. Dadurch wird das in der ersten Verfahrensstufe entstehende Polymerisat schalenförmig um das Saatlatex herum gelagert. Analog werden die Monomerbestandteile des ersten Schalenmaterials (zweite Zusammensetzung) unter solchen Bedingungen zu dem Emulsionspolymerisat zugegeben, dass die Bildung neuer Teilchen vermieden wird. Dadurch wird das in der zweiten Stufe entstehende Polymerisat schalenförmig um den bestehenden Kern herum gelagert. Diese Vorgeherisweise ist für jede weitere Schale entsprechend zu . - wiederholen. Gemäß einer weiteren bevorzugten Ausführungsform der vorliegenden Erfindung werden die erfindungsgemäßen Kern-Schale-Teilchen durch ein Emulsionspolymerisationsverfahren erhalten werden, bei dem man anstatt des Saatlatexes einen langkettigen, aliphatischen Alkohol, vorzugsweise mit 12 bis 20 Kohlenstoffatomen, emulgiert vorlegt. In einer bevorzugten Ausführungsform dieses Verfahrens wird Stearylalkohol als langkettiger, aliphatischer Alkohol verwendet. Die Kern-Schale-Struktur wird analog zur oben beschriebenen Vorgehensweise durch schrittweise Zugabe und Polymerisation der entsprechenden Monomere unter Vermeidung der Bildung neuer Teilchen erhalten. Weitere Einzelheiten zum Polymerisationsverfahren kann der Fachmann den Patentschriften DE 3343766, DE 3210891 , DE 2850105, DE 2742178 und DE 3701579 entnehmen.The monomer components of the actual core, ie the first composition, are preferably added to the seed latex under conditions such that the formation of new particles is avoided. As a result, the polymer formed in the first stage of the process is stored in a shell-like manner around the seed latex. Analogously, the monomer components of the first shell material (second composition) are added to the emulsion polymer under conditions such that the formation of new particles is avoided. As a result, the polymer produced in the second stage is stored in a shell-like manner around the existing core. This procedure is appropriate for each additional bowl. - to repeat. According to a further preferred embodiment of the present invention, the core-shell particles according to the invention are obtained by an emulsion polymerization process in which, instead of the seed latex, a long-chain, aliphatic alcohol, preferably having 12 to 20 carbon atoms, is initially emulsified. In a preferred embodiment of this process, stearyl alcohol is used as the long-chain, aliphatic alcohol. The core-shell structure is obtained analogously to the procedure described above by stepwise addition and polymerization of the corresponding monomers while avoiding the formation of new particles. The person skilled in the art can obtain further details on the polymerization process from the patents DE 3343766, DE 3210891, DE 2850105, DE 2742178 and DE 3701579.
Unabhängig von der konkreten Vorgehensweise hat es sich jedoch im Rahmen der vorliegenden Erfindung als ganz besonders günstig erwiesen, die zweite und die -dritte Monomermischung nach Maßgabe des Verbrauchs zuzudosieren.Regardless of the specific procedure, however, it has proven to be particularly advantageous in the context of the present invention to meter in the second and third monomer mixtures in accordance with the consumption.
Die Einstellung der Kettenlängen, insbesondere der (Co) Polymerisate der zweiten Schale, kann durch Polymerisation des Monomers bzw. des Monomerengemisches in Gegenwart von Molekulargewichtsreglern erfolgen, wie insbesondere von den dafür bekannten Mercaptanen, wie beispielsweise n-Butylmercaptan, n-Dodecylmercaptan, 2- Mercaptoethanol oder 2-Ethylhexylthioglycolat, Pentaerythrittetrathioglycolat; wobei die Molekulargewichtsregler im allgemeinen in Mengen von 0,05 bis 5 Gew.-% bezogen auf das Monomerengemisch, bevorzugt in Mengen von 0,1 bis 2 Gew.-% und besonders bevorzugt in Mengen von 0,2 bis 1 Gew.-% auf das Monomerengemisch eingesetzt werden (vgl. beispielsweise H. Rauch- Puntigam, Th. Völker, "Acryl- und Methacrylverbindungen", Springer, Heidelberg, 1967; Houben-Weyl, Methoden der organischen Chemie, Bd. XIV/1. Seite 66, Georg Thieme, Heidelberg, 1961 oder Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 1 , Seiten 296ff, J. Wiley, New York, 1978). Bevorzugt wird als Molekulargewichtsregler n- Dodecylmercaptan eingesetzt.The chain lengths, in particular the (co) polymers of the second shell, can be adjusted by polymerizing the monomer or the monomer mixture in the presence of molecular weight regulators, such as, in particular, the mercaptans known for this, such as, for example, n-butyl mercaptan, n-dodecyl mercaptan, 2- Mercaptoethanol or 2-ethylhexylthioglycolate, pentaerythritol tetrathioglycolate; the molecular weight regulators generally in amounts of 0.05 to 5% by weight, based on the monomer mixture, preferably in amounts of 0.1 to 2% by weight and particularly preferably in amounts of 0.2 to 1% by weight be used on the monomer mixture (see, for example, H. Rauch-Puntigam, Th. Völker, "Acryl- und Methacrylverbindungen", Springer, Heidelberg, 1967; Houben-Weyl, Methods of Organic Chemistry, Vol. XIV / 1. Page 66, Georg Thieme, Heidelberg, 1961 or Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 1, pages 296ff, J. Wiley, New York, 1978). The molecular weight regulator used is preferably n-dodecyl mercaptan.
Nach Abschluss der Polymerisation kann zur Restmonomerentfernung in Anwendung bekannter Methoden nachpolymerisiert werden, beispielsweise mittels initiierter Nachpolymerisation.After the polymerization has ended, postpolymerization can be carried out using known methods to remove residual monomers, for example by means of initiated postpolymerization.
Da sich das erfindungsgemäße Verfahren insbesondere zur Herstellung von wässrigen Dispersionen mit hohem Feststoffgehalt größer 50 Gew.-%, bezogen auf das Gesamtgewicht der wässrigen Dispersion, eignet, wählt man die relativen Anteile aller Substanzen zweckmäßigerweise derart, dass das Gesamtgewicht der Monomere, bezogen auf das Gesamtgewicht der wässrigen Dispersion, größer 50,0 Gew.-%, zweckmäßigerweise größer 51 ,0 Gew.-%, vorzugsweise größer 52,0 Gew.-%, ist. Zu den in diesem Zusammenhang zu berücksichtigen Substanzen gehören neben den Monomeren auch alle anderen eingesetzten Substanzen, wie Wasser, Emulgator, Initiator, ggf. Regler und Schutzkolloide usw..Since the process according to the invention is particularly suitable for the production of aqueous dispersions with a high solids content of more than 50% by weight, based on the total weight of the aqueous dispersion, the relative proportions of all substances are expediently chosen such that the total weight of the monomers, based on the Total weight of the aqueous dispersion, greater than 50.0% by weight, suitably greater than 51.0% by weight, preferably greater than 52.0% by weight. In addition to the monomers, the substances to be considered in this connection also include all other substances used, such as water, emulsifier, initiator, possibly regulators and protective colloids, etc.
Die durch das erfindungsgemäße Verfahren erhältlichen wässrigen Dispersionen zeichnen sich einen niedrigen Koagulatgehalt aus, welcher, bezogen auf das Gesamtgewicht der wässrigen Dispersion, vorzugsweise weniger als 5,0 Gew.-%, zweckmäßigerweise weniger als 3,0 Gew.-%, insbesondere weniger als 1 ,5 Gew.-% ist. Gemäß einer ganz besonders bevorzugten Ausführungsform der vorliegenden Erfindung weist die wässrige Dispersion, bezogen auf ihr Gesamtgewicht, weniger als 1 ,0 Gew.-%, vorzugsweise weniger als 0,5 Gew.-%, zweckmäßigerweise weniger als 0,25 Gew.-%, insbesondere 0,10 Gew.-% oder weniger, Koagulat auf. Dabei bezeichnet der Begriff "Koagulat" in diesem Zusammenhang wasserunlösliche Bestandteile, welche vorzugsweise durch Filtration der Dispersion zweckmäßigerweise über eine Filtermanschette mit eingespanntem Filtergewebe Nr. 0.90 DIN 4188 abfiltriert werden können.The aqueous dispersions obtainable by the process according to the invention are characterized by a low coagulum content which, based on the total weight of the aqueous dispersion, is preferably less than 5.0% by weight, advantageously less than 3.0% by weight, in particular less than 1.5 wt%. According to a very particularly preferred embodiment of the present invention, the aqueous dispersion, based on its total weight, has less than 1.0% by weight, preferably less than 0.5% by weight, suitably less than 0.25% by weight , in particular 0.10 wt .-% or less, coagulate. In this context, the term “coagulate” denotes water-insoluble constituents which can preferably be filtered off, preferably by filtration of the dispersion, using a filter sleeve with clamped filter fabric No. 0.90 DIN 4188.
Das erfindungsgemäße Kern-Schale-Teilchen kann aus der Dispersion beispielsweise durch Sprühtrocknen, Gefrierkoagulation, Ausfällen durch Elektrolytzusatz oder durch mechanische oder thermische Belastung, wie sie gemäß DE 27 50 682 A1 oder US 4 110 843 mittels eines Entgasungsextruders durchführbar ist, gewonnen werden. Das Verfahren der Sprühtrocknung ist am gebräuchlichsten, obwohl die anderen genannten Verfahren den Vorzug haben, dass dabei die wasserlöslichen Polymerisationshilfsstoffe wenigstens teilweise von dem Polymerisat abgetrennt werden.The core-shell particle according to the invention can be obtained from the dispersion, for example, by spray drying, freeze coagulation, precipitation by adding electrolyte or by mechanical or thermal stress, as can be carried out according to DE 27 50 682 A1 or US 4 110 843 by means of a degassing extruder. The spray drying process is the most common, although the other processes mentioned have the advantage that the water-soluble polymerization auxiliaries are at least partially separated from the polymer.
Das erfindungsgemäße Kern-Schale-Teilchen dient zur Verbesserung der Kerbschlagzähigkeit von harten thermoplastischen Kunststoffen, die mit der Hartphase verträglich sind, vorzugsweise von Poly(meth)acrylat- Formmassen, insbesondere von Polymethylmethacrylat.The core-shell particle according to the invention serves to improve the notched impact strength of hard thermoplastics which are compatible with the hard phase, preferably of poly (meth) acrylate molding compositions, in particular of polymethyl methacrylate.
Die Poly(meth)acrylat-Formmassen enthalten vorzugsweise weitere Polymere, um die Eigenschaften in geeigneter Weise zu modifizieren. Hierzu gehören insbesondere Polyacrylnitrile, Polystyrole, Polyether, Polyester, Polycarbonate und Polyvinylchloride. Diese Polymere können einzeln oder als Mischung eingesetzt werden, wobei im Rahmen einer ganz besonders bevorzugten Ausführungsform der vorliegenden Erfindung Copolymere, die von den zuvor genannten Polymere ableitbar sind, den Formmassen beigefügt werden. Zu diesen gehören insbesondere Styrol-Acrylnitril-Copolymere (SAN), die vorzugsweise den Formmassen in einer Menge von bis zu 45 Gew.-% beigefügt werden. Besonders bevorzugte Styrol-Acrylnitril-Copolymere können durch dieThe poly (meth) acrylate molding compositions preferably contain further polymers in order to modify the properties in a suitable manner. These include in particular polyacrylonitriles, polystyrenes, polyethers, polyesters, polycarbonates and polyvinyl chlorides. These polymers can be used individually or as a mixture, copolymers which can be derived from the aforementioned polymers being added to the molding compositions in the context of a very particularly preferred embodiment of the present invention. These include, in particular, styrene-acrylonitrile copolymers (SAN), which are preferably added to the molding compositions in an amount of up to 45% by weight. Particularly preferred styrene-acrylonitrile copolymers can be obtained through the
Polymerisation von Mischungen erhalten werden, die ausPolymerization of mixtures obtained from
70,0 bis 92,0 Gew.-% Styrol70.0 to 92.0 wt% styrene
8,0 bis 30,0 Gew.-% Acrylnitril und8.0 to 30.0% by weight of acrylonitrile and
0,0 bis 22,0 Gew.-% weiterer Comonomere, jeweils bezogen auf das0.0 to 22.0% by weight of further comonomers, in each case based on the
Gesamtgewicht der zu polymerisierenden Monomere, bestehen.Total weight of the monomers to be polymerized.
In der Regel werden 100 Teilen der zu modifizierenden Formmasse 10 bis 60 Teile des Schlagzäh-Modifizierungsmittels zugemischt.As a rule, 100 parts of the molding composition to be modified are admixed with 10 to 60 parts of the impact modifier.
Erfindungsgemäß besonders bevorzugte Formmasse enthalten, jeweils bezogen auf ihr Gesamtgewicht,:According to the invention, particularly preferred molding compositions contain, in each case based on their total weight:
A) 1 ,0 bis 50,0 Gew.-% mindestens eines Kern-Schale-Teilchens gemäß mindestens einem der Ansprüche 1 bis 9;A) 1.0 to 50.0% by weight of at least one core-shell particle according to at least one of claims 1 to 9;
B) 1 ,0 bis 99,0 Gew.-% mindestens eines (Meth)acrylpolymers,B) 1.0 to 99.0% by weight of at least one (meth) acrylic polymer,
C) 0,0 bis 45 Gew.-%, vorzugsweise 1 ,0 bis 45 Gew.-%, Styrol-Acrylnitril- Copolymere undC) 0.0 to 45 wt .-%, preferably 1, 0 to 45 wt .-%, styrene-acrylonitrile copolymers and
D)0,0 bis 10,0 Gew.-% weiterer Zusatzstoffe wobei sich die Gewichtsprozente zu 100,0 Gew.-% addieren.D) 0.0 to 10.0% by weight of further additives, the weight percentages adding up to 100.0% by weight.
Dabei umfasst das (Meth)acrylpolymer, jeweils bezogen auf sein Gesamtgewicht, vorzugsweise a) 50,0 bis 100,0 Gew.-%, zweckmäßigerweise 60,0 bis 100,0 Gew.-%, besonders bevorzugt 75,0 bis 100,0 Gew.-%, insbesondere 85,0 bis 99,5 Gew.-%, Alkylmethacrylat-Wiederholungseinheiten mit 1 bis 20, vorzugsweise 1 bis 12, zweckmäßigerweise 1 bis 8, insbesondere 1 bis 4, Kohlenstoffatomen im Alkylrest, b) 0,0 bis 40,0 Gew.-%, vorzugsweise 0,0 bis 25,0 Gew.-%, insbesondere 0,1 bis 15,0 Gew.- %, Alkylacrylat-Wiederholungseinheiten mit 1 bis 20, vorzugsweise 1 bis 12, zweckmäßigerweise 1 bis 8, insbesondere 1 bis 4, Kohlenstoffatomen im Alkylrest und c) 0,0 bis 8,0 Gew.-% styrolische Wiederholungseinheiten der allgemeinenThe (meth) acrylic polymer comprises, in each case based on its total weight, preferably a) 50.0 to 100.0% by weight, advantageously 60.0 to 100.0% by weight, particularly preferably 75.0 to 100, 0% by weight, in particular 85.0 to 99.5% by weight, of repeating alkyl methacrylate units with 1 to 20, preferably 1 to 12, advantageously 1 to 8, in particular 1 to 4, carbon atoms in the alkyl radical, b) 0, 0 to 40.0% by weight, preferably 0.0 to 25.0% by weight, in particular 0.1 to 15.0% by weight, of alkyl acrylate repeating units with 1 to 20, preferably 1 to 12, expediently 1 to 8, in particular 1 to 4, carbon atoms in the alkyl radical and c) 0.0 to 8.0 wt .-% styrene repeat units of the general
Formel (I), wobei sich die Gewichtsprozente zu 100,0 Gew.-% addieren.Formula (I), the percentages by weight adding up to 100.0% by weight.
Gemäß einer besonders bevorzugten Ausführungsform der vorliegenden Erfindung enthält das (Meth)acrylpolymer, bezogen auf sein Gesamtgewicht, mindestens 50,0 Gew.-%, zweckmäßigerweise mindestens 60,0 Gew.-%, vorzugsweise mindestens 75,0 Gew.-%, insbesondere mindestens 85,0 Gew.-% Methylmethacrylat- Wiederholungseinheiten.According to a particularly preferred embodiment of the present invention, the (meth) acrylic polymer, based on its total weight, contains at least 50.0% by weight, advantageously at least 60.0% by weight, preferably at least 75.0% by weight, in particular at least 85.0% by weight methyl methacrylate repeat units.
Weiterhin weist das (Meth)acrylpolymer vorzugsweise ein Zahlenmittel des Molekulargewichtes im Bereich von 1.000 bis 100.000.000 g/mol, vorzugsweise im Bereich von 10.000 bis 1.000.000 g/mol, insbesondere im Bereich von 50.000 bis 500.000 g/mol auf. Dabei kann das Molekulargewicht, beispielsweise mittels Gelpermeationschromatographie unter Eichung auf Polystyrol ermittelt werden.Furthermore, the (meth) acrylic polymer preferably has a number average molecular weight in the range from 1,000 to 100,000,000 g / mol, preferably in the range from 10,000 to 1,000,000 g / mol, in particular in the range from 50,000 to 500,000 g / mol. The molecular weight can be determined, for example by means of gel permeation chromatography with calibration for polystyrene.
Derartige Mischungen können auf verschiedene Weise hergestellt werden. Man kann beispielsweise die Dispersion des Kern-Schale-Teilchens mit einer wässrigen Dispersion der Abmischkomponente vermischen und die Mischung koagulieren, die Wasserphase abtrennen und das Koagulat zu einer Formmasse verschmelzen. Bei diesem Verfahren iässt sich eine besonders gleichmäßige Vermischung der beiden Massen erzielen. Die Komponenten können auch getrennt hergestellt und isoliert und in Form ihrer Schmelzen oder als Pulver oder Granulate gemischt und in einem Mehrschneckenextruder oder auf einem Walzenstuhl homogenisiert werden. Übliche Zusätze können in jeder dazu geeigneten Verarbeitungsstufe zugemischt werden. Dazu zählen u. a. Farbstoffe, Pigmente, Füllstoffe, Verstärkungsfasern, Gleitmittel, UV-Schutzmittel usw..Mixtures of this type can be prepared in various ways. For example, the dispersion of the core-shell particle can be mixed with an aqueous dispersion of the mixing component and the mixture coagulated, the water phase separated and the coagulate melted into a molding compound. With this method, a particularly uniform mixing of the two masses can be achieved. The components can also be prepared and isolated separately and mixed in the form of their melts or as powders or granules and homogenized in a multi-screw extruder or on a roller mill. Usual additives can be mixed in at any suitable processing stage. These include dyes, pigments, fillers, reinforcing fibers, lubricants, UV protection agents, etc.
Im Rahmen einer ganz besonders bevorzugten Ausführungsform der vorliegenden Erfindung enthält die Formmasse, jeweils bezogen auf ihr Gesamtgewicht, 0,1 bis 10 Gew.-%, vorzugsweise 0,5 bis 5,0 Gew.-%, insbesondere 1 ,0 bis 4,0 Gew.-%, eines weiteren Polymerisates (AP), welches im Vergleich mit dem (Meth)acrylpolymer ein um mindestens 10 %, vorzugsweise mindestens 50 %, insbesondere mindestens 100 % höheres Gewichtsmittel des Molekulargewichtes aufweist. Dabei kann das Molekulargewicht, beispielsweise mittels Gelpermeationschromatographie unter Eichung auf Polystyrol ermittelt werden.In the context of a very particularly preferred embodiment of the present invention, the molding composition contains, based in each case on its total weight, 0.1 to 10% by weight, preferably 0.5 to 5.0% by weight, in particular 1.0 to 4, 0% by weight of a further polymer (AP) which, in comparison with the (meth) acrylic polymer, has a weight average molecular weight which is at least 10%, preferably at least 50%, in particular at least 100% higher. The molecular weight can be determined, for example by means of gel permeation chromatography with calibration for polystyrene.
Erfindungsgemäß besonders geeignete Polymerisate (AP) umfassen, jeweils bezogen auf ihr Gesamtgewicht, vorzugsweise a) 50,0 bis 100,0 Gew.-%, zweckmäßigerweise 60,0 bis 100,0 Gew.-%, besonders bevorzugt 75,0 bis 100,0 Gew.-%, insbesondere 85,0 bis 99,5 Gew.-%, Alkylmethacrylat-Wiederholungseinheiten mit 1 bis 20, vorzugsweise 1 bis 12, zweckmäßigerweise 1 bis 8, insbesondere 1 bis 4, Kohlenstoffatomen im Alkylrest, b) 0,0 bis 40,0 Gew.-%, vorzugsweise 0,0 bis 25,0 Gew.-%, insbesondere 0,1 bis 15,0 Gew.- %, Alkylacrylat-Wiederholungseinheiten mit 1 bis 20, vorzugsweise 1 bis 12, zweckmäßigerweise 1 bis 8, insbesondere 1 bis 4, Kohlenstoffatomen im Alkylrest und c) 0,0 bis 8,0 Gew.-% styrolische Wiederholungseinheiten der allgemeinen Formel (l), wobei sich die Gewichtsprozente zu 100,0 Gew.-% addieren. Gemäß einer besonders bevorzugten Ausführungsform der vorliegenden Erfindung enthält das Polymerisat (AP), bezogen auf sein Gesamtgewicht, mindestens 50,0 Gew.-%, zweckmäßigerweise mindestens 60,0 Gew.-%, vorzugsweise mindestens 75,0 Gew.-%, insbesondere mindestens 85,0 Gew.-% Methylmethacrylat-Wiederholungseinheiten.Polymers (AP) which are particularly suitable according to the invention comprise, based on their total weight, preferably a) 50.0 to 100.0% by weight, advantageously 60.0 to 100.0% by weight, particularly preferably 75.0 to 100 , 0 wt .-%, in particular 85.0 to 99.5 wt .-%, alkyl methacrylate repeating units having 1 to 20, preferably 1 to 12, advantageously 1 to 8, in particular 1 to 4, carbon atoms in the alkyl radical, b) 0 , 0 to 40.0% by weight, preferably 0.0 to 25.0% by weight, in particular 0.1 to 15.0% by weight, repeating alkyl acrylate units with 1 to 20, preferably 1 to 12, expediently 1 to 8, in particular 1 to 4, carbon atoms in the alkyl radical and c) 0.0 to 8.0% by weight of styrene repeat units of the general formula (I), the weight percentages adding up to 100.0% by weight. According to a particularly preferred embodiment of the present invention, the polymer (AP), based on its total weight, contains at least 50.0% by weight, advantageously at least 60.0% by weight, preferably at least 75.0% by weight, in particular at least 85.0% by weight methyl methacrylate repeat units.
Weiterhin weist das Polymerisat (AP) vorzugsweise ein Gewichtsmittel des Molekulargewichtes im Bereich von 10.000 bis 100.000.000 g/mol, vorzugsweise im Bereich von 50.000 bis 5.000.000 g/mol, zweckmäßigerweise im Bereich von 100.000 bis 1.000.000 g/mol, insbesondere im Bereich von 250.000 bis 600.000 g/mol auf. Dabei kann das Molekulargewicht, beispielsweise mittelsFurthermore, the polymer (AP) preferably has a weight average molecular weight in the range from 10,000 to 100,000,000 g / mol, preferably in the range from 50,000 to 5,000,000 g / mol, advantageously in the range from 100,000 to 1,000,000 g / mol, in particular in the range from 250,000 to 600,000 g / mol. The molecular weight can be, for example, by means of
Gelpermeationschromatographie unter Eichung auf Polystyrol ermittelt werden.Gel permeation chromatography with calibration on polystyrene can be determined.
Abmischungen der Kern-Schale-Teilchen, insbesondere mit Polymethylmethacrylat, eignen sich insbesondere zur Herstellung von Formkörpern, zweckmäßigerweise mit einer Wanddicke über 1 mm, wie extrudierten Bahnen von 1 bis 10 mm Dicke, die sich gut stanzen lassen und beispielsweise zur Herstellung bedruckbarer Blenden für Elektrogeräte brauchbar sind, oder zur Herstellung von gespritzten Formkörpern hoher Qualität, z. B. Kraftfahrzeugscheiben. Dünnere Folien von beispielsweise 50 μ Dicke können ebenfalls daraus hergestellt werden. Die erfindungsgemäß erhältlichen Formartikel zeichnen sichMixtures of the core-shell particles, in particular with polymethyl methacrylate, are particularly suitable for the production of moldings, expediently with a wall thickness of more than 1 mm, such as extruded webs of 1 to 10 mm in thickness, which can be easily punched and for example for the production of printable screens for Electrical devices are useful, or for the production of molded high-quality moldings, for. B. automotive windows. Thinner films, for example 50 μm thick, can also be produced therefrom. The molded articles obtainable according to the invention stand out
* vorzugsweise durch eine Vicat-Erweichungstemperatur nach ISO 306 (B50) von mindestens 85 °C, bevorzugt von mindestens 90 °C und besonders bevorzugt von mindestens 93 °C,* preferably by a Vicat softening temperature according to ISO 306 (B50) of at least 85 ° C, preferably of at least 90 ° C and particularly preferably of at least 93 ° C,
* vorzugsweise durch eine Kerbschlagzähigkeit KSZ (Izod 180/1eA) nach ISO 180 von mindestens 5,8 kJ/m2, günstigerweise größer 6,0 kJ/m2, bei 23 °C und vorzugsweise von mindestens 3,7 kJ/m2 bei -20°C und* preferably by a notched impact strength KSZ (Izod 180 / 1eA) according to ISO 180 of at least 5.8 kJ / m 2 , advantageously greater than 6.0 kJ / m 2 , at 23 ° C and preferably of at least 3.7 kJ / m 2 at -20 ° C and
* vorzugsweise durch einen E-Modul nach ISO 527-2 von mindestens 1450 MPa aus.* preferably with a modulus of elasticity according to ISO 527-2 of at least 1450 MPa.
Im Rahmen einer besonders bevorzugten Ausführungsform der vorliegenden Erfindung werden die erfindungsgemäßen Formkörper als Spiegelgehäuse oder Spoiler eines Fahrzeugs, als Rohr, als eine Folie für Sportartikel, als Abdeckung oder als Bauelement eines Kühlschranks eingesetzt.In the context of a particularly preferred embodiment of the present invention, the moldings according to the invention are used as a mirror housing or spoiler of a vehicle, as a tube, as a film for sports articles, as a cover or as a component of a refrigerator.
Die nachfolgenden Beispiele und Vergleichsbeispiele dienen zur Erläuterung der vorliegenden Erfindung, ohne dass hierdurch eine Beschränkung des Erfindungsgedankens erfolgen soll.The following examples and comparative examples serve to explain the present invention, without this being intended to limit the inventive concept.
I. Kern-Schale-TeilchenI. Core-shell particles
A. Herstellung des SaatlatexA. Production of the seed latex
Ein Saatlatex wurde mittels Emulsionspolymerisation einer Monomerzusammensetzung enthaltend 98 Gew.-% Ethylacrylat und 2 Gew.-% Allylmethacrylat hergestellt. Diese im Durchmesser ca. 20 nm großen Partikel lagen zu ca. 10 Gew,-% in Wasser vor. B. Herstellung der Kern-Schale-TeilchenA seed latex was made by emulsion polymerization of a monomer composition containing 98% by weight of ethyl acrylate and 2% by weight of allyl methacrylate. These particles, about 20 nm in diameter, were about 10% by weight in water. B. Preparation of core-shell particles
Alle im folgenden beschriebenen Kern-Schale-Teilchen wurden mittels Emulsionspolymerisation gemäß der nachfolgenden allgemeinen Herstellungsvorschrift hergestellt. Dabei wurden die in Tabelle 1 angegebenen Emulsionen I bis III eingesetzt.All of the core-shell particles described below were produced by means of emulsion polymerization in accordance with the general preparation instructions below. The emulsions I to III given in Table 1 were used.
Bei 83 °C (Kessel-Innentemperatur) wurden unter Rühren 19,416 kg Wasser in einem Polymerisationskessel vorgelegt. Es erfolgte eine Zugabe von 16,2 g Natriumcarbonat und 73 g Saatlatex. Anschließend wurde die Emulsion I über 1 h zudosiert. 10 min nach Zulaufende der Emulsion I wurde die Emulsion II über einen Zeitraum von ca. 2 h zudosiert. Anschließend wurde ca. 90 min nach Zulaufende der Emulsion II Emulsion III über einen Zeitraum von ca. 1 h zudosiert. 30 min nach Zulaufende der Emulsion III wurde auf 30 °C abgekühlt.19.416 kg of water were introduced into a polymerization kettle at 83 ° C. (internal temperature of the kettle) with stirring. 16.2 g of sodium carbonate and 73 g of seed latex were added. Emulsion I was then metered in over 1 h. 10 minutes after the end of emulsion I, emulsion II was metered in over a period of about 2 hours. Then about 90 min after the end of the emulsion II, emulsion III was metered in over a period of about 1 h. 30 minutes after the end of the emulsion III was cooled to 30 ° C.
Zur Separation der Kern-Schale-Teilchen wurde die Dispersion über 2 d bei -20 °C eingefroren, danach wieder aufgetaut und die koagulierte Dispersion über ein Filtergewebe abgetrennt. Die Trocknung des Feststoffs erfolgte bei 50 °C im Trockenschrank (Dauer: ca. 3 d).To separate the core-shell particles, the dispersion was frozen for 2 d at -20 ° C., then thawed again and the coagulated dispersion was separated off using a filter cloth. The solid was dried at 50 ° C. in a drying cabinet (duration: approx. 3 d).
Die Teilchengröße der Kern-Schale-Teilchen (s. Tabelle 2) wurde mit Hilfe eines Coulter N4 Gerätes bestimmt, wobei die Partikel in Dispersion vermessen wurden. The particle size of the core-shell particles (see Table 2) was determined using a Coulter N4 device, the particles being measured in dispersion.
Tabelle 1 : Zusammensetzung der einzelnen Emulsionen (alle Angaben in fei)Table 1: Composition of the individual emulsions (all figures in fine)
__ __ __ — — -__ __ __ - - -
Emulsion IEmulsion I
Wasser 8109,65 8109,65 8109,65 8109,65 8109,65Water 8109.65 8109.65 8109.65 8109.65 8109.65
Natriumpersulfat 8,24 8,24 8,24 8,24 8,24Sodium persulfate 8.24 8.24 8.24 8.24 8.24
Aerosol OT 75 65,88 65,88 65,88 65,88 65,88Aerosol OT 75 65.88 65.88 65.88 65.88 65.88
Methylmethacrylat 14216,72 14216,72 14216,72 14216,72 14216,72Methyl methacrylate 14216.72 14216.72 14216.72 14216.72 14216.72
Ethylacrylat 593,6 593,6 593,6 593,6 593,6Ethyl acrylate 593.6 593.6 593.6 593.6 593.6
Allylmethacrylat 29,68 29,68 29,68 29,68 29,68Allyl methacrylate 29.68 29.68 29.68 29.68 29.68
Emulsion IIEmulsion II
Wasser 7081 ,18 7081 ,18 7081 ,18 7081 ,18 7081 ,18Water 7081, 18 7081, 18 7081, 18 7081, 18 7081, 18
Natriumpersulfat 18,59 18,59 18,59 18,59 18,59Sodium persulfate 18.59 18.59 18.59 18.59 18.59
Aerosol OT 75 84,71 84,71 84,71 84,71 84,71Aerosol OT 75 84.71 84.71 84.71 84.71 84.71
Butylacrylat 15454,8 18793,8 17839,8 17744,4 17649Butyl acrylate 15454.8 18793.8 17839.8 17744.4 17649
Styrol 3453,48 954 954 954Styrene 3453.48 954 954 954
Allylmethacrylat 171 ,72 286,2 286,2 381 ,6 477Allyl methacrylate 171, 72 286.2 286.2 381, 6 477
Emulsion IIIEmulsion III
Wasser 2992,59 2992,59 2992,59 2992,59 2992,59Water 2992.59 2992.59 2992.59 2992.59 2992.59
Natriumpersulfat 8,24 8,24 8,24 8,24 8,24Sodium persulfate 8.24 8.24 8.24 8.24 8.24
Aerosol OT 75 10,59 10,59 10,59 10,59 10,59Aerosol OT 75 10.59 10.59 10.59 10.59 10.59
Methylmethacrylat 7632 7632 7632 7632 7632Methyl methacrylate 7632 7632 7632 7632 7632
Ethylacrylat 848 848 848 848 848 II. FormassenEthyl acrylate 848 848 848 848 848 II. Molding
A. Abmischung der FormmassenA. Mixing the molding compounds
Eine Formmasse auf Polymethylmethacrylat-Basis, PLEXIGLAS® 7 N (Fa. Röhm GmbH & Co. KG, Darmstadt) wurde mit den jeweiligen Kern- Schale-Teilchen mittels Extruder abgemischt. Die Zusammensetzungen der einzelnen Beispiele und Vergleichsbeispiele sind in Tabelle 2 dokumentiert.A molding composition based on polymethyl methacrylate, PLEXIGLAS ® 7 N (Fa. Röhm GmbH & Co. KG, Darmstadt) was mixed with the respective core-shell particles by means of the extruder. The compositions of the individual examples and comparative examples are documented in Table 2.
B. Prüfung der FormmassenB. Testing the molding compounds
Aus den abgemischten Formmassen wurden Prüfkörper hergestellt. Die Formmassen bzw. die entsprechenden Prüfkörper wurden gemäß den folgenden Messmethoden geprüft:Test specimens were produced from the mixed molding compositions. The molding compounds and the corresponding test specimens were tested according to the following measurement methods:
• Schmelzviskosität ηs (220 °C/5 MPa): DIN 54811 (1984)• melt viscosity ηs (220 ° C / 5 MPa): DIN 54811 (1984)
• Strangaufweitung B: DIN 54811 (1984)• Strand expansion B: DIN 54811 (1984)
• Vicat-Erweichungstemperatur (16 h/80 °C): DIN 1 SO 306 (Aug. 1994)Vicat softening temperature (16 h / 80 ° C): DIN 1 SO 306 (Aug. 1994)
• Izod - Kerbschlagzähigkeit: ISO 180 (1993)Izod impact strength: ISO 180 (1993)
• Charpy - Kerbschlagzähigkeit: ISO 179 (1993)• Charpy - impact strength: ISO 179 (1993)
• E-Modul: ISO 527-2• Modulus of elasticity: ISO 527-2
Die Ergebnisse der Prüfungen sind ebenfalls in Tabelle 2 zu sehen.The results of the tests can also be seen in Table 2.
Man erkennt eindeutig die Vorteile der erfindungsgemäßen Abmischungen gegenüber den herkömmlich schlagzähmodifizierten Formmassen (Vergleich A und B):The advantages of the mixtures according to the invention over the conventionally impact-modified molding compositions (comparison A and B) can be clearly seen:
=> Bei vergleichbarem Gehalt der Kern-Schale-Teilchen (< 40 Gew.-%) liegt die Kerbschlagzähigkeit der erfindungsgemäßen Formmassen bei -20 °C deutlich höher als die der Vergleichsformmassen. Dabei weisen alle Mischungen eine vergleichbare Kerbschlagzähigkeit bei Raumtemperatur auf. Auch eine Zähphase ohne Styrol führt zu keiner Verbesserung der=> With a comparable content of the core-shell particles (<40% by weight), the notched impact strength of the molding compositions according to the invention is significantly higher at -20 ° C. than that of the comparative molding compositions. All mixtures have a comparable impact strength at room temperature. Even a tough phase without styrene does not improve the
Kältekerbschlagzähigkeit der entsprechenden Formmassen.Cold impact strength of the corresponding molding compounds.
Die gute Kältekerbschlagzähigkeit wird erreicht, ohne die anderen wichtigen Eigenschaften der Formmassen, insbesondere dieThe good low-temperature impact strength is achieved without the other important properties of the molding compositions, in particular the
Viskosität, die Vicat-Erweichungstemperatur und den E-Modul zu verschlechtern.Viscosity, the Vicat softening temperature and the modulus of elasticity deteriorate.
Im Vergleich zu den in den Patenten DE 2253 689, DE 41 21 652 undIn comparison to those in the patents DE 2253 689, DE 41 21 652 and
DE 41 36 993 offenbarten Formmassen wird eine deutlich geringereDE 41 36 993 molding compositions disclosed is a significantly lower
Menge an Kern-Schale-Teilchen benötigt, um eine vergleichbareAmount of core-shell particles needed to be comparable
Kerbschlagzähigkeit bei tiefen Temperaturen zu erreichen. To achieve notched impact strength at low temperatures.
Tabelle 2: Prüfergebnisse der schlagzähmodifizierten FormmassenTable 2: Test results of the impact modified molding compounds
Abmischung Vergleich Vergleich A B C A BMixing Comparison Comparison A B C A B
Kern-Schale-Teilchen VB1 VB2 B1 B2 B3Core-shell particles VB1 VB2 B1 B2 B3
Teilchenradius [nm] 190 168 190 176 178Particle radius [nm] 190 168 190 176 178
Gehalt an Kern-Schale- 38,4 38,4 38,6 38,8 39Core-shell content - 38.4 38.4 38.6 38.8 39
Teilchen in Plexiglas® 7NParticles in Plexiglas® 7N
[Gew.-%][Wt .-%]
Viskosität ηs [Pa s] 3210 3160 3510 3400 3850Viscosity ηs [Pa s] 3210 3160 3510 3400 3850
3,8 5 3,5 1 ,4 0,93.8 5 3.5 1, 4 0.9
Strangauf weitung B [%]Strand expansion B [%]
Vicat- 95,6 95,9 98 98,5 98,3Vicat-95.6 95.9 98 98.5 98.3
Erweichungstemperatur [°C]Softening temperature [° C]
Izod - KerbschlagzähigkeitIzod - impact strength
23°C: [kJ/m2] 6,2 3,8 6,4 6,4 6,423 ° C: [kJ / m 2 ] 6.2 3.8 6.4 6.4 6.4
-10°C: [kJ/m2] 4,1 4,6 4,8 4,7-10 ° C: [kJ / m 2 ] 4.1 4.6 4.8 4.7
-20°C: [kJ/m2] 2,7 1 ,7 3,9 4,3 4,3-20 ° C: [kJ / m 2 ] 2.7 1, 7 3.9 4.3 4.3
Charpy -Charpy -
Kerbschlagzähigkeit 7,4 7,3 7,4 7,4Notched impact strength 7.4 7.3 7.4 7.4
23°C: [kJ/m2] 3,9 4,9 4,7 5,023 ° C: [kJ / m 2 ] 3.9 4.9 4.7 5.0
-10°C: [kJ/m2] 2,9 4,0 4,7 4,6-10 ° C: [kJ / m 2 ] 2.9 4.0 4.7 4.6
-20°C: [kJ/m2]-20 ° C: [kJ / m 2 ]
E-Modul [MPa] 1660 1550 1620 1650 Modulus of elasticity [MPa] 1660 1550 1620 1650

Claims

Patentansprüche claims
1. Kern-Schale-Teilchen, das einen Kern, eine erste Schale und gegebenenfalls einer zweiten Schale aufweist, wobei: i) der Kern, bezogen auf sein Gesamtgewicht, mindestens 75,0 Gew.- % (Meth)acrylat-Wiederholungseinheiten umfasst; ii) die erste Schale eine Glasübergangstemperatur kleiner 30 °C aufweist; iii) die gegebenenfalls vorhandene zweite Schale, bezogen auf ihr Gesamtgewicht, mindestens 75,0 Gew.-% (Meth)acrylat- Wiederholungseinheiten umfasst; dadurch gekennzeichnet, dass iv) die erste Schale, bezogen auf ihr Gesamtgewicht, die nachstehenden Bestandteile umfasst:1. core-shell particles comprising a core, a first shell and optionally a second shell, wherein: i) the core, based on its total weight, comprises at least 75.0% by weight of (meth) acrylate repeating units; ii) the first shell has a glass transition temperature below 30 ° C; iii) the optionally present second shell, based on its total weight, comprises at least 75.0% by weight of (meth) acrylate repeating units; characterized in that iv) the first shell, based on its total weight, comprises the following components:
E) 92,0 bis 98,0 Gew.-% (Meth)acrylat-Wiederholungseinheiten undE) 92.0 to 98.0% by weight of (meth) acrylate repeating units and
F) 2,0 bis 8,0 Gew.-% styrolische Wiederholungseinheiten der allgemeinen Formel (I)F) 2.0 to 8.0% by weight of styrene repeat units of the general formula (I)
wobei die Reste R1 bis R5 jeweils unabhängig voneinander Wasserstoff, ein Halogen, eine Cι-6-Alkylgruppe oder eine C2-6- Alkenylgruppe bezeichnen und der Rest R6 Wasserstoff oder eine Alkylgruppe mit 1 bis 6 Kohlenstoffatomen ist, wobei sich die Gewichtsprozente von E) und F) zu 100,0 Gew.-% addieren, und dass v) der Radius des Kern-Schale-Teilchens inklusive der gegebenenfalls vorhandenen zweiten Schale, gemessen nach dem Coulter- Verfahren, im Bereich von größer 160,0 bis 240,0 nm liegt. where the radicals R 1 to R 5 are each independently hydrogen, a halogen, a Cι -6 alkyl group or a C 2-6 - alkenyl group, and denote the radical R 6 is hydrogen or an alkyl group having 1 to 6 carbon atoms, where the Add weight percentages of E) and F) to 100.0% by weight, and that v) the radius of the core-shell particle, including the optionally present second shell, measured by the Coulter method, is in the range from greater than 160.0 to 240.0 nm.
2. Kern-Schale-Teilchen nach Anspruch 1 , dadurch gekennzeichnet, dass, jeweils bezogen auf sein Gesamtgewicht, i) der Kern 5,0 bis 50,0 Gew.-%, ii) die erste Schale 20,0 bis 75,0 Gew.-% und iü)die zweite Schale 0,0 bis 50,0 Gew.-% ausmacht, wobei sich die Gewichtsprozente zu 100,0 Gew.-% addieren.2. core-shell particles according to claim 1, characterized in that, in each case based on its total weight, i) the core 5.0 to 50.0 wt .-%, ii) the first shell 20.0 to 75.0 % By weight and i) the second shell is 0.0 to 50.0% by weight, the weight percentages adding up to 100.0% by weight.
3. Kern-Schale-Teilchen nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass der Kern, jeweils bezogen auf sein Gesamtgewicht,3. core-shell particles according to claim 1 or 2, characterized in that the core, in each case based on its total weight,
A)50,0 bis 99,9 Gew.-% Aikylmethacrylat-Wiederholungseinheiten mitA) 50.0 to 99.9 wt .-% aikyl methacrylate repeat units with
1 bis 20 Kohlenstoffatomen im Alkylrest, B) 0,0 bis 40,0 Gew.-% Alkylacrylat-Wiederholungseinheiten mit 1 bis1 to 20 carbon atoms in the alkyl radical, B) 0.0 to 40.0% by weight alkyl acrylate repeat units with 1 to
20 Kohlenstoff atomen im Alkylrest, C) 0,1 bis 2,0 Gew.-% vernetzende Wiederholungseinheiten und D)0,0 bis 8,0 Gew.-% styrolische Wiederholungseinheiten der allgemeinen Formel (I) umfasst, wobei sich die Gewichtsprozente zu 100,0 Gew.-% addieren. 20 carbon atoms in the alkyl radical, C) 0.1 to 2.0 wt .-% crosslinking repeating units and D) 0.0 to 8.0 wt .-% styrenic repeating units of the general formula (I), the percentages by weight increasing Add 100.0% by weight.
4. Kern-Schale-Teilchen nach Anspruch 3, dadurch gekennzeichnet, dass der Kern, jeweils bezogen auf sein Gesamtgewicht, 80,0 bis 99,0 Gew.-% Methylmethacrylat-Wiederholungseinheiten und 1 ,0 bis 20,0 Gew.-% Alkylacrylat-Wiederholungseinheiten mit 1 bis 4 Kohlenstoffatomen im Alkylrest enthält, wobei sich die Gewichtsprozente zu 100,0 Gew.-% addieren.4. core-shell particles according to claim 3, characterized in that the core, in each case based on its total weight, 80.0 to 99.0 wt .-% methyl methacrylate repeating units and 1.0 to 20.0 wt .-% Contains alkyl acrylate repeating units with 1 to 4 carbon atoms in the alkyl radical, the weight percentages adding up to 100.0% by weight.
5. Kern-Schale-Teilchen nach mindestens einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass die erste Schale, jeweils bezogen auf ihr Gesamtgewicht,5. core-shell particles according to at least one of the preceding claims, characterized in that the first shell, in each case based on their total weight,
E-1) 90,0 bis 97,9 Gew.-% Alkylacrylat-Wiederholungseinheiten mit 3 bis 8 Kohlenstoffatomen im Alkylrest und/oder Alkylmethacrylat- Wiederholungseinheiten mit 7 bis 14 Kohlenstoffatomen im Alkylrest,E-1) 90.0 to 97.9% by weight of alkyl acrylate repeat units with 3 to 8 carbon atoms in the alkyl radical and / or alkyl methacrylate repeat units with 7 to 14 carbon atoms in the alkyl radical,
E-2) 0,1 bis 2,0 Gew.-% vernetzende Wiederholungseinheiten undE-2) 0.1 to 2.0% by weight crosslinking repeating units and
F) 2,0 bis 8,0 Gew.-% styrolische Wiederholungseinheiten der allgemeinen Formel (I) umfasst, wobei sich die Gewichtsprozente zu 100,0 Gew.-% addieren.F) comprises 2.0 to 8.0% by weight of styrene repeat units of the general formula (I), the percentages by weight adding up to 100.0% by weight.
6. Kern-Schale-Teilchen nach Anspruch 5, dadurch gekennzeichnet, dass die Alkylacrylat-Wiederholungseinheiten mit 3 bis 8 Kohlenstoffatomen im Alkylrest und/oder Alkylmethacrylat- Wiederholungseinheiten mit 7 bis 14 Kohlenstoffatomen im Alkylrest Butylacrylat- und/oder Dodecylmethacrylat-Wiederholungseinheiten sind.6. core-shell particles according to claim 5, characterized in that the alkyl acrylate repeat units having 3 to 8 carbon atoms in the alkyl radical and / or alkyl methacrylate repeat units having 7 to 14 carbon atoms in the alkyl radical are butyl acrylate and / or dodecyl methacrylate repeat units.
7. Kern-Schale-Teilchen nach mindestens einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass es eine zweite Schale aufweist, welche, jeweils bezogen auf ihr Gesamtgewicht, G)50,0 bis 100,0 Gew.-% Alkylmethacrylat-Wiederholungseinheiten mit 1 bis 20 Kohlenstoffatomen im Alkylrest, H)0,0 bis 40,0 Gew.-% Alkylacrylat-Wiederholungseinheiten mit 1 bis7. core-shell particles according to at least one of the preceding claims, characterized in that it has a second shell, which, based in each case on its total weight, G) 50.0 to 100.0% by weight alkyl methacrylate repeating units with 1 up to 20 carbon atoms in the alkyl radical, H) 0.0 to 40.0% by weight alkyl acrylate repeat units with 1 to
20 Kohlenstoffatomen im Alkylrest und I) 0,0 bis 8,0 Gew.-% styrolische Wiederholungseinheiten der allgemeinen Formel (I) umfasst, wobei sich die Gewichtsprozente zu 100,0 Gew.-% addieren.20 carbon atoms in the alkyl radical and I) 0.0 to 8.0 wt .-% styrenic repeat units of the general formula (I), wherein the weight percent add up to 100.0 wt .-%.
8. Kern-Schale-Teilchen nach mindestens einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass der Kern eine Glasübergangstemperatur von mindestens 30 °C aufweist.8. core-shell particles according to at least one of the preceding claims, characterized in that the core has a glass transition temperature of at least 30 ° C.
9. Kern-Schale-Teilchen nach mindestens einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass es eine zweite Schale aufweist, welche eine Glasübergangstemperatur von mindestens 30 °C aufweist.9. core-shell particles according to at least one of the preceding claims, characterized in that it has a second shell, which has a glass transition temperature of at least 30 ° C.
10. Verfahren zur Herstellung eines Kern-Schale-Teilchens gemäß mindestens einem der vorangehenden Ansprüche 1 bis 9, dadurch gekennzeichnet, dass man eine mehrstufige Emulsionspolymerisation durchführt.10. A method for producing a core-shell particle according to at least one of the preceding claims 1 to 9, characterized in that one carries out a multi-stage emulsion polymerization.
11. Formmasse enthaltend jeweils bezogen auf ihr Gesamtgewicht:11. Molding composition each based on their total weight:
A) 1 ,0 bis 50,0 Gew.-% mindestens eines Kern-Schale-Teilchens gemäß mindestens einem der Ansprüche 1 bis 9;A) 1.0 to 50.0% by weight of at least one core-shell particle according to at least one of claims 1 to 9;
B) 1 ,0 bis 99,0 Gew.-% mindestens eines (Meth)acrylpolymers,B) 1.0 to 99.0% by weight of at least one (meth) acrylic polymer,
C) 0,0 bis 45 Gew.-% Styrol-Acrylnitril-Copolymere, und D)0,0 bis 10,0 Gew.-% weiterer Zusatzstoffe wobei sich die Gewichtsprozente zu 100,0 Gew.-% addieren. C) 0.0 to 45% by weight of styrene-acrylonitrile copolymers, and D) 0.0 to 10.0% by weight of further additives, the percentages by weight adding up to 100.0% by weight.
12. Formmasse gemäß Anspruch 11 , dadurch gekennzeichnet, dass das (Meth)acryl)polymer, jeweils bezogen auf sein Gesamtgewicht, a) 50,0 bis 100,0 Gew.-% Alkylmethacrylat-Wiederholungseinheiten mit 1 bis 20 Kohlenstoffatomen im Alkylrest, b) 0,0 bis 40,0 Gew.-% Alkylacrylat-Wiederholungseinheiten mit 1 bis 20 Kohlenstoffatomen im Alkylrest und c) 0,0 bis 8,0 Gew.-% styrolische Wiederholungseinheiten der allgemeinen Formel (I) umfasst, wobei sich die Gewichtsprozente zu 100,0 Gew.-% addieren.12. Molding composition according to claim 11, characterized in that the (meth) acrylic) polymer, based in each case on its total weight, a) 50.0 to 100.0% by weight alkyl methacrylate repeating units having 1 to 20 carbon atoms in the alkyl radical, b ) 0.0 to 40.0% by weight of alkyl acrylate repeat units with 1 to 20 carbon atoms in the alkyl radical and c) 0.0 to 8.0% by weight of styrene repeat units of the general formula (I), the weight percentages add to 100.0% by weight.
13. Formmasse gemäß Anspruch 11 oder 12, dadurch gekennzeichnet, dass die Formmasse Styrol-Acrylnitril-Copolymere enthält, wobei die Styrol-Acrylnitril-Copolymere durch Polymerisation einer Mischung erhalten wurden, die aus13. Molding composition according to claim 11 or 12, characterized in that the molding composition contains styrene-acrylonitrile copolymers, the styrene-acrylonitrile copolymers being obtained by polymerizing a mixture which consists of
70 bis 92 Gew.-% Styrol 8 bis 30 Gew.-% Acrylnitril und70 to 92 wt .-% styrene 8 to 30 wt .-% acrylonitrile and
0 bis 22 Gew.-% weiterer Comonomere, jeweils bezogen auf das Gesamtgewicht der zu polymerisierenden Monomere, besteht.0 to 22% by weight of further comonomers, based in each case on the total weight of the monomers to be polymerized.
14. Formmasse gemäß mindestens einem der Ansprüche 11 bis 13, dadurch gekennzeichnet, dass sie, bezogen auf ihr Gesamtgewicht, 0,1 bis 10 Gew.-% eines weiteren Polymerisates enthält, welches im Vergleich mit dem (Meth)acrylpolymer B) ein um mindestens 10 % höheres Gewichtsmittel des Molekulargewichtes aufweist.14. Molding composition according to at least one of claims 11 to 13, characterized in that it contains, based on its total weight, 0.1 to 10 wt has at least 10% higher weight average molecular weight.
15. Formartikel erhältlich aus einer Formmasse gemäß mindestens einem der Ansprüche 11 bis 14. 15. Shaped article obtainable from a molding composition according to at least one of claims 11 to 14.
16. Formartikel gemäß Anspruch 15, dadurch gekennzeichnet, dass der Formartikel eine Vicat-Erweichungstemperatur nach ISO 306 (B50) von mindestens 85 °C, bevorzugt von mindestens 90 °C und besonders bevorzugt von mindestens 93 °C, eine Kerbschlagzähigkeit KSZ (Izod 180/1θA) nach ISO 180 von mindestens 5,8 kJ/m2 bei 23 °C und von mindestens 3,7 kJ/m2 bei -20°C, einen E-Modul nach ISO 527-2 von mindestens 1500 MPa, aufweist.16. Shaped article according to claim 15, characterized in that the shaped article has a Vicat softening temperature according to ISO 306 (B50) of at least 85 ° C, preferably of at least 90 ° C and particularly preferably of at least 93 ° C, a notched impact strength KSZ (Izod 180 / 1θA) according to ISO 180 of at least 5.8 kJ / m 2 at 23 ° C and of at least 3.7 kJ / m 2 at -20 ° C, has a modulus of elasticity according to ISO 527-2 of at least 1500 MPa ,
17. Formartikel gemäß Anspruch 14, dadurch gekennzeichnet, dass der Formkörper ein Spiegelgehäuse oder ein Spoiler eines Fahrzeugs, ein Rohr, eine Folie für Sportgeräte, eine Abdeckung oder ein Bauelement eines Kühlschranks ist. 17. Shaped article according to claim 14, characterized in that the shaped body is a mirror housing or a spoiler of a vehicle, a tube, a film for sports equipment, a cover or a component of a refrigerator.
EP03769412A 2002-12-19 2003-10-18 Core and shell particle for modifying impact resistance of a mouldable poly(meth)acrylate material Withdrawn EP1572768A2 (en)

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DE10260065 2002-12-19
DE10260065A DE10260065A1 (en) 2002-12-19 2002-12-19 Core-shell particles for toughening of poly (meth) acrylate molding compounds
PCT/EP2003/011541 WO2004056892A2 (en) 2002-12-19 2003-10-18 Core and shell particle for modifying impact resistance of a mouldable poly(meth)acrylate material

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AU2003278101A1 (en) 2004-07-14
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CN1726238A (en) 2006-01-25
US20060147714A1 (en) 2006-07-06
KR20050085769A (en) 2005-08-29
TW200422342A (en) 2004-11-01
RU2330716C2 (en) 2008-08-10
WO2004056892A2 (en) 2004-07-08
RU2005122819A (en) 2006-01-20
TWI249554B (en) 2006-02-21
KR100781068B1 (en) 2007-11-30
WO2004056892A3 (en) 2005-03-17
US7695813B2 (en) 2010-04-13
HK1086286A1 (en) 2006-09-15
JP4582638B2 (en) 2010-11-17
DE10260065A1 (en) 2004-07-01

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