WO2010023114A1 - Composition de résine destinée à être utilisée dans des disques blu-ray - Google Patents

Composition de résine destinée à être utilisée dans des disques blu-ray Download PDF

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WO2010023114A1
WO2010023114A1 PCT/EP2009/060530 EP2009060530W WO2010023114A1 WO 2010023114 A1 WO2010023114 A1 WO 2010023114A1 EP 2009060530 W EP2009060530 W EP 2009060530W WO 2010023114 A1 WO2010023114 A1 WO 2010023114A1
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Prior art keywords
component
resin composition
graft
composition according
unsaturated monocarboxylic
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PCT/EP2009/060530
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German (de)
English (en)
Inventor
Leonie Felicitas Braun
Wenke FRÄßDORF
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Basf Se
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Publication of WO2010023114A1 publication Critical patent/WO2010023114A1/fr

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    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/253—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates
    • G11B7/2533—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/16—Homopolymers or copolymers of alkyl-substituted styrenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • 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
    • 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
    • C08L51/06—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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

  • the present application relates to a resin composition, a medium for optically recording data containing such a resin composition, the use of a resin composition for producing media for optically recording data, and a process for producing such a medium.
  • New technologies such as HDTV, HD video and broadband Internet, will require data carriers with ever greater storage capacity.
  • a data carrier with a very large storage capacity is, for example, the BluRay disc.
  • methods for producing such data carriers and materials for these data carriers have been proposed.
  • WO 2006/003666 A2 discloses optical storage media having a multilayer structure. According to WO 2006/003666 A2, such multi-layer optical data carriers can be obtained from virtually all known polymeric materials. Polymethylmethacrylates, polyacrylonitriles, polybutadienes, polyamides, polyvinyl alcohol, polystyrenes, polyalkylstyrenes and the like are mentioned by way of example. According to the cited document, a particularly preferred material for producing the said optical storage media is polycarbonate.
  • WO 2003/037983 A3 discloses molded optical data carriers for recording and reproducing audio and / or optical data such as CDs or DVDs.
  • the thermoplastic polymer material used therefor comprises 60 to 95% by weight of a material selected from a methyl methacrylate homopolymer, a copolymer containing methyl methacrylate monomers, a mixture of a methyl methacrylate homopolymer and / or a copolymer with a substituted or unsubstituted styrene copolymer and at least one monomer selected from (Meth ) acrylonitrile, maleic anhydride and maleimides or a glutarimide polymer, which may optionally be mixed with a substituted or unsubstituted styrene copolymer, and 5 to 40% by weight of at least one impact modifier in the form of particles having an average size of 10 to 200 nm.
  • WO 03/102110 A1 discloses a polymer composition comprising a thermoplastic resin or a blend of thermoplastic resins and a graft rubber comprising a grafting base to which one or more monomers have been grafted.
  • suitable thermoplastic resins are selectable from a large group of polymers comprising polycarbonates, polyesters, polyolefins, styrene polymers and styrene copolymers, PVC, polyamides, and the like.
  • WO 2003/1021 10 A1 does not disclose resin compositions containing two graft rubbers ,
  • the object of the present invention is to provide a resin composition which is particularly suitable for use in the manufacture of optical data storage media. It is important to ensure that the resin composition of the invention has a sufficient mechanical stability and resistance. For this, the resin composition must have all the characteristics necessary for storage and reproduction of optically stored data, such as low water uptake, chemical stability and good electrostatic properties.
  • the term resin composition means a mixture of the copolymers (A), (B), (C) and optionally further additives (D).
  • the resin composition of the present invention comprises 74.8 to 84.8% by weight, preferably 77 to 83% by weight, more preferably 78 to 81% by weight of a copolymer containing at least one ⁇ , ⁇ -unsaturated monocarboxylic acid nitrile and at least one aromatic vinyl monomer.
  • component (A) is the hard component, i.
  • Component (A) has a higher degree of hardness than components (B) or (C).
  • Suitable ⁇ , ⁇ -unsaturated monocarboxylic acid nitriles are selected from the group consisting of acrylonitrile, methacrylonitrile and mixtures thereof.
  • Suitable aromatic vinyl monomers in component (A) may be compounds of the general formula (I)
  • R 1 is independently hydrogen, Ci-Cio-alkyl, Ci-Cio-cycloalkyl, C1-C10 alkoxy, Ce-ds-alkyl, C 6 -C 8 -A-alkyl, C 6 -C s aryloxy, chloro, or Bromine and
  • R 2 independently of one another are hydrogen, C 1 -C 10 -alkyl, chlorine or bromine.
  • Preferred aromatic vinyl monomers of the general formula (I) are selected from the group consisting of styrene, 3-methylstyrene, 3,5-dimethylstyrene, 4-n-propylstyrene, ⁇ -methylstyrene, ⁇ -methylvinyltoluene, ⁇ -chlorostyrene, ⁇ -bromostyrene, Dichlorsty- rol, dibromostyrene and mixtures thereof.
  • Particularly preferred aromatic vinyl monomers are styrene and / or ⁇ -methylstyrene.
  • Component (A) can be obtained by all methods known to those skilled in the art, for example free-radical, anionic or cationic polymerization.
  • Component (A) is preferably obtained by continuous or discontinuous polymerization in bulk or in solution.
  • the polymerization solution contains as solvent from 0 to 20% by weight of an aromatic solvent, for example toluene, xylene or ethylbenzene.
  • Component (A) can be obtained by a method, as for example in the Plastics Handbook, Vieweg-Daumiller, Volume V, (polystyrene), Carl Hanser Verlag, Kunststoff 1969, pages 122 f. is described.
  • the hard component (A) is also commercially available.
  • component (A) contains acrylonitrile as the ⁇ , ⁇ -unsaturated monocarbonitrile and ⁇ -methylstyrene as the aromatic vinyl monomer.
  • component (A) of the resin composition according to the invention is an AMSAN copolymer which is composed of acrylonitrile and ⁇ -methylstyrene.
  • this AMSAN copolymer is acrylonitrile in a proportion of 20 to 40 wt .-%, preferably 25 to 35 wt .-% and ⁇ -methyl styrene in an amount of 60 to 80 wt .-%, preferably 65 to 75 parts by weight. % before, the sum of the amounts of the two monomers being 100% by weight.
  • Polystyrene calibration standards were used in molecular weight measurements. A 5 * MixedB column was used.
  • the weight average molecular weight M w of the polymer used as component (A) is preferably 20,000 to 110,000 g / mol, more preferably 50,000 to 95,000 g / mol, in each case measured by GPC with UV detection.
  • the number-average molecular mass M n of the polymer used as component (A) is preferably from 10,000 to 40,000 g / mol, more preferably from 20,000 to 35,000 g / mol, in each case measured by GPC with UV detection.
  • the molecular mass M p of the polymer used as component (A) is preferably 20,000 to 90,000 g / mol, particularly preferably 50,000 to 85,000 g / mol, in each case measured by GPC with UV detection.
  • the polydispersity M w / M n with respect to the molecular masses M w and M n measured by GPC with UV detection is preferably 2.0 to 3.5.
  • the weight average molecular weight M w of the polymer used as component (A) is preferably from 20,000 to 80,000 g / mol, particularly preferably from 50,000 to 70,000 g / mol, in each case measured by GPC with Rl (refractive index).
  • the number-average molecular mass M n of the polymer used as component (A) is preferably from 10,000 to 40,000 g / mol, particularly preferably from 20,000 to 30,000 g / mol, in each case measured by GPC with Rl (refractive index).
  • the molecular mass M p of the polymer used as component (A) is preferably 20,000 to 80,000 g / mol, more preferably 50,000 to 70,000 g / mol, in each case measured by GPC with Rl (refractive index).
  • the polydispersity M w / M n with respect to the molecular masses M w and M n measured by GPC with Rl (refractive index) is preferably 2.0 to 3.5.
  • the viscosity number (VZ) of the polymer used as component (A) is in a preferred embodiment, measured according to DIN 53726 at 25 0 C in a 0.5 wt .-% solution in DMF, 40 to 90 ml / g, particularly preferred 50 to 60 ml / g, most preferably 53 to 58 ml / g.
  • the hard component (A) is commercially available under the name Luran® KR 2556 from BASF Aktiengesellschaft.
  • Component (B) in the resin composition according to the invention is a graft rubber comprising a graft base b1 composed of at least one ⁇ , ⁇ -unsaturated monocarboxylic acid ester having an average particle size of 50 to 150 nm and at least one graft shell b2 composed of at least one aromatic vinyl monomer and at least one ⁇ , ⁇ -unsaturated monocarboxylic acid nitrile.
  • the resin composition of the invention comprises 0.1 to 4.9 wt .-%, preferably 1 to 4 wt .-%, particularly preferably 2 to 3 wt .-% of a graft rubber, which has a graft base b1 and at least one graft shell b2.
  • the graft base b1 is composed of at least one ⁇ , ⁇ -unsaturated monocarboxylic acid ester and has an average particle size of 50 to 150 nm.
  • the ⁇ , ⁇ -unsaturated monocarboxylic acid ester is derived from an ⁇ , ⁇ -unsaturated monocarboxylic acid selected from the group consisting of methacrylic acid, acrylic acid and mixtures thereof.
  • ⁇ , ß-unsaturated monocarboxylic acid ester obtained said ⁇ , ß-unsaturated monocarboxylic acid is reacted with an alcohol.
  • This alcohol is a saturated or unsaturated aliphatic alcohol having 1 to 12 carbon atoms. In a preferred embodiment, this alcohol has 1 to 8, more preferably 2 to 6 carbon atoms.
  • the alcohol component of the ⁇ , ß-unsaturated monocarboxylic acid ester can be constructed linear or branched.
  • the alcohol residue of the ester is linear.
  • Particularly suitable as C 1 -C 12 -alkyl esters of acrylic acid are ethyl acrylate, 2-ethylhexyl acrylate and n-butyl acrylate. Preference is given to 2-ethylhexyl acrylate and n-butyl acrylate, very particular preference to n-butyl acrylate. It is also possible to use mixtures of different alkyl acrylates which differ in their alkyl radical.
  • the ⁇ , ⁇ -unsaturated monocarboxylic acid ester is n-butyl acrylate. Therefore, in a preferred embodiment, the graft base b1 is a polyacrylic acid butyl ester. In a further preferred embodiment, the polyacrylic acid butyl ester used as the graft base b1 is crosslinked. This cross-linking can be carried out by all methods known to the person skilled in the art, for example by adding crosslinking monomers.
  • Such monomers are bi- or polyfunctional comonomers having at least two olefinic double bonds, for example butadiene and isoprene, divinyl esters of dicarboxylic acids such as succinic and adipic acid, diallyl and divinyl ether bifunctional alcohols such as ethylene glycol and butane-1, 4-diol, diesters of acrylic acid and methacrylic acid with said bifunctional alcohols, 1, 4-divinylbenzene and triallyl cyanurate.
  • bi- or polyfunctional comonomers having at least two olefinic double bonds, for example butadiene and isoprene, divinyl esters of dicarboxylic acids such as succinic and adipic acid, diallyl and divinyl ether bifunctional alcohols such as ethylene glycol and butane-1, 4-diol, diesters of acrylic acid and methacrylic acid with said bifunctional alcohols, 1, 4-divinylbenzene and trially
  • acrylic acid ester of tricyclodecenyl alcohol see DE-OS 12 60 135), which is known under the name Dihydrodicyc- lopentadienylacrylat (DCPA), and the allyl esters of acrylic acid and methacrylic acid.
  • DCPA Dihydrodicyc- lopentadienylacrylat
  • the graft base b1 used in component (B) has a swelling index of 5 to 25, particularly preferably 10 to 18, very particularly preferably 12 to 16.
  • the swelling index is a measure of the swellability of a polymer by a solvent.
  • Typical swelling agents are, for example, methyl ethyl ketone or toluene.
  • the determination of the swelling index is carried out, for example, by a process in which about 0.2 g of the solid of a graft base dispersion which has been converted by evaporation of the water in an amount of e.g. 50 g of toluene are swollen. After e.g. The toluene is filtered off with suction for 24 hours and the sample is weighed out. After drying the sample in vacuo, it is weighed again.
  • the swelling index is the ratio of the weight after the swelling process to the weight dry after re-drying.
  • the graft base b1 used in component (B) has a gel content of more than 80%, preferably more than 90%, more preferably more than 94%.
  • the gel content is that product content which is crosslinked and thus insoluble in a solvent.
  • the gel content is preferably determined in the same solvent as the swelling index.
  • the gel content is calculated as the ratio of the dry weight after the swelling step to the weigh in before the swelling step (x 100%).
  • the graft base b1 present in component (B) generally has an average particle size d.sub.50 of 50 to 150 nm, preferably 60 to 120 nm, more preferably 70 to 90 nm. These particle sizes are determined by the hydrodynamic fractionation method (HDF). In HDF measurement, a liquid carrier material flows through a column packed with a polymeric carrier material. While small particles that also fit into smaller spaces traverse the column at a low flow rate, larger diameter particles are transported faster. At the end of the column, the particle size is determined by means of a UV detector (at a wavelength of 254 nm).
  • HDF hydrodynamic fractionation method
  • the samples to be tested are preferably diluted to a concentration of 0.5 g / l of the liquid carrier material, then subjected to a filtration process and then added to the column.
  • Commercially available HDF devices are offered, for example, by Pointer-Laboratories. The stated HDF values refer to the volume distribution.
  • graft rubber used as component (B) is further at least one graft shell b2 constructed of at least one aromatic vinyl monomer and at least one ⁇ , ß-unsaturated monocarboxylic acid before.
  • the at least one aromatic vinyl monomer in the graft shell b2 in a preferred embodiment likewise corresponds to compounds of the general formula (I) with the meanings given for R 1 and R 2 .
  • the at least one aromatic vinyl monomer in the graft shell b2 is selected from styrene, ⁇ -methylstyrene and mixtures thereof.
  • the ⁇ , ß-unsaturated monocarboxylic acid contained in the graft shell b2 is selected in a preferred embodiment of acrylonitrile or methacrylonitrile or mixtures thereof. Preferably, acrylonitrile is used.
  • the ratio of aromatic vinyl polymer to ⁇ , ⁇ -unsaturated monocarbonitrile in the graft shell b2 is preferably 5: 1 to 1: 1, more preferably 4: 1 to 2: 1, most preferably 3.5: 1 to 2.5: 1 ,
  • the graft base b1 is present in an amount of from 40 to 80, preferably from 50 to 70, particularly preferably 60,% by weight, based on component (B).
  • the graft shell b2 is in a preferred embodiment in an amount of 20 to 60, preferably 30 to 50, particularly preferably 40 wt .-%, each based on Component (B) before.
  • the amounts of graft base b1 and graft shell b2 add up to 100 wt .-%.
  • a graft rubber is used as component (B), which has a cross-linked polyacrylic acid butyl ester as graft base b1 and a copolymer of styrene and acrylonitrile as graft shell b2.
  • the graft shell b2 can be partially or completely grafted onto the graft base b1.
  • potassium peroxodisulfate is preferably used as a radical initiator. It is also possible to use sodium and / or ammonium peroxodisulfate. It is also possible to use a redox initiator system, in particular containing an organic peroxide and at least one reducing agent.
  • Suitable organic peroxides are selected from the group consisting of: di-tert-butyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide and p-menthane hydroperoxide or mixtures thereof.
  • the reducing agent used is generally at least one water-soluble compound having a reducing action, selected from the group: salts of sulfinic acid, salts of sulfurous acid, sodium dithionite, sodium sulfite, sodium hyposulfite, sodium hydrogensulfite, ascorbic acid and salts thereof, Rongalit C (sodium formaldehyde sulfoxylate), Mono- and dihydroxyacetone, sugars, iron (II) salts, tin (II) salts and titanium (III) salts.
  • the amount of free radical initiator used based on the total amount of monomers, 0.01 to 5 wt .-%, preferably 0.1 to 3 wt .-% and particularly preferably 0.2 to 1, 5 wt .-%.
  • Suitable preparation processes for the graft copolymers (B) are, for example, emulsion polymerization, solution polymerization, suspension polymerization or bulk polymerization, the graft copolymers (B) preferably being prepared by aqueous free-radical emulsion polymerization.
  • Suitable polymerization methods are described inter alia in WO-A 2002/10222, DE-A 28 26 925 and in EP-A 022 200.
  • graft polymer (B) For the preparation of the graft polymer (B), an emulsion polymerization using a redox initiator system containing cumene hydroperoxide, dextrose and iron (II) salt or using a peroxide, for example potassium peroxodisulfate, are performed.
  • the preparation of the graft base b1 can be carried out, for example, by free-radically initiated aqueous emulsion polymerization by initially charging a subset of the monomers in an aqueous reaction medium and adding any remaining amount of monomers in the aqueous reaction medium after initiating the free-radical polymerization reaction.
  • the feed may also be in the form of a mixture, for example as an aqueous monomer emulsion.
  • the radical initiator used in the preparation of the graft base b1 is a peroxodisulfate, in particular potassium peroxodisulfate (KPS), in conjunction with further auxiliary components. It can come un- ter alia, a buffer (e.g., bicarbonate) and potassium stearate or K30 ® as soap used.
  • KPS potassium peroxodisulfate
  • MR molecular weight regulator
  • TDM tertiary dodecyl mercaptan
  • the way in which the regulator is added can affect the properties of the final product.
  • no controller is used.
  • dispersants are also used which keep both the monomer droplets and the polymer particles formed dispersed in the aqueous medium and thus ensure the stability of the aqueous polymer dispersion produced.
  • Suitable dispersants (DM) are both the protective colloids customarily used for carrying out free-radical aqueous emulsion polymerizations and commercially available emulsifiers.
  • Suitable protective colloids are, for example, polyvinyl alcohols, polyalkylene glycols, alkali metal salts of polyacrylic acids and polymethacrylic acids and gelatin derivatives.
  • Suitable protective colloids are e.g. Acrylic acid, methacrylic acid, maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid and / or 4-styrenesulfonic acid-containing copolymers and their alkali metal salts.
  • Suitable protective colloids are furthermore also N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylcarbazole, 1-vinylimidazole, 2-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, acrylamide, methacrylamide, acrylates containing amino groups, methacrylates, acrylamides and / or methacrylamides Homopolymers and copolymers.
  • suitable protective colloids can also be found in Houben-Weyl, "Methods of Organic Chemistry", Volume XIV / 1, Macromolecular Materials, Georg Thieme Verlag, Stuttgart, 1961, pages 41 1 to 420.
  • dispersants used are exclusively emulsifiers whose relative molecular weights, in contrast to the protective colloids, are usually below 1000. They may be anionic, cationic or non-ionic in nature. In the case of mixtures of surfactants, the individual components should be compatible with each other. In general, anionic emulsifiers are compatible with each other and with nonionic emulsifiers.
  • emulsifiers are used in particular as dispersants anionic, cationic or nonionic surfactants
  • Common nonionic emulsifiers include, for example, oxylated mono-, di- and trialkylphenols as well as ethoxylated fatty alcohols
  • Typical anionic emulsifiers are, for example, alkali metal and ammonium salts of alkyl sulfates (with alkyl radicals of Cs-C12 ), of sulfuric acid half-esters of ethoxylated alkanols (alkyl radical: C12-C18) and of ethoxylated alkylphenols (alkyl radicals: C4-C12) and of alkylsulfonic acids (alkyl radical: C12-)
  • Suitable cationic emulsifiers include C ⁇ -Cis-alkyl, alkylaryl or heterocyclic radicals, primary, secondary, tertiary or quaternary ammonium salts, pyridinium salts, imidazolinium salts, oxozolinium salts, morpholinium salts, tropylium salts, sulfonium salts and phosphonium salts.
  • Exemplary compounds include i.a. Dodecylammonium acetate or the corresponding sulphate, disulphates or acetates of the various 2- (N, N, N-trimethylammonium) ethyl paraffins, N-
  • the emulsifiers and protective colloids can also be used as mixtures.
  • the emulsifiers preferably used as dispersants are advantageously used in a total amount of 0.005 to 5 wt .-%, preferably from 0.01 to 5 wt .-%, in particular from 0.1 to 3 wt .-%, each based on the monomer Total concentration, used.
  • the total amount of the protective colloids used as dispersing agents in addition to or instead of the emulsifiers is often from 0.1 to 10% by weight and frequently from 0.2 to 7% by weight, based in each case on the total monomer concentration.
  • the customary buffer substances PS
  • pH values preferably from 6 to 11, such as sodium bicarbonate and sodium pyrophosphate
  • MR molecular weight regulator
  • the buffer substances can also have a complexing effect.
  • the reaction of the polymerization can be carried out advertising the in the range from 0 to 170 0 C. In general, temperatures between 40 and 120 0 C, often between 50 and 1 10 ° C and often between 60 and 100 0 C applied.
  • the free-radically initiated aqueous emulsion polymerization in the presence of a polymer seed for example in the presence of 0.01 to 3 wt .-%, often from 0.03 to 2 wt .-% and often from 0.04 to 1, 5 wt. -% of a polymer seed, in each case based on the total amount of monomer, take place.
  • a polymer seed can be used in particular if the particle size of the polymer particles to be produced by means of free-radical aqueous emulsion polymerization should be specifically adjusted, as described in US Pat. Nos. 2,520,959 and 3,397,165.
  • the polymers prepared in the manner described above (b1) are suitable as a graft base for the preparation of the graft copolymers (B).
  • graft yield An important parameter for graft copolymers is the graft yield, the graft yield being 100% for a complete grafting.
  • graft copolymers with the highest possible graft yield are advantageous, since they contain only small amounts of free polymer of the monomers.
  • the polymer which is not bound to the rubber can have a negative influence on the physical properties of the copolymer, which manifests itself in particular in mixtures with other components.
  • the graft shell (b2) is produced, optionally after agglomeration, by an emulsion polymerization process.
  • the graft shell (b2) is polymerized in the presence of the graft core (b1) obtained by the processes described above from a monomer mixture comprising the components styrene, acrylonitrile and optionally other monomers.
  • the monomers (and optionally further monomers) can be added individually or in mixtures with one another. For example, one can first graft styrene alone and then a mixture of styrene and acrylonitrile.
  • the graft copolymerization for producing the graft shell (b2) can be carried out in the same system as the emulsion polymerization for the preparation of the graft base (b1), wherein, if necessary, further emulsifiers and auxiliaries can be added.
  • the monomer mixture to be grafted in accordance with one embodiment of the invention can be added to the reaction mixture all at once, distributed over several stages, for example to build up a plurality of graft coatings, or continuously during the polymerization.
  • the monomers especially styrene and acrylonitrile
  • the monomers especially styrene and acrylonitrile
  • the degree of grafting is the amount of grafting monomers used (e.g., amount of styrene plus amount of acrylonitrile) divided by the sum of the amount of grafting base (e.g., amount of ⁇ , ⁇ -unsaturated monocarboxylic acid ester) and the amount of grafting monomers employed.
  • the graft copolymerization of the mixture of the components present in the graft shell and, if appropriate, further monomers in the presence of the graft base (b1) is carried out such that a degree of grafting of from 10 to 70% by weight, preferably from 20 to 60% by weight, in particular from 30 to 55 Wt .-% results. Since the grafting yield (PA) is generally not 100%, the actual grafted portion of the polymers is smaller than the amount used. It follows that a lot of free polymers is formed.
  • the control of the grafting yield in the graft polymerization can be effected inter alia by the metering rate of the monomers or by addition of initiator and regulator. For example, a larger amount of regulator employed (e.g., mercaptans) will result in a greater amount of free polymers.
  • graft-active and water-soluble redox systems can be used.
  • you can conventional water-soluble starters such.
  • sodium sulfite, sodium disulfite, sodium hydrogen sulfite, sodium dithionite, ascorbic acid, sugar or the sodium salt of hydroxymethanesulfonic use as a redox system.
  • Such redox systems often lead to coarser dispersions.
  • redox catalysts with high grafting activity are water-soluble starter systems such as redox systems of hydrogen peroxide and heavy metal ions such as cerium, manganese or iron (II) salts, as described e.g. in Houben-Weyl, "Methods of Organic Chemistry", 4th Edition, Volume E 20, page 2168.
  • Particularly suitable is potassium peroxodisulfate.
  • the polymerization can be carried out so that the heavy metal salt of the redox system such.
  • the iron (II) salt is added to the approach before the polymerization, while the peroxide is added simultaneously with the monomers, but separately.
  • the iron (II) salt is used, for example, in concentrations of 1 to 200 mg / l Fe (II) ions, based on the total dispersion used, with higher and lower concentrations are possible.
  • the supply of the redox initiator system can be carried out in various ways, for example by addition in portions as in WO 2001/30901 or in WO
  • the oxidizing agent cumene hydroperoxide is used (optionally in admixture with cumene), this being fed in particular partly continuously and partly as a portion (for example once).
  • redox initiators In addition to the redox initiators, conventional initiators such as oil-soluble or sparingly water-soluble organic peroxides or azo initiators can be used. Advantages are, for example, the addition of further reducing agents, which are preferably initially charged with the iron salt prior to the polymerization.
  • a reducing agent As a reducing agent z.
  • sodium sulfite sodium disulfite, sodium bisulfite, sodium dithionite, ascorbic acid, reducing sugars and the sodium salt of Hydroxymethansulfon- acid in question.
  • the molecular weight of the grafted polymer can be further adjusted by the use of chain transfer agents or molecular weight regulators (MR) such as. N-dodecylmercaptan, t-dodecylmercaptan, n-butylmercaptan or t-butyl
  • MR molecular weight regulators
  • Butyl mercaptan also suitable are odorless regulators such as terpinolens, see also EP-A 1 191 044.
  • the polymerization is often carried out at pH values of 2.5 to 12, preferably at pH values of 8 to 11.
  • the pH can be adjusted to the desired value before or during the polymerization with customary acids such as hydrochloric acid, sulfuric acid or acetic acid or else with bases such as sodium hydroxide solution, potassium hydroxide solution, ammonia or ammonium carbonate.
  • customary acids such as hydrochloric acid, sulfuric acid or acetic acid
  • bases such as sodium hydroxide solution, potassium hydroxide solution, ammonia or ammonium carbonate.
  • Preference is given to adjusting the pH of the aqueous polymer dispersions to 7 to 11 after the polymerization by adding sodium hydroxide solution, potassium hydroxide solution or ammonia.
  • an agglomeration step can be carried out in order to adjust the particle sizes and particle size distributions in a targeted manner.
  • Various processes for the partial or complete agglomeration of the graft base (b1) are known to the person skilled in the art, see, for example, EP-A 1 305 345, EP-A 029 613, EP-A 007 810, DE-A 12 33 131, DE-A 12 58 076 and DE-A 21 01 650.
  • the agglomeration can also be carried out by other methods known to those skilled in the art. These can have a considerable influence on the quality of the molding compounds and on the costs of the overall process.
  • physical agglomeration processes such as seer coagulation, freeze or pressure agglomeration processes can also be used, but chemical methods are generally used.
  • chemical methods are generally used.
  • electrolytes for example magnesium sulfate, or of inorganic or organic acids.
  • the rubber latex can be agglomerated. This is usually done by adding a dispersion of a Acrylesterpolymerisat.es.
  • a dispersion of a Acrylesterpolymerisat.es Preferably, dispersions of copolymers of (C 1 -C 4 -alkyl) esters of acrylic acid, preferably of ethyl acrylate, with monomers containing from 0.1 to 10% by weight of polar polymers, e.g. Acrylic acid, methacrylic acid, acrylamide or methacrylamide, N-methylol-methacrylamide or N-vinylpyrrolidone used.
  • the agglomerating dispersion may also contain several of the stated acrylic ester polymers.
  • concentration of the acrylic ester polymers in the dispersion used for agglomeration should generally be between 3 and 40% by weight.
  • agglomeration 0.2 to 20, preferably 1 to 5, parts by weight of the agglomerating dispersion are generally used per 100 parts of the rubber latex, calculated in each case on solids.
  • the agglomeration is carried out by adding the agglomerating dispersion to the rubber.
  • the rate of addition may be varied, generally lasting from about 1 to 60 minutes at a temperature between 20 ° and 90 ° C, preferably between 30 ° and 75 ° C.
  • the rubber latex may in principle also be obtained by other agglomerating agents, such as e.g. Acetic anhydride are agglomerated. Agglomeration by pressure or freezing is possible, but not very advantageous. The methods mentioned have long been known to the person skilled in the art. Under the conditions described so far, however, often only a part of the rubber particles is agglomerated, so that a bi- or polymodal distribution arises.
  • agglomerating agents such as e.g. Acetic anhydride are agglomerated. Agglomeration by pressure or freezing is possible, but not very advantageous.
  • the methods mentioned have long been known to the person skilled in the art. Under the conditions described so far, however, often only a part of the rubber particles is agglomerated, so that a bi- or polymodal distribution arises.
  • the resulting partially agglomerated rubber latex is relatively stable so that it can be readily stored and transported without coagulation occurring.
  • a copolymerizable, polyfunctional, agglomerating component which comprises at least one copolymer of C 1 - to C 12 -alkyl acrylates or C 1 - to C 12 -methalkylacrylates and polar comonomers from the group of acrylamide, methylacrylamide, is suitable for the agglomeration of rubber particles serving as graft base. Containing ethylacrylamide, n-butylacrylamide or maleic acid amide.
  • agglomeration polymers for example, polyethylene oxide polymers, polyvinyl nylether or polyvinyl alcohol are known.
  • agglomeration polymers are copolymers which have other than the above-mentioned polar comonomers.
  • the particularly suitable agglomeration polymers include, in particular, the copolymers of C 1 - to C 12 -alkyl acrylates or C 1 -C 12 -methalkylacrylates and polar comonomers, such as acrylamide, methacrylamide, ethacrylamide, n-butylacrylamide or maleic acid amide, see also EP-A 1 305 345th
  • no agglomeration step is performed.
  • the particles of component (B) preferably have an average particle size d ⁇ o of 60 to 200 nm, particularly preferably 60 to 170 nm, for example 84 nm.
  • This mean particle size (d) is the weight average particle size as determined by analytical ultracentrifuge according to the method of W. Gurchtle, S. Harding (ed.), Analytical Ultracentrifuge (AUC) in Biochemistry and Polymer Science , Royal Society of Cambridge Chemistry, UK 1992, pp. 1447-1475. Ultracentrifuge measurement provides the integral mass distribution of the particle diameter of a sample. From this it can be seen how many percent by weight of the particles have a diameter equal to or smaller than a certain size.
  • Component (C) in the resin composition according to the invention is a graft rubber comprising a graft base d composed of at least one ⁇ , ⁇ -unsaturated monocarboxylic acid ester having an average particle size of 300 to 600 nm and at least one graft shell c2 composed of at least one aromatic vinyl monomer and at least one ⁇ , ß-unsaturated monocarbonitrile.
  • the resin composition of the invention comprises 15.1 to 25 wt .-%, preferably 16 to 20 wt .-%, particularly preferably 17 to 18 wt .-% of a graft rubber, which has a graft base d and at least one graft cup c2 ,
  • Component (C) is a graft rubber which has a graft base d composed of at least one ⁇ , ⁇ -unsaturated monocarboxylic acid ester having an average particle size of 300 to 600 nm.
  • These particle sizes are determined by the hydrodynamic fractionation method (HDF).
  • HDF hydrodynamic fractionation method
  • a liquid carrier material flows through a column packed with a polymeric carrier material. While small particles, which also fit into smaller spaces, pass through the column at a low flow rate, particles become particles transported faster with a larger diameter.
  • the particle size is determined by means of a UV detector (at a wavelength of 254 nm).
  • the samples to be examined are preferably diluted to a concentration of 0.5 g / l of the liquid carrier material, then subjected to a filtration process and then added to the column.
  • Commercially available HDF devices are offered, for example, by Polymer Laboratories. The stated HDF values refer to the volume distribution.
  • the ⁇ , ⁇ -unsaturated monocarboxylic acid ester is derived from an ⁇ , ⁇ -unsaturated monocarboxylic acid selected from the group consisting of methacrylic acid, acrylic acid and mixtures thereof.
  • said ⁇ , ⁇ -unsaturated monocarboxylic acid is reacted with an alcohol.
  • This alcohol is a saturated or unsaturated aliphatic alcohol having 1 to 12 carbon atoms. In a preferred embodiment, this alcohol has 1 to 8, more preferably 2 to 6 carbon atoms.
  • the alcohol component of the ⁇ , ß-unsaturated monocarboxylic acid ester can be constructed linear or branched.
  • the alcohol residue of the ester is linear.
  • Particularly suitable as C 1 -C 12 -alkyl esters of acrylic acid are ethyl acrylate, 2-ethylhexyl acrylate and n-butyl acrylate. Preference is given to 2-ethylhexyl acrylate and n-butyl acrylate, very particular preference to n-butyl acrylate. It is also possible to use mixtures of different alkyl acrylates which differ in their alkyl radical.
  • the ⁇ , ⁇ -unsaturated monocarboxylic acid ester is butyl acrylate. Therefore, in a preferred embodiment, the grafting base d is a polyacrylic acid butyl ester. In a further preferred embodiment, the polyacrylic acid butyl ester used as the graft base b1 is crosslinked. This cross-linking can be carried out by all methods known to the person skilled in the art, for example by adding crosslinking monomers.
  • Such monomers are bi- or polyfunctional comonomers having at least two olefinic double bonds, for example butadiene and isoprene, divinyl esters of dicarboxylic acids such as succinic and adipic acid, diallyl and divinyl ether bifunctional alcohols such as ethylene glycol and butane-1, 4-diol, diesters of acrylic acid and methacrylic acid with said bifunctional alcohols, 1, 4-divinylbenzene and triallyl cyanurate.
  • bi- or polyfunctional comonomers having at least two olefinic double bonds, for example butadiene and isoprene, divinyl esters of dicarboxylic acids such as succinic and adipic acid, diallyl and divinyl ether bifunctional alcohols such as ethylene glycol and butane-1, 4-diol, diesters of acrylic acid and methacrylic acid with said bifunctional alcohols, 1, 4-divinylbenzene and trially
  • acrylic acid ester of tricyclodecenyl alcohol see DE-OS 12 60 135), which is known under the name Dihydrodicyc- lopentadienylacrylat (DCPA), and the allyl esters of acrylic acid and methacrylic acid.
  • DCPA Dihydrodicyc- lopentadienylacrylat
  • the graft base d used in component (C) has a swelling index of 5 to 25, particularly preferably 7 to 18, very particularly preferably 8 to 12.
  • the swelling index is a measure of swellability a polymer by a solvent.
  • Typical swelling agents are, for example, methyl ethyl ketone or toluene.
  • the swelling index is determined, for example, by a process in which about 0.2 g of the solid of a graft-base dispersion microfilmed by evaporation of the water is swollen in an amount of, for example, 50 g of toluene. After 24 hours, for example, the toluene is filtered off with suction and the sample is weighed out. After drying the sample in vacuo, it is weighed again.
  • the swelling index is the ratio of the weight after the swelling process to the weight dry after re-drying.
  • the graft base d used in component (C) has a gel content of more than 80%, particularly preferably more than 90%, particularly preferably more than 94%.
  • the gel content is that product content that is cross-linked and thus insoluble in a particular solvent.
  • the gel content is preferably determined in the same solvent as the swelling index. The gel content is calculated from the ratio of the dry weight after the swelling step to the weight before the swelling step (x 100%).
  • the graft base d present in component (C) generally has an average particle size of 300 to 600 nm, preferably 350 to 580 nm, more preferably 400 to 560 nm. These particle sizes are determined by the hydrodynamic fractionation method (HDF).
  • HDF hydrodynamic fractionation method
  • graft rubber used as component (C) is further at least one graft shell c2 constructed of at least one aromatic vinyl monomer and at least one ⁇ , ß-unsaturated monocarboxylic acid before.
  • the at least one aromatic vinyl monomer in the graft shell c2 in a preferred embodiment likewise corresponds to compounds of the general formula (I) with the meanings given for R 1 and R 2 .
  • the at least one aromatic vinyl monomer in the graft cup c2 is selected from styrene, ⁇ -methylstyrene and mixtures thereof.
  • the ⁇ , ß-unsaturated monocarboxylic acid contained in the graft shell c2 is selected in a preferred embodiment of acrylonitrile or methacrylonitrile or mixtures thereof. Preferably, acrylonitrile is used.
  • the graft base d is present in an amount of from 40 to 80, preferably from 50 to 70, particularly preferably 60,% by weight, based on component (C).
  • the graft shell c2 is present in an amount of from 20 to 60, preferably from 30 to 50, particularly preferably 40,% by weight, based in each case on component (C).
  • the amounts of graft base d and graft shell c2 add up to 100 wt .-%.
  • the ratio of aromatic vinyl polymer to ⁇ , ß-unsaturated monocarboxylic acid in the graft cup c2 is preferably 8: 1 to 2: 1, more preferably 6: 1 to 4: 1, most preferably 5.5: 1 to 4.5 :1.
  • a graft rubber is used as component (C), which has a crosslinked polyacrylic acid butyl ester as the graft base C1 and a copolymer of styrene and acrylonitrile as the graft shell c2.
  • the graft shell c2 can be partially or completely grafted onto the grafting base d.
  • a process for preparing a graft rubber present as component (C) in the resin composition according to the invention are known to the person skilled in the art and have already been described with respect to component (B) of the molding composition according to the invention
  • component (C) is obtained by introducing the graft base d, and the monomers contained in the graft shell are added and polymerized.
  • more than 30%, but preferably not more than 50%, of the aromatic vinyl polymer, based on the total amount of aromatic vinyl polymer, is added before the addition of the ⁇ , ⁇ -unsaturated monocarboxylic acid nitrile is begun.
  • the particles of component (C) preferably have an average particle size d.sub.50 of from 400 to 700 nm, more preferably from 500 to 600 nm, for example 557 nm.
  • This mean particle size (d) is the weight average particle size as determined by analytical ultracentrifuge according to the method of W. Gurchtle, S. Harding (ed.), Analytical Ultracentrifuge (AUC) in Biochemistry and Polymer Science , Royal Society of Cambridge Chemistry, UK 1992, pp. 1447-1475. Ultracentrifuge measurement provides the integral mass distribution of the particle diameter of a sample. From this it can be seen how many percent by weight of the particles have a diameter equal to or smaller than a certain size.
  • the ⁇ , ⁇ -unsaturated monocarboxylic acid ester is an acrylic acid or methacrylic acid alkyl ester derived from an alcohol having 1 to 8 carbon atoms.
  • the aromatic vinyl monomer is styrene.
  • the ⁇ , ⁇ -unsaturated monocarboxylic acid nitrile is acrylonitrile.
  • the components (A), (B) and (C) can be mixed by all methods known to the person skilled in the art, for example by means of extrusion or compounding.
  • the graft rubber (C) can be coagulated before mixing by proceeding as already described for component (B).
  • the coagulated graft rubbers (B) and (C) are optionally subjected to a centrifuging step so that the water content is lowered to 60 to 95% by weight.
  • the wet graft rubbers (B) and (C) are dried before being fed to the extruder. Suitable methods for drying corresponding graft rubbers are known to the person skilled in the art. However, it is also possible that the wet graft rubbers (B) and (C) are fed directly to the extruder to mix with the hard component (A). In this case, the water is removed during the extrusion step.
  • the combination of components (B) and (C) has a bimodal particle size distribution with respect to the graft bases b1 and d, respectively. if one considers the particle size distribution with respect to b1 and d over the mixture of (B) and (C), then there are two maxima.
  • the resin composition according to the invention has as component (D) 0 to 10 wt .-%, preferably 0 to 6 wt .-%, particularly preferably 0 to 3 wt .-% additives. If additives are present as component (D) in the resin composition according to the invention, they are preferably present in an amount of from 0.5 to 6% by weight, more preferably in an amount of from 0.5 to 1.5% by weight.
  • Suitable additives (D) are all those substances which are customarily used for processing or finishing the polymers. Mention may be made, for example, of dyes, pigments, colorants, antistatic agents, antioxidants, stabilizers for improving the thermal stability, stabilizers for increasing the light stability, stabilizers for increasing the hydrolysis resistance and the resistance to chemicals, agents against the decomposition of heat and, in particular, lubricants / lubricants which are suitable for the Production of moldings or moldings are appropriate.
  • the dosing of these other additives can be done at any stage of the manufacturing process, but preferably at an early stage, to take advantage of the stabilizing effects (or other specific effects) of the additive at an early stage.
  • customary auxiliaries and additives for example, "Plastics Additives Handbook", Ed. Gumbleter and Muller, 4th edition, Hanser Publ., Kunststoff, 1996.
  • Suitable pigments are titanium dioxide, phthalocyanines, ultramarine blue, iron oxides or carbon black, as well as the entire class of organic pigments.
  • Suitable colorants are e.g. all which can be used for the transparent, semitransparent or non-transparent coloring of polymers, in particular those which are suitable for coloring styrene copolymers selected from dyes, pigments and special effect pigments.
  • flame retardants e.g. the halogen-containing or phosphorus-containing compounds known to those skilled in the art, magnesium hydroxide, as well as other conventional compounds, or mixtures thereof are used.
  • Suitable antioxidants are, for. B. sterically hindered mononuclear or polynuclear phenolic antioxidants, which may be substituted in various ways and may also be bridged via substituents. These include not only monomeric but also oligomeric compounds which can be composed of several phenolic basic bodies. Also suitable are hydroquinones and hydroquinone-analogous, substituted compounds, as well as antioxidants based on tocopherols and their derivatives. Also mixtures of different antioxidants can be used. In principle, all commercially available or suitable for styrene copolymers compounds can be used, e.g. Irganox®.
  • co-stabilizers can be used, in particular phosphorus or sulfur-containing co-stabilizers.
  • P- or S-containing co-stabilizers are known to the person skilled in the art.
  • Preferred heat stabilizers (antioxidants) are substituted thiophenols, for example 4,4'-thio-bis (6-t-butyl-3-methyl-phenol).
  • Suitable light stabilizers are various substituted resorcinols, salicylates, benzotriazoles and benzophenones.
  • Suitable matting agents are both inorganic substances such as talc, glass spheres or metal carbonates (Such as MgC ⁇ 3, CaC ⁇ 3) into account, as well as polymer particles - in particular spherical particles with diameters CJ50 (weight average) over 1 mm - on the basis of eg methyl methacrylate, styrene compounds, acrylonitrile or mixtures thereof.
  • polymers which comprise copolymerized acidic and / or basic monomers are also possible to use.
  • Suitable anti-dripping agents are, for example, polytetrafluoroethylene (Teflon) polymers and ultrahigh molecular weight polystyrene (molecular weight M w greater than 2,000,000).
  • fibrous or pulverulent fillers are carbon or glass fibers in the form of glass fabrics, glass mats or glass silk rovings, chopped glass, glass beads and wollastonite, particularly preferably glass fibers.
  • glass fibers When glass fibers are used, they can be provided with a size and an adhesion promoter for better compatibility with the blend components.
  • the incorporation of the glass fibers can take place both in the form of short glass fibers and in the form of endless strands (rovings).
  • particulate fillers are z.
  • carbon black amorphous silica, magnesium carbonate (chalk), powdered quartz, mica, mica, bentonites, talc, feldspar or in particular calcium silicates such as wollastonite and kaolin.
  • Suitable antistatic agents are, for example, amine derivatives such as N, N-bis (hydroxyalkyl) alkylamines or -alkyleneamines, polyethylene glycol esters, copolymers of ethylene oxide glycol and propylene oxide (especially diblock or
  • Suitable stabilizers are, for example, hindered phenols, but also vitamin E or analogously constructed compounds, as well as butylated condensation products of p-cresol and dicyclopentadiene.
  • Hindered amine light stabilizers, benzophenones, resorcinols, salicylates, benzotriazoles are also suitable.
  • Other suitable compounds are, for example, thiocarboxylic acid esters. It is also possible to use C6-C20-fatty acid esters of thiopropionic acid, in particular the stearyl esters and lauryl esters.
  • dilauryl thiodipropionate dilauryl thiodipropionate
  • thiodipropionic acid diester sterol disearyl thiodipropionate
  • HALS absorbers such as bis (2, 2,6,6-tetramethyl-4-piperidyl) sebazate
  • UV absorbers such as 2H-benzotriazol-2-yl (4-methyphenol).
  • additives are usually used in amounts of 0.01 to 2 wt .-% (based on the total mixture).
  • Suitable lubricants and mold release agents are stearic acids, stearyl alcohol, stearic acid esters, amide waxes (bisstearylamide), polyolefin waxes or generally higher fatty acids, their derivatives and corresponding fatty acid mixtures having 12 to 30 carbon atoms.
  • amide waxes bisstearylamide
  • polyolefin waxes or generally higher fatty acids, their derivatives and corresponding fatty acid mixtures having 12 to 30 carbon atoms.
  • Ethylene-bis-stearamide eg Irgawax, manufacturer Ciba, Switzerland
  • the amounts of these additives are in the range of 0.05 to 5 wt .-%.
  • Silicone oils, oligomeric isobutylene or similar substances are also suitable as additives.
  • the usual amounts, if used, are from 0.001 to 3% by weight.
  • pigments, dyes, color brighteners, such as ultramarine blue, phthalocyanines, titanium dioxide, cadmium sulfides, derivatives of perylenetetracarboxylic acid are usable.
  • Processing aids and stabilizers such as UV stabilizers, heat stabilizers (eg, butylated reaction products of p-cresol and dicyclopentadiene, Wingstay L, manufacturer: Goodyear, or thiodipropionic acid dilauryl ester, Irganox, manufacturer: Ciba), lubricants and antistatics (eg, ethylene oxide -Propylene oxide copolymers such as Pluronic (manufacturer: BASF)), if used, are usually used in amounts of 0.01 to 5 wt .-%, based on the total molding composition.
  • UV stabilizers eg, butylated reaction products of p-cresol and dicyclopentadiene, Wingstay L, manufacturer: Goodyear, or thiodipropionic acid dilauryl ester, Irganox, manufacturer: Ciba
  • lubricants and antistatics eg, ethylene oxide -Propylene oxide copolymers such as Pl
  • the mixing of the components (A, (B), (C) and optionally (D) can be carried out by any known method, but preferably the mixing of the components is carried out by compounding, extruding, kneading or rolling the components, eg at temperatures in the range from 180 to 400 ° C., wherein the components, if required, are previously isolated from the solution or aqueous dispersion obtained in the polymerization
  • the products of the graft copolymerization obtained in aqueous dispersion can be precipitated, for example, with magnesium sulfate are only partially dehydrated and mixed as moist crumbs (for example with a residual moisture content of 1 to 40%, in particular 20 to 40%) with the matrix polymers, during which the complete drying of the graft copolymers takes place during the mixing Particles can also be carried out according to DE-A 19907136.
  • the present invention also relates to a medium for optically recording data containing a resin composition of the present invention.
  • Media for optical recording of data are for example CDs, DVDs, CD-R, CD-RW or BluRay discs.
  • the present invention relates to a BluRay disc containing the resin composition of the invention. These media may have additional layers for labeling or protection.
  • the BluRay disc consists in a preferred embodiment of the substrate or carrier material of the resin composition of the invention and one or more reflection, writing and / or protective layers and a cover layer.
  • the topcoat may be specially designed to improve scratch resistance and / or contamination sensitivity and be provided with further coatings.
  • the BluRay disc can also be provided with a protective film, for example by gluing.
  • Chemical, optical, magnetic or electronic substances, components, devices or components for counterfeiting, data and / or copy protection can also be integrated into the resin composition or a disc produced therefrom, for example chemical tracer substances, magnetic data carriers, microchips or RFID Crisps.
  • the present invention relates to the use of the resin composition according to the invention for the production of media for the optical recording of data.
  • the present invention relates to a method for producing a medium for optical recording of data, wherein a resin composition of the present invention is molded into such a medium.
  • a resin composition of the present invention is molded into such a medium.
  • the deformation of resin compositions into corresponding moldings is known to the person skilled in the art.
  • the resin composition according to the invention can be molded into the corresponding moldings by injection molding, injection compression molding, compression molding or by extrusion followed by stamping and / or pressing at elevated temperature.
  • the resin composition according to the invention has particularly good mechanical and electrostatic properties. Furthermore, moldings produced from the resin composition according to the invention show a very low water absorption.
  • the resin composition of the present invention has good chemical resistance, which has advantages in production by resistance to solvents and chemicals in the coating process and in use against skin fat, detergents and the like. results.
  • Articles made from the resin composition of the present invention have high scratch resistance. This provides advantages in use and minimizes the tendency to wear.
  • articles made of the resin composition of the present invention have high rigidity, which also has advantages in use due to the low sag. Therefore, the resin composition of the invention is particularly well suited for the production of BluRay discs.
  • the notched impact strength is determined on specimens (80 x 10 x 4 mm, prepared according to ISO 294 in a family tool, at a melt temperature of 240 0 C and a mold temperature of 60 0 C), at 23 0 C and -30 0 C according to ISO 179-2 / 1 eA (F) or ISO 179-2 / 1 eU.
  • the flowability is determined on a polymer melt at 220 0 C and 10 kg load according to ISO 1 133 B.
  • the elasticity is on test specimens (produced to ISO 294 at a melt temperature of 240 0 C and a mold temperature of 60 0 C) tested according to ISO 527- 2/1 A / 50th
  • the mean particle size (d) is the weight average particle size, as determined by means of an analytical ultracentrifuge according to the method of W. Gurchtle, S. Harding (ed.), Analytical Ultracentrifuge (AUC) in Biochemistry and Polymer Science, Royal Society of Cambridge Chemistry, UK 1992, pp. 1447-1475. Ultracentrifuge measurement provides the integral mass distribution of the particle diameter of a sample. From this it can be seen how many percent by weight of the particles have a diameter equal to or smaller than a certain size.
  • the determination of the particle size can also be done by Hydrodynamic Fractionation
  • HDF High-F measurement
  • a liquid carrier material flows through a column packed with a polymeric carrier material. While small particles that also fit into smaller spaces traverse the column at a low flow rate, larger diameter particles are transported faster.
  • the particle size is determined by means of a UV detector (at a wavelength of 254 nm).
  • the samples to be tested are preferably diluted to a concentration of 0.5 g / l of the liquid carrier material, then subjected to a filtration process and then added to the column.
  • Commercially available HDF devices are offered, for example, by Polymer Laboratories.
  • the stated HDF values refer to the volume distribution.
  • the weight-average particle diameter dso indicates the particle diameter at which 50% by weight of all particles have a larger particle size and 50% by weight have a smaller particle diameter.
  • a film was prepared by evaporating the water. 0.2 g of this film was mixed with 50 g of toluene. After 24 hours, the toluene was aspirated from the swollen sample and the sample was weighed out. After 16 hours drying the sample in vacuo at 1 10 0 C was re-weighed.
  • Vz The viscosity number (Vz) is determined according to DIN 53726 on a 0.5% solution of the polymer in DMF.
  • a method for characterizing the crosslinking state of polymers is the measurement of NMR relaxation times of the mobile protons, the so-called T2 times.
  • T2 times the more highly crosslinked a particular polymer is, the lower its T2 times.
  • Typical T2 times for the graft bases according to the invention are T2 times in the range 1 to 50 ms, preferably 2.5 to 40 ms and particularly preferably 2.5 to 30 ms, in each case measured on filmed samples at 80 ° C.
  • the T 2 time is determined by measuring the NMR relaxation of a dewatered and filmed sample of the graft base dispersion. For this purpose, for example, the sample is dried overnight after evaporation in a vacuum and then measured with a suitable measuring device. Comparable are only samples that were measured by the same method, since the relaxation is strongly temperature-dependent.
  • the effective transverse relaxation time of the materials measured at a proton resonance frequency of 20 MHz and a temperature of 140 ° C. is in the range between see 1 and 50 ms.
  • a magnetization decay curve composed of a solid-state echo and multiple spin echo measurements is used.
  • the effective relaxation time is the time after which the magnetization decay curve has fallen to a factor of 1 / e in relation to the output amplitude determined by means of the solid-state echo.
  • the puncture is on platelets (60 x 60 x 2 mm, prepared according to ISO 294 in a family tool, at a melt temperature of 240 0 C and a mold temperature of 50 0 C), determined in accordance with ISO 6603-2.
  • Component (A) 79.8% by weight of the hard component (A) consisting of 58% by weight of ⁇ -methylstyrene-acrylonitrile (based on the total weight of components (A), (B) and (C)), wherein ⁇ -methylstyrene-acrylonitrile consisting of 30% by weight of acrylonitrile and 70% by weight of ⁇ -methylstyrene, and 21.8% by weight of styrene-acrylonitrile (based on the total weight of components (A), (B) and (C) ), wherein the styrene acrylonitrile consists of 35% by weight of acrylonitrile and 65% by weight of styrene.
  • a graft rubber (B) comprising 60% by weight of a crosslinked polyacrylic acid butyl ester as graft base b1 with an average particle size of 80 nm, a swelling index of 14 and a gel content of more than 94% , and 40 wt .-% of a graft shell b2 obtainable by the polymerization of 75 wt
  • the graft rubber was coagulated with MgSO 4 .
  • a BluRay disc is produced from the resin composition according to Example 1, a BluRay disc is produced. Impression of the surface with structures in the nanometer range of this disc is 95% or better. A corresponding disc made of polycarbonate also shows an impression of> 95%. Also, the flatness of the BluRay disc made of the resin composition of Example 1 is comparable to the polycarbonate disc in the tangential and radial directions. The BluRay disc according to the invention is therefore as good as polycarbonate disc of the prior art in terms of surface relief and flatness.
  • NK 23/50 means conditioning at 23 0 C and a relative humidity of 50%.
  • the following classification can serve as an orienting classification:
  • Characteristic 4 to 6 reduced charging tendency characteristic value 7 to 9: high charging tendency

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de résine, qui comprend 74,8 à 84,8 % en poids d’un copolymère contenant en tant que constituants de base au moins un nitrile d’acide monocarboxylique α,β-insaturé et au moins un monomère de vinyle aromatique en tant que composant (A), 0,1 à 4,9 % en poids d’un caoutchouc greffé contenant une base de greffage b1 construite à partir d’au moins un ester d’acide monocarboxylique α,β-insaturé ayant une taille de particules moyenne de 50 à 150 nm et au moins une enveloppe de greffage b2 construite à partir d’au moins un monomère de vinyle aromatique et d’au moins un nitrile d’acide monocarboxylique α,β-insaturé en tant que composant (B), 15,1 à 25 % en poids d’un caoutchouc greffé contenant une base de greffage d construite à partir d’au moins un ester d’acide monocarboxylique α,β-insaturé ayant une taille de particules moyenne de 300 à 600 nm et au moins une enveloppe de greffage c2 construite à partir d’au moins un polymère de vinyle aromatique et d’au moins un nitrile d’acide monocarboxylique α,β-insaturé en tant que composant (C) et 0 à 10 % en poids d’additifs en tant que composant (D), la somme des quantités des composants (A), (B), (C) et (D) étant de 100 % en poids. L’invention concerne également un support pour l’enregistrement optique de données, contenant une telle composition de résine.
PCT/EP2009/060530 2008-08-26 2009-08-14 Composition de résine destinée à être utilisée dans des disques blu-ray WO2010023114A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011138185A1 (fr) 2010-05-07 2011-11-10 Basf Se Masse de matière à mouler à dispersion de la lumière réduite
US8440764B2 (en) 2010-05-07 2013-05-14 Styrolution GmbH Molding composition with reduced light scattering

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0074046A1 (fr) * 1981-09-05 1983-03-16 BASF Aktiengesellschaft Composition à mouler thermoplastique
DE19542619A1 (de) * 1995-11-15 1997-05-22 Basf Ag Thermoplastische Formmassen
DE19846205A1 (de) * 1998-10-07 2000-04-13 Basf Ag Gehäuse für Geräte zur Informationsverarbeitung und -übermittlung

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0074046A1 (fr) * 1981-09-05 1983-03-16 BASF Aktiengesellschaft Composition à mouler thermoplastique
DE19542619A1 (de) * 1995-11-15 1997-05-22 Basf Ag Thermoplastische Formmassen
DE19846205A1 (de) * 1998-10-07 2000-04-13 Basf Ag Gehäuse für Geräte zur Informationsverarbeitung und -übermittlung

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011138185A1 (fr) 2010-05-07 2011-11-10 Basf Se Masse de matière à mouler à dispersion de la lumière réduite
US8440764B2 (en) 2010-05-07 2013-05-14 Styrolution GmbH Molding composition with reduced light scattering

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