EP2758474A1 - Thermoplastic molding compound having improved notch impact strength - Google Patents

Thermoplastic molding compound having improved notch impact strength

Info

Publication number
EP2758474A1
EP2758474A1 EP12756512.5A EP12756512A EP2758474A1 EP 2758474 A1 EP2758474 A1 EP 2758474A1 EP 12756512 A EP12756512 A EP 12756512A EP 2758474 A1 EP2758474 A1 EP 2758474A1
Authority
EP
European Patent Office
Prior art keywords
components
weight
total weight
thermoplastic
group
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.)
Withdrawn
Application number
EP12756512.5A
Other languages
German (de)
French (fr)
Inventor
Sachin Jain
Sameer Nalawade
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.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP12756512.5A priority Critical patent/EP2758474A1/en
Publication of EP2758474A1 publication Critical patent/EP2758474A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • 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
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—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 halogen; Compositions of derivatives of such polymers
    • C08L27/02—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 halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—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 halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four 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
    • 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
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups

Definitions

  • thermoplastic molding composition comprising:
  • thermoplastic selected from the group consisting of: polyvinyl chloride, polystyrene, polymethyl methacrylate, polyamide, polybutylene terephthalate and polyoxymethylene;
  • nucleating agents e.g., 0-15% by weight, based on the total weight of components i to iv, nucleating agents, lubricants and antiblocking agents, waxes, antistatic agents, antifogging agents or dyes; and
  • the aim of the present invention was therefore to find plasticizers, in particular for amorphous thermoplastics, which do not have the abovementioned disadvantages.
  • thermoplastic A by incorporating from 2 to 30% by weight of a polymer mixture B, the notched impact strength of a thermoplastic A can be markedly improved.
  • the polymer blends B are therefore outstandingly suitable as plasticizers in thermoplastics.
  • Component A can be understood as meaning all common thermoplastics.
  • a thermoplastic is a partially crystalline polymer selected from the group consisting of: polyamide, polybutylene terephthalate and polyoxymethylene and more preferably an amorphous polymer selected from the group consisting of: polyvinyl chloride, polystyrene and polymethyl methacrylate understood.
  • the plasticizer effect of the polymer mixture B is particularly pronounced.
  • Component B denotes a polymer mixture comprising: i) from 30 to 70% by weight, based on the total weight of components i to ii, of at least one polyester based on aliphatic and / or aromatic dicarboxylic acids and an aliphatic dihydroxy compound; ii) from 70 to 30% by weight, based on the total weight of components i to ii, of polylactic acid; iii) 0 to 10% by weight, based on the total weight of components i to iv, of an epoxy group-containing copolymer based on styrene, acrylate and / or methacrylic acid esters; iv) 0-15% by weight, based on the total weight of components i to iv, of nucleating agents, lubricants and antiblocking agents, waxes, antistatic agents, antifogging agents or dyes.
  • Component B preferably comprises a mixture comprising: i) 39.9 to 49.9% by weight, based on the total weight of components i to iv, of at least one polyester based on aliphatic and aromatic dicarboxylic acids and an aliphatic dihydroxy compound; ii) from 59.9 to 39.9% by weight, based on the total weight of components i to iv, of polylactic acid; iii) from 0.1 to 1% by weight, based on the total weight of components i to iv, of an epoxy group-containing copolymer based on styrene, acrylate and / or methacrylic acid esters; iv) 0.1-2% by weight, based on the total weight of components i to iv, of nucleating agents, lubricants and antiblocking agents, waxes, antistatic agents, antifogging agents or dyes.
  • Component i is to be understood as meaning aliphatic or partially aromatic (aliphatic-aromatic) polyesters.
  • aliphatic polyesters are polyesters of aliphatic C 2 -C 12 -alkanediols and aliphatic C 4 -C 36 -alkanedicarboxylic acids such as polybutylene succinate (PBS), polybutylene adipate (PBA), polybutylene sucocyanate adipate (PBSA), polybutylene succinate sebacate (PBSSe), polybutylene sebacate adipate (PBSeA), polybutylene sebacate (PBSe ) or corresponding polyesteramides understood.
  • PBS polybutylene succinate
  • PBA polybutylene adipate
  • PBSA polybutylene sucocyanate adipate
  • PBSSe polybutylene succinate sebacate
  • PBSeA polybutylene sebacate adipate
  • PBSe polybutylene sebacate
  • the aliphatic polyesters generally have viscosity numbers according to DIN 53728 of 150 to 320 cm 3 / g and preferably 150 to 250 cm 3 / g.
  • MVR Melt volume rate
  • EN ISO 1133 190 ° C, 2.16 kg weight
  • the acid numbers according to DIN EN 12634 are generally from 0.01 to 1.2 mg KOH / g, preferably from 0.01 to 1.0 mg KOH / g and particularly preferably from 0.01 to 0.7 mg KOH / g
  • Partaromatic polyesters which are likewise suitable as component i) consist of aliphatic diols and aliphatic and aromatic dicarboxylic acids. Suitable partially aromatic polyesters include linear non-chain extended polyesters (WO 92/09654).
  • aliphatic / aromatic polyesters of butanediol, terephthalic acid and aliphatic C4-C8 dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid and brassylic acid (for example as described in WO 2006/097353 to 56) are suitable mixing partners.
  • Chain-extended and / or branched partially aromatic polyesters are preferably used as component i. The latter are known from the aforementioned documents WO 96/15173 to 15176, 21689 to 21692, 25446, 25448 or WO 98/12242, to which reference is expressly made. Mixtures of different partially aromatic polyesters are also possible.
  • biodegradable, aliphatic-aromatic polyesters which contain: a) 40 to 70 mol%, based on components a to b, of one or more dicarboxylic acid derivatives or dicarboxylic acids selected from the group consisting of: succinic acid, adipic acid, Sebacic acid, azelaic acid and brassylic acid; b) 60 to 30 mol%, based on components a to b, of a terephthalic acid derivative; c) 98 to 102 mol%, based on the components a to b, of a C2-C8-alkylenediol or C2-C6-oxyalkylenediol; d) 0.00 to 2 wt .-%, based on the total weight of components a to d, of a chain extender and / or branching agent selected from the group consisting of: a di or polyfunctional isocyanate, isocyanurate, oxazoline
  • Preferred aliphatic-aromatic polyesters used comprise: a) from 50 to 65, based on components a to b, of one or more dicarboxylic acid derivatives or dicarboxylic acids selected from the group consisting of succinic acid, azelaic acid, brassylic acid and preferably adipic acid, particularly preferably sebacic acid; b) 50 to 35, based on components a to b, of a terephthalic acid derivative; c) 98 to 102 mol%, based on the components a to b, 1, 4-butanediol and d) 0 to 2 wt .-%, preferably 0, 01 to 2 wt .-%, based on the total weight of components a to d, a chain extender and / or branching agent selected from the group consisting of: a polyfunctional isocyanate, isocyanurate, oxazoline, carboxylic anhydride such as maleic anhydride, ep
  • aliphatic dicarboxylic acids are preferably succinic acid, adipic acid and particularly preferably sebacic acid.
  • the diacids mentioned have the advantage that they are also available as renewable raw materials.
  • 96/15173 or preferably in WO-A 09/127555 and WO-A 09/127556.
  • ren preferably in a two-stage reaction cascade.
  • the dicarboxylic acid derivatives are reacted together with the diol in the presence of a transesterification catalyst to form a prepolyester.
  • This prepolyester generally has a viscosity number (CV) of 50 to 100 ml / g, preferably 60 to 80 ml / g.
  • the catalysts used are usually zinc, aluminum and in particular titanium catalysts.
  • Titanium catalysts such as tetra (isopropyl) orthotitanate and in particular tetrabutyl orthotitanate (TBOT) have the advantage over the tin, antimony, cobalt and lead catalysts frequently used in the literature, such as, for example, tin dioctanate, that residual amounts of catalyst remaining in the product or a secondary product of the catalyst are less toxic. This fact is particularly important in the case of biodegradable polyesters, since they can go directly into the environment via composting.
  • TBOT tetra (isopropyl) orthotitanate
  • TBOT tetrabutyl orthotitanate
  • the polyesters i are subsequently produced in a second step according to the processes described in WO-A 96/15173 and EP-A 488 617.
  • the prepolyester is reacted with chain extenders d, for example with diisocyanates or with epoxide-containing polymethacrylates, in a chain extension reaction to give a polyester having a viscosity of 150 to 320 ml / g, preferably 180 to 250 ml / g.
  • Branching agent (d ') and / or chain extender (d) selected from the group consisting of: a polyfunctional isocyanate, isocyanurate, oxazoline, epoxide, peroxide, carboxylic anhydride, an at least trifunctional alcohol or an at least trifunctional carboxylic acid.
  • Suitable chain extenders d are polyfunctional and in particular difunctional isocyanates, isocyanurates, oxazolines, carboxylic anhydride or epoxides.
  • Chain extenders and alcohols or carboxylic acid derivatives having at least three functional groups can also be understood as crosslinkers d '.
  • Particularly preferred compounds have three to six functional groups. Examples include: tartaric acid, citric acid, malic acid; Trimethylolpropane, trimethylolethane; pentaerythritol; Polyether triols and glycerol, trimesic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid and pyromellitic dianhydride. Preference is given to polyols such as trimethylolpropane, pentaerythritol and in particular glycerol.
  • biodegradable polyesters with a structural viscosity can be built up.
  • the rheological behavior of the melts improves;
  • the biodegradable polyesters are easier to process.
  • the compounds d are shear-thinning, i. the viscosity at higher shear rates becomes lower.
  • the polyesters i generally have a number average molecular weight (Mn) in the range from 10,000 to 100,000, in particular in the range from 15,000 to 75,000 g / mol, preferably in the range from 20,000 to 38,000 g / mol, a weight-average molecular weight (Mw) of 30,000 to 300,000, preferably 60000 to 200,000 g / mol and a Mw / Mn ratio of 1 to 6, preferably 2 up to 4.
  • Mn number average molecular weight
  • Mw weight-average molecular weight
  • the viscosity number is between 150 and 320, preferably from 180 to 250 g / ml (measured in o-dichlorobenzene / phenol (weight ratio 50/50).)
  • the melting point is in the range of 85 to 150, preferably in the range of 95 to 140 ° C.
  • the abovementioned polyesters can have hydroxyl and / or carboxyl end groups in any desired ratio.
  • the semiaromatic polyesters can also be end-group-modified, for example OH end groups can be obtained by reaction with phthalic acid, phthalic anhydride, trimellitic acid, trimellitic anhydride, pyromellitic acid or pyromel polyesters with acid numbers of less than 1.5 mg KOH / g are preferred.
  • the biodegradable polyesters i may contain further ingredients known to the person skilled in the art but not essential to the invention.
  • plastics technology such as stabilizers; nucleating agents; Lubricants and release agents such as stearates (especially calcium stearate); Plasticizers such as citric acid esters (especially acetyl tributyl citrate), glyceric acid esters such as triacetylglycerol or ethylglycol derivatives, surfactants such as polysorbates, palmitates or laurates; Waxes such as beeswax or beeswax esters; Antistatic, UV absorber; UV-stabilizer; Antifog agents or dyes.
  • the additives are used in concentrations of from 0 to 5% by weight, in particular from 0.1 to 2% by weight, based on the polyesters according to the invention.
  • polylactic acid having the following property profile is preferably used: a melt volume rate (MVR at 190 ° C. and 2.16 kg according to ISO 1 133 of 0.5 to 15, preferably 1 to 9, particularly preferably 2 to 8 ml / 10 minutes)
  • NatureWorks® examples include Ingeo® 2002 D, 4032 D, 4042 D and 4043 D, 8251 D, 3251 D and in particular 8051 D and 8052D.
  • NatureWorks Ingeo® 8051 D and 8052 D are polylactic acids from NatureWorks, with the following product properties: Tg: 65.3 ° C, Tm: 153.9 ° C, MVR: 6.9 [ml / 10 minutes], M w : 186000,
  • polylactic acids having an MVR according to ISO 1 133 [190 ° C./2.16 kg] of 5 to 8 ml / 10 minutes have proven to be advantageous.
  • Component iii) is described in more detail below.
  • Epoxides are understood as meaning, in particular, epoxide-group-containing copolymer based on styrene, acrylic acid ester and / or methacrylic acid ester.
  • the epoxy groups bearing units are preferably glycidyl (meth) acrylates.
  • Copolymers having a glycidyl methacrylate content of greater than 20, particularly preferably greater than 30 and especially preferably greater than 50% by weight, of the copolymer have proven to be advantageous.
  • the epoxy equivalent weight (EEW) in these polymers is preferably 150 to 3000, and more preferably 200 to 500 g / equivalent.
  • the weight average molecular weight Mw of the polymers is preferably from 2,000 to 25,000, in particular from 3,000 to 8,000.
  • the number average molecular weight M n of the polymers is preferably from 400 to 6,000, in particular from 1,000 to 4,000.
  • the polydispersity (Q) is generally between 1 .5 and 5 epoxide groups-containing copolymers of the above type are sold for example by BASF Resins BV under the trademark Joncryl ® ADR. Particularly suitable as a chain is Jonc- ryl ® ADR 4368th
  • component iv is understood as meaning one or more of the following additives: stabilizer, nucleating agent, lubricant and release agent, surfactant, wax, antistatic agent, antifogging agent, dye, pigment, UV absorber, UV stabilizer or other plastic additive.
  • Component iv is preferably used in an amount of from 0.5 to 1% by weight, based on components i and iv.
  • the molding compositions of the invention contain 69 to 98 wt .-%, preferably 75 to 92 wt .-%, and particularly preferably 80 to 90 wt .-% of the thermoplastic A and, accordingly, 2 to 31 wt .-%, preferably 8 to 25 wt. %, and more preferably 10 to 20 wt .-% of the polymer mixture B.
  • the notch toughness increases as a rule with increasing proportion of the polymer mixture B.
  • the additives C are used in amounts of 0 to 40 wt .-%, in particular 0.5 to 30 wt .-%, based on the components A to C.
  • the high weight fractions are particularly suitable for fillers.
  • Preferred fibrous fillers C are carbon fibers, aramid fibers, glass fibers and potassium titanate fibers, glass fibers being particularly preferred as E glass. These are used as rovings in the commercial forms.
  • the glass fibers used according to the invention as a roving have a diameter of 6 to 20 ⁇ m, preferably of 10 to 18 ⁇ m, the cross section of the glass fibers being round, oval or angular.
  • E-glass fibers are used according to the invention.
  • the fibrous fillers can be surface-pretreated for better compatibility with the thermoplastics with a silane compound.
  • Suitable silane compounds are those of the general formula (X- (CH 2) n) k -Si (O-C m H 2 m + 1) 4-k in which the substituents have the following meanings: n is an integer from 2 to 10, preferably 3 to 4
  • n is an integer from 1 to 5, preferably 1 to 2
  • k is an integer from 1 to 3, preferably 1 Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl group as substituent X.
  • the silane compounds are generally used in amounts of 0.01 to 2, preferably 0.025 to 1, 0 and in particular 0.05 to 0.5 wt .-% (based on C)) for surface coating.
  • Suitable coating agents are based on isocyanates.
  • the L / D (length / diameter) ratio is 100 to 4000, in particular 350 to 2000 and very particularly 350 to 700.
  • thermoplastic molding compositions furthermore advantageously contain a lubricant C.
  • a lubricant C the molding compositions of the invention may be from 0 to 3, preferably from 0.05 to 3, preferably from 0.1 to 1.5 and in particular from 0.1 to 1,% by weight. % one
  • Lubricant based on the total amount of components A to C included.
  • metal salts Preference is given to aluminum, alkali metal, alkaline earth metal salts or ester or amides of fatty acids having 10 to 44 C atoms, preferably having 14 to 44 C atoms.
  • the metal ions are preferably alkaline earth and aluminum (Al), with calcium (Ca) or magnesium being particularly preferred.
  • Preferred metal salts are Ca-stearate and Ca-montanate as well as Al-stearate. It is also possible to use mixtures of different salts, the mixing ratio being arbitrary.
  • the carboxylic acids can be 1- or 2-valent. Examples which may be mentioned are pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid and particularly preferred Stearic acid, capric acid and montanic acid (mixture of fatty acids having 30 to 40 carbon atoms) called.
  • the aliphatic alcohols can be 1 - to 4-valent.
  • examples of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, with glycerol and pentaerythritol being preferred.
  • the aliphatic amines can be 1 - to 3-valent. Examples of these are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di (6-aminohexyl) amine, with ethylenediamine and hexamethylenediamine being particularly preferred.
  • Preferred esters or amides are correspondingly glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate and pentaerythritol tetrastearate.
  • thermoplastic molding compositions As a further component C thermoplastic molding compositions according to the invention conventional processing aids such as stabilizers, oxidation retardants, other agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, flame retardants, etc. included.
  • processing aids such as stabilizers, oxidation retardants, other agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, flame retardants, etc. included.
  • oxidation inhibitors and heat stabilizers are phosphites and further amines (eg TAD), hydroquinones, various substituted representatives of these groups and mixtures thereof in concentrations of up to 1% by weight, based on the weight of the thermoplastic molding compositions.
  • TAD phosphites and further amines
  • hydroquinones various substituted representatives of these groups and mixtures thereof in concentrations of up to 1% by weight, based on the weight of the thermoplastic molding compositions.
  • UV stabilizers which are generally used in amounts of up to 2 wt .-%, based on the molding composition, various substituted resorcinols, salicylates, Benzotriazo- le and benzophenones may be mentioned.
  • inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide and carbon black and / or graphite, furthermore organic pigments such as phthalocyanines, quinacridones, perylenes and also dyes such as nigrosine and anthraquinones as colorants.
  • organic pigments such as phthalocyanines, quinacridones, perylenes and also dyes such as nigrosine and anthraquinones.
  • nucleating agents sodium phenylphosphinate, alumina, silica and preferably talc may be used.
  • Flame retardants include red phosphorus, flame retardants containing P and N, and halogenated flame retardant systems and their synergists.
  • the determination of the viscosity number was carried out according to DIN 53728 Part 3, January 3, 1985.
  • the solvent used was the mixture: phenol / dichlorobenzene in a weight ratio of 50/50.
  • the Charpy notched impact strength was determined at 23 ° C or -30 ° C according to ISO 179-2 / 1 eA.
  • the yield stress, Young's modulus and elongation at break were determined according to ISO 527-2: 1993.
  • the pulling speed was 5 mm / min.
  • Ecoflex ® C1200 (old product name: Ecoflex FBX ® 701 1) - a Polyb- utylenadipat-co-terephthalate from BASF SE, 32 wt .-% of polylactic acid (PLA) Ingeo ® 4043D of NatureWorks. LLC; 0.1% by weight of Joncryl® ADR 4368 - an epoxide group-containing copolymer based on styrene, acrylic ester and / or methacrylic ester from BASF Resins BV
  • Baerostab M25-85 from Baerlocher GmbH (Baerostab M25-85 is a modified butyl-tin-mercaptide.) This product contains a non-migrating lubricant, and de developed as a PVC stabilizer. Density at 20 ° C: 1080 g / l, viscosity at 20 ° C: 80 mPa.s)
  • Cii Acrawax C from Lonza AG (consists of ⁇ , ⁇ '-ethylenebisstearamide (CAS: 1 10-30-5), N, N'-ethane-1,2-diylbishexadecane-1-amide (CAS: 5518-18 -3), C 4 -18 fatty acids (CAS: 67701 -02-4), melting point: 140-145 ° C)
  • Ciii Irganox 98 from BASF SE (N, N'-hexane-1, 6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide)], CAS Number: 23128-74-7, Melting point: 156-165 ° C)
  • Civ Talc IT from Mondo Minerals (CAS: 14807-96-6, density: 2750 g / l)
  • Example 1 Civ: Talc IT from Mondo Minerals (CAS: 14807-96-6, density: 2750 g / l)
  • the specimens used to determine the properties were produced by means of a DSM injection molding machine.
  • the 180 ° C hot melt mixture produced in the DSM Mini Extruder was pressed at 15 bar into the 70 ° C hot tool.
  • the notch was milled into the Charpystab according to ISO 179-2 / 1 eA (F) and tested.
  • Example 1 with the polymer mixture B according to the invention had a notched impact strength 42% higher than Comparative Example 1.
  • Example 2
  • test specimens used to determine the properties were prepared by means of a Battenfeld 50 injection molding machine.
  • the granules produced under 2) and 3) were melted and pressed into the mold at a speed of rotation of the screw at 100 rpm and a residence time of 50 s.
  • the test specimens for the stress tests were produced according to ISO 527-2 / 1 A 50 and the test specimens for the impact measurements according to ISO 179-2 / 1 eA (F).
  • the injection temperature was 260 ° C, the mold temperature 80 ° C.
  • Table 2 Influence of component B on the notched impact strength of polyamide
  • Example 2 with 10% by weight of the polymer mixture B according to the invention had a notched impact strength of 45% (19%) at 23 ° C. (-30 ° C.) compared to Comparative Example 2.
  • Example 3 with 30 wt .-% of the polymer mixture B according to the invention had at 23 ° C (-30 ° C) by 141% (85%) higher notched impact strength than Comparative Example 2 on.
  • Example 3 The tensile properties: elongation at break, tensile strength and modulus of elasticity were improved in Example 3 according to the invention compared with Example 2 and at a level similar to Comparative Example 2V.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to a thermoplastic molding compound, comprising: A) 69 to 98 weight percent, in relation to the components A and B, of a thermoplastic, selected from the group consisting of: polyvinyl chloride, polystyrene, polymethyl methacrylate, polyamide, polybutylene teraphthalate and polyoxymethylene; B) 2 to 31 weight percent in relation to the components A and B of a polymer blend, comprising: i) 30 to 70 weight percent in relation to the total weight of components i and ii, of at least one polyester on the basis of aliphatic and/or aromatic dicarboxylic acid and an aliphatic dihydroxy compound; ii) 70 to 30 weight percent in relation to the total weight of the components i to ii, of polylactic acid; iii) 0 to 10 weight percent, in relation to the total weight of the components i to iv, of an epoxide group-containing copolymer on the basis of styrene, acrylic acid ester and/or methacrylic acid ester; iv) 0 to 15 weight percent in relation to the total weight of the components i to iv, of nucleation agents, lubricants and antiblocking agents, waxes, antistatic agents, antifog means or dyes; and C) 0 to 40 weight percent, in relation to the components A to C, of further additives.

Description

THERMOPLASTISCHE FORMMASEE MIT VERBESSERTER KERBSCHLAGZÄHIGKEIT  THERMOPLASTIC MOLDING LAYER WITH IMPROVED HARDWORKING STRENGTH
Beschreibung Die Erfindung betrifft eine thermoplastische Formmasse, enthaltend:  Description The invention relates to a thermoplastic molding composition comprising:
A) 69 bis 98 Gew.-%, bezogen auf die Komponenten A und B, eines Thermoplasten ausgewählt aus der Gruppe bestehend aus: Polyvinylchlorid, Polystyrol, Polymethylmethacrylat, Polyamid, Polybutylenterephthalat und Polyoxymethylen; A) 69 to 98 wt .-%, based on the components A and B, of a thermoplastic selected from the group consisting of: polyvinyl chloride, polystyrene, polymethyl methacrylate, polyamide, polybutylene terephthalate and polyoxymethylene;
B) 2 bis 31 Gew.-%, bezogen auf die Komponenten A und B, einer Polymermischung enthaltend: B) 2 to 31 wt .-%, based on the components A and B, of a polymer mixture comprising:
30 bis 70 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten i bis ii, mindestens eines Polyesters auf Basis von aliphatischen und/oder aromatischen Dicar- bonsäuren und einer aliphatischen Dihydroxyverbindung; From 30 to 70% by weight, based on the total weight of components i to ii, of at least one polyester based on aliphatic and / or aromatic dicarboxylic acids and an aliphatic dihydroxy compound;
70 bis 30 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten i bis ii, Po- lymilchsäure; From 70 to 30% by weight, based on the total weight of components i to ii, of polylactic acid;
0 bis 10 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten i bis iv, eines Epoxidgruppen-haltigen Copolymers auf Basis Styrol, Acrylsäureester und/oder Methacrylsäureester; 0 to 10 wt .-%, based on the total weight of components i to iv, of an epoxide group-containing copolymer based on styrene, acrylic acid ester and / or methacrylic acid ester;
0 - 15 % Gew.-%, bezogen auf das Gesamtgewicht der Komponenten i bis iv, Nuk- leierungsmittel, Gleit- und Antiblockmittel, Wachse, Antistatika, Antifog-Mittel oder Farbstoffe; und 0-15% by weight, based on the total weight of components i to iv, nucleating agents, lubricants and antiblocking agents, waxes, antistatic agents, antifogging agents or dyes; and
C) 0 bis 40 Gew.-%, bezogen auf die Komponenten A bis C, weiterer Zusatzstoffe. C) 0 to 40 wt .-%, based on the components A to C, other additives.
Zahlreiche technische Kunststoffe sind spröde. Sie weisen eine geringe Schlagzähigkeit und insbesondere Kerbschlagzähigkeit auf. Dieses Problem tritt insbesondere bei den amorphen Polymeren wie beispielsweise Polyvinylchlorid, Polystyrol oder Polymethylmethacrylat auf. Aber auch technische Kunststoffe wie Polyamid, Polybutylenterephthalat und Polyoxymethylen sind für manche Anwendungen hinsichtlich ihrer Schlagzähigkeit noch nicht optimal. Many engineering plastics are brittle. They have a low impact strength and in particular impact strength. This problem occurs especially in amorphous polymers such as polyvinyl chloride, polystyrene or polymethyl methacrylate. But also technical plastics such as polyamide, polybutylene terephthalate and polyoxymethylene are not optimal for some applications in terms of their impact strength.
Bisher versuchte man das Problem der Sprodigkeit durch Copolymerisation mit geeigneten Monomeren (sogenannte innere Weichmacher) oder durch Zusatz von niedermolekularen Substanzen (äußere Weichmacher) zu lösen. Die beiden bisherigen Ansätze weisen jedoch Nachteile auf. Das Prinzip der inneren Weichmacher setzt ein individuell abgestimmtes Herstellverfahren, wie beispielsweise das Herstellverfahren von HIPS (High Impact PolyStyrene) voraus. Äußere Weichmacher wie Phthalate, Alkylsufonsäureester des Phenols, oder Trialkylcitrate sind niedermolekulare Verbindungen, die mit der Zeit aus dem Kunststoff entweichen (ausschwit- zen). Dies führt zum einen zum nachträglichen Verspröden des Kunststoffs und weiterhin sind einige Weichmacher wie Phthalate wegen ihrer hormonähnlichen Wirkung bedenklich. So far, the problem of sprouting was attempted by copolymerization with suitable monomers (so-called internal plasticizers) or by the addition of low molecular weight substances (external plasticizers) to solve. However, the two previous approaches have disadvantages. The principle of the internal plasticizer requires an individually tailored manufacturing process, such as the manufacturing process of HIPS (High Impact PolyStyrene). External plasticizers such as phthalates, alkylsulfonic acid esters of phenol, or trialkyl citrates are low molecular weight compounds which escape from the plastic over time (swelling). Zen). This leads to a subsequent embrittlement of the plastic and also some plasticizers such as phthalates are questionable because of their hormone-like effect.
Ziel der vorliegenden Erfindung war es demnach Weichmacher insbesondere für amorphe Thermoplasten zu finden, die die obengenannten Nachteile nicht aufweisen. The aim of the present invention was therefore to find plasticizers, in particular for amorphous thermoplastics, which do not have the abovementioned disadvantages.
Überraschenderweise wurde gefunden, dass durch Einarbeiten von 2 bis 30 Gew.-% einer Polymermischung B die Kerbschlagzähigkeit eines Thermoplasten A deutlich verbessert werden kann. Die Polymermischungen B eignen sich daher hervorragend als Weichmacher in Thermo- plasten. Surprisingly, it has been found that by incorporating from 2 to 30% by weight of a polymer mixture B, the notched impact strength of a thermoplastic A can be markedly improved. The polymer blends B are therefore outstandingly suitable as plasticizers in thermoplastics.
Im Folgenden wird die Erfindung näher beschrieben: The invention is described in more detail below:
Unter Komponente A können alle gängigen Thermoplaste verstanden werden. Vorzugsweise wird unter einem Thermoplasten ein teilkristallines Polymer ausgewählt aus der Gruppe bestehend aus: Polyamid, Polybutylenterephthalat und Polyoxymethylen und besonders bevorzugt ein amorphes Polymer ausgewählt aus der Gruppe bestehend aus: Polyvinylchlorid, Polystyrol und Polymethylmethacrylat verstanden. Bei den amorphen Polymeren ist der Weichmachereffekt der Polymermischung B besonders stark ausgeprägt. Component A can be understood as meaning all common thermoplastics. Preferably, a thermoplastic is a partially crystalline polymer selected from the group consisting of: polyamide, polybutylene terephthalate and polyoxymethylene and more preferably an amorphous polymer selected from the group consisting of: polyvinyl chloride, polystyrene and polymethyl methacrylate understood. In the amorphous polymers, the plasticizer effect of the polymer mixture B is particularly pronounced.
Komponente B bedeutet eine Polymermischung enthaltend: i) 30 bis 70 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten i bis ii, mindestens eines Polyesters auf Basis von aliphatischen und/oder aromatischen Dicarbonsäuren und einer aliphatischen Dihydroxyverbindung; ii) 70 bis 30 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten i bis ii, Polymilch- säure; iii) 0 bis 10 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten i bis iv, eines Epo- xidgruppen-haltigen Copolymers auf Basis Styrol, Acrylsäureester und/oder Methacrylsäu- reester; iv) 0 - 15 % Gew.-%, bezogen auf das Gesamtgewicht der Komponenten i bis iv, Nukleie- rungsmittel, Gleit- und Antiblockmittel, Wachse, Antistatika, Antifog-Mittel oder Farbstoffe. Component B denotes a polymer mixture comprising: i) from 30 to 70% by weight, based on the total weight of components i to ii, of at least one polyester based on aliphatic and / or aromatic dicarboxylic acids and an aliphatic dihydroxy compound; ii) from 70 to 30% by weight, based on the total weight of components i to ii, of polylactic acid; iii) 0 to 10% by weight, based on the total weight of components i to iv, of an epoxy group-containing copolymer based on styrene, acrylate and / or methacrylic acid esters; iv) 0-15% by weight, based on the total weight of components i to iv, of nucleating agents, lubricants and antiblocking agents, waxes, antistatic agents, antifogging agents or dyes.
Vorzugsweise bedeutet Komponente B einer Mischung, enthaltend: i) 39,9 bis 49,9 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten i bis iv, mindestens eines Polyesters auf Basis von aliphatischen und aromatischen Dicarbonsäuren und einer aliphatischen Dihydroxyverbindung; ii) 59,9 bis 39,9 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten i bis iv, Poly- milchsäure; iii) 0,1 bis 1 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten i bis iv, eines Epo- xidgruppen-haltigen Copolymers auf Basis Styrol, Acrylsäureester und/oder Methacrylsäu- reester; iv) 0,1 - 2 % Gew.-%, bezogen auf das Gesamtgewicht der Komponenten i bis iv, Nukleie- rungsmittel, Gleit- und Antiblockmittel, Wachse, Antistatika, Antifog-Mittel oder Farbstoffe. Component B preferably comprises a mixture comprising: i) 39.9 to 49.9% by weight, based on the total weight of components i to iv, of at least one polyester based on aliphatic and aromatic dicarboxylic acids and an aliphatic dihydroxy compound; ii) from 59.9 to 39.9% by weight, based on the total weight of components i to iv, of polylactic acid; iii) from 0.1 to 1% by weight, based on the total weight of components i to iv, of an epoxy group-containing copolymer based on styrene, acrylate and / or methacrylic acid esters; iv) 0.1-2% by weight, based on the total weight of components i to iv, of nucleating agents, lubricants and antiblocking agents, waxes, antistatic agents, antifogging agents or dyes.
Als Komponente i sind aliphatische oder teilaromatische (aliphatisch-aromatische) Polyester zu verstehen. Component i is to be understood as meaning aliphatic or partially aromatic (aliphatic-aromatic) polyesters.
Als Komponente i) sind wie erwähnt rein aliphatische Polyester geeignet. Unter aliphatischen Polyestern werden Polyester aus aliphatischen C2-Ci2-Alkandiolen und aliphatischen C4-C36- Alkandicarbonsäuren wie Polybutylensuccinat (PBS), Polybutylenadipat (PBA), Polybutylensuc- cinatadipat (PBSA), Polybutylensuccinatsebacat (PBSSe), Polybutylensebacatadipat (PBSeA), Polybutylensebacat (PBSe) oder entsprechende Polyesteramide verstanden. Die aliphatischen Polyester werden beispielsweise von den Firmen Showa Highpolymers unter dem Namen Bionolle® und von Mitsubishi unter dem Namen GSPIa® vermarktet. Neuere Entwicklungen sind in der WO 2010/03471 1 beschrieben. As component i), as mentioned, purely aliphatic polyesters are suitable. Among aliphatic polyesters are polyesters of aliphatic C 2 -C 12 -alkanediols and aliphatic C 4 -C 36 -alkanedicarboxylic acids such as polybutylene succinate (PBS), polybutylene adipate (PBA), polybutylene sucocyanate adipate (PBSA), polybutylene succinate sebacate (PBSSe), polybutylene sebacate adipate (PBSeA), polybutylene sebacate (PBSe ) or corresponding polyesteramides understood. The aliphatic polyesters are marketed, for example, by the companies Showa Highpolymers under the name Bionolle® and by Mitsubishi under the name GSPIa®. More recent developments are described in WO 2010/03471 1.
Die aliphatischen Polyester weisen in der Regel Viskositätszahlen nach DIN 53728 von 150 bis 320 cm3/g und vorzugsweise 150 bis 250 cm3/g auf. The aliphatic polyesters generally have viscosity numbers according to DIN 53728 of 150 to 320 cm 3 / g and preferably 150 to 250 cm 3 / g.
Der MVR (Schmelzvolumenrate) nach EN ISO 1 133 (190°C, 2,16 kg Gewicht) liegt im Allgemeinen bei 0,1 bis 70, bevorzugt bei 0,8 bis 70 und insbesondere bei 1 bis 60 cm3/10 min. Die Säurezahlen nach DIN EN 12634 liegen im Allgemeinen bei 0,01 bis 1 ,2 mg KOH/g, vorzugsweise bei 0,01 bis 1 ,0 mg KOH/g und insbesondere bevorzugt bei 0,01 bis 0,7 mg KOH/g. Teilaromatische Polyester, die ebenfalls als Komponente i) geeignet sind, bestehen aus aliphatischen Diolen und aliphatischen sowie aromatischen Dicarbonsäuren. Zu den geeigneten teilaromatischen Polyestern gehören lineare nicht kettenverlängerte Polyester (WO 92/09654). Insbesondere sind aliphatisch/aromatische Polyester aus Butandiol, Terephthalsäure und aliphatischen C4-Ci8-Dicarbonsäuren wie Bernsteinsäure, Glutarsäure, Adipinsäure, Korksäure, Azelainsäure, Sebazinsäure und Brassylsäure (beispielsweise wie in WO 2006/097353 bis 56 beschrieben) geeignete Mischungspartner. Bevorzugt werden kettenverlängerte und/oder verzweigte teilaromatische Polyester als Komponente i eingesetzt. Letztere sind aus den eingangs genannten Schriften WO 96/15173 bis 15176, 21689 bis 21692, 25446, 25448 oder der WO 98/12242, bekannt, auf die ausdrücklich Bezug genommen wird. Mischungen unterschiedlicher teilaromatischer Polyester kommen ebenso in Betracht. Insbesondere geeignet sind biologisch abbaubare, aliphatisch-aromatischer Polyester i, die enthalten: a) 40 bis 70 mol %, bezogen auf die Komponenten a bis b, eines oder mehrerer Dicarbon- säurederivate oder Dicarbonsauren ausgewählt aus der Gruppe bestehend aus: Bernsteinsäure, Adipinsäure, Sebazinsäure, Azelainsäure und Brassylsäure; b) 60 bis 30 mol %, bezogen auf die Komponenten a bis b, eines Terephthalsäurederivats; c) 98 bis 102 mol %, bezogen auf die Komponenten a bis b, eines C2-C8-Alkylendiols oder C2-C6-Oxyalkylendiols; d) 0,00 bis 2 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten a bis d, eines Kettenverlängerers und /oder Verzweigers ausgewählt aus der Gruppe bestehend aus: einem di oder polyfunktionellen Isocyanat, Isocyanurat, Oxazolin , Epoxid, Peroxid, Carbonsäureanhydrid und /oder einem mindestens trifunktionellen Alkohol oder einer mindestens trifunktionellen Carbonsäure. MVR (melt volume rate) according to EN ISO 1133 (190 ° C, 2.16 kg weight) is generally 0.1 to 70, preferably from 0.8 to 70 and in particular from 1 to 60 cm 3/10 min. The acid numbers according to DIN EN 12634 are generally from 0.01 to 1.2 mg KOH / g, preferably from 0.01 to 1.0 mg KOH / g and particularly preferably from 0.01 to 0.7 mg KOH / g , Partaromatic polyesters which are likewise suitable as component i) consist of aliphatic diols and aliphatic and aromatic dicarboxylic acids. Suitable partially aromatic polyesters include linear non-chain extended polyesters (WO 92/09654). In particular, aliphatic / aromatic polyesters of butanediol, terephthalic acid and aliphatic C4-C8 dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid and brassylic acid (for example as described in WO 2006/097353 to 56) are suitable mixing partners. Chain-extended and / or branched partially aromatic polyesters are preferably used as component i. The latter are known from the aforementioned documents WO 96/15173 to 15176, 21689 to 21692, 25446, 25448 or WO 98/12242, to which reference is expressly made. Mixtures of different partially aromatic polyesters are also possible. Particularly suitable are biodegradable, aliphatic-aromatic polyesters i which contain: a) 40 to 70 mol%, based on components a to b, of one or more dicarboxylic acid derivatives or dicarboxylic acids selected from the group consisting of: succinic acid, adipic acid, Sebacic acid, azelaic acid and brassylic acid; b) 60 to 30 mol%, based on components a to b, of a terephthalic acid derivative; c) 98 to 102 mol%, based on the components a to b, of a C2-C8-alkylenediol or C2-C6-oxyalkylenediol; d) 0.00 to 2 wt .-%, based on the total weight of components a to d, of a chain extender and / or branching agent selected from the group consisting of: a di or polyfunctional isocyanate, isocyanurate, oxazoline, epoxide, peroxide, carboxylic anhydride and / or an at least trifunctional alcohol or an at least trifunctional carboxylic acid.
Bevorzugt eingesetzte aliphatisch-aromatische Polyester i enthalten: a) 50 bis 65, bezogen auf die Komponenten a bis b, eines oder mehrerer Dicarbonsäurede- rivate oder Dicarbonsäuren ausgewählt aus der Gruppe bestehend aus Bernsteinsäure, Azelainsäure, Brassylsäure und vorzugsweise Adipinsäure, insbesondere bevorzugt Sebazinsäure; b) 50 bis 35, bezogen auf die Komponenten a bis b, eines Terephthalsäurederivats; c) 98 bis102 mol %, bezogen auf die Komponenten a bis b, 1 ,4-Butandiol und d) 0 bis 2 Gew.-%, vorzugsweise 0, 01 bis 2 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten a bis d, eines Kettenverlängerers und /oder Verzweigers ausgewählt aus der Gruppe bestehend aus: einem polyfunktionellen Isocyanat , Isocyanurat, Oxazolin, Carbonsäureanhydrid wie Maleinsäureanhydrid, Epoxid (insbesondere eines epoxidhalti- gen Poly(meth)acrylats) und /oder einem mindestens trifunktionellen Alkohol oder einer mindestens trifunktionellen Carbonsäure. Preferred aliphatic-aromatic polyesters used comprise: a) from 50 to 65, based on components a to b, of one or more dicarboxylic acid derivatives or dicarboxylic acids selected from the group consisting of succinic acid, azelaic acid, brassylic acid and preferably adipic acid, particularly preferably sebacic acid; b) 50 to 35, based on components a to b, of a terephthalic acid derivative; c) 98 to 102 mol%, based on the components a to b, 1, 4-butanediol and d) 0 to 2 wt .-%, preferably 0, 01 to 2 wt .-%, based on the total weight of components a to d, a chain extender and / or branching agent selected from the group consisting of: a polyfunctional isocyanate, isocyanurate, oxazoline, carboxylic anhydride such as maleic anhydride, epoxide (in particular an epoxy-containing poly (meth) acrylate) and / or an at least trifunctional alcohol or at least one trifunctional carboxylic acid.
Als aliphatische Dicarbonsäuren eignen sich vorzugsweise, Bernsteinsäure, Adipinsäure und insbesondere bevorzugt Sebazinsäure. Die genannten Disäuren haben den Vorteil, dass sie auch als nachwachsende Rohstoffe zur Verfügung stehen. As aliphatic dicarboxylic acids are preferably succinic acid, adipic acid and particularly preferably sebacic acid. The diacids mentioned have the advantage that they are also available as renewable raw materials.
Die Synthese der beschriebenen Polyester i erfolgt nach den in WO-A 92/09654, WO-A The synthesis of the described polyester i is carried out according to the methods described in WO-A 92/09654, WO-A
96/15173 oder vorzugsweise in WO-A 09/127555 und WO-A 09/127556 beschriebenen Verfah- ren, vorzugweise in einer zweistufigen Reaktionskaskade. Zunächst werden die Dicarbonsäu- rederivate zusammen mit dem Diol in Anwesenheit eines Umesterungskatalysators zu einem Präpolyester umgesetzt. Dieser Präpolyester weist im Allgemeinen eine Viskositätszahl (VZ) von 50 bis 100mL/g, vorzugsweise 60 bis 80 mL/g auf. Als Katalysatoren werden üblicherweise Zink-, Aluminium- und insbesondere Titankatalysatoren eingesetzt. Titankatalysatoren wie Tet- ra(isopropyl)orthotitanat und insbesondere Tetrabutylorthotitanat (TBOT) haben gegenüber den in der Literatur häufig verwendeten Zinn-, Antimon-, Kobalt- und Bleikatalysatoren wie beispielsweise Zinndioctanat den Vorteil, dass im Produkt verbleibende Restmengen des Katalysators oder Folgeprodukt des Katalysators weniger toxisch sind. Dieser Umstand ist bei den biologisch abbaubaren Polyestern besonders wichtig, da sie über die Kompostierung unmittelbar in die Umwelt gelangen können. 96/15173 or preferably in WO-A 09/127555 and WO-A 09/127556. ren, preferably in a two-stage reaction cascade. First, the dicarboxylic acid derivatives are reacted together with the diol in the presence of a transesterification catalyst to form a prepolyester. This prepolyester generally has a viscosity number (CV) of 50 to 100 ml / g, preferably 60 to 80 ml / g. The catalysts used are usually zinc, aluminum and in particular titanium catalysts. Titanium catalysts, such as tetra (isopropyl) orthotitanate and in particular tetrabutyl orthotitanate (TBOT), have the advantage over the tin, antimony, cobalt and lead catalysts frequently used in the literature, such as, for example, tin dioctanate, that residual amounts of catalyst remaining in the product or a secondary product of the catalyst are less toxic. This fact is particularly important in the case of biodegradable polyesters, since they can go directly into the environment via composting.
Die Polyester i werden anschließend in einem zweiten Schritt nach den in WO-A 96/15173 und EP-A 488 617 beschriebenen Verfahren hergestellt. Der Präpolyester wird mit Kettenverlänge- ren d, beispielsweise mit Diisocyanaten oder mit epoxidhaltigen Polymethacrylaten in einer Kettenverlängerungsreaktion zu einem Polyester mit einer VZ von 150 bis 320 mL/g, vorzugsweise 180 bis 250 mL/g umgesetzt. The polyesters i are subsequently produced in a second step according to the processes described in WO-A 96/15173 and EP-A 488 617. The prepolyester is reacted with chain extenders d, for example with diisocyanates or with epoxide-containing polymethacrylates, in a chain extension reaction to give a polyester having a viscosity of 150 to 320 ml / g, preferably 180 to 250 ml / g.
In der Regel werden 0,01 bis 2 Gew-%, vorzugsweise 0,1 bis 1 ,0 Gew.-% und insbesondere bevorzugt 0,1 bis 0,3 Gew.-% bezogen auf das Gesamtgewicht der Komponenten i bis iii, eines Verzweigers (d') und/oder Kettenverlängerers (d) ausgewählt aus der Gruppe bestehend aus: einem polyfunktionellen Isocyanat, Isocyanurat, Oxazolin, Epoxid, Peroxid, Carbonsäureanhydrid, einem mindestens trifunktionellen Alkohol oder einer mindestens trifunktionellen Carbonsäure eingesetzt. Als Kettenverlängerer d kommen polyfunktionelle und insbesondere difunktionelle Isocyanate, Isocyanurate, Oxazoline, Carbonsäureanhydrid oder Epoxide in Frage. In general, 0.01 to 2% by weight, preferably 0.1 to 1, 0 wt .-% and particularly preferably 0.1 to 0.3 wt .-% based on the total weight of components i to iii, one Branching agent (d ') and / or chain extender (d) selected from the group consisting of: a polyfunctional isocyanate, isocyanurate, oxazoline, epoxide, peroxide, carboxylic anhydride, an at least trifunctional alcohol or an at least trifunctional carboxylic acid. Suitable chain extenders d are polyfunctional and in particular difunctional isocyanates, isocyanurates, oxazolines, carboxylic anhydride or epoxides.
Kettenverlängerer sowie Alkohole oder Carbonsäurederivate mit mindestens drei funktionellen Gruppen können auch als Vernetzer d' aufgefasst werden. Besonders bevorzugte Verbindungen haben drei bis sechs funktionelle Gruppen. Beispielhaft seien genannt: Weinsäure, Zitronensäure, Äpfelsäure; Trimethylolpropan, Trimethylolethan; Pentaerythrit; Polyethertriole und Glycerin, Trimesinsäure, Trimellitsäure, Trimellitsäureanhydrid, Pyromellitsäure und Pyromel- litsäuredianhydrid. Bevorzugt sind Polyole wie Trimethylolpropan, Pentaerythrit und insbesondere Glycerin. Mittels der Komponenten d und d' lassen sich biologisch abbaubare Polyester mit einer strukturellen Viskosität aufbauen. Das rheologische Verhalten der Schmelzen verbessert sich; die biologisch abbaubaren Polyester lassen sich leichter verarbeiten. Die Verbindungen d wirken scherentzähend, d.h. die Viskosität bei höheren Schergeschwindigkeiten wird geringer. Chain extenders and alcohols or carboxylic acid derivatives having at least three functional groups can also be understood as crosslinkers d '. Particularly preferred compounds have three to six functional groups. Examples include: tartaric acid, citric acid, malic acid; Trimethylolpropane, trimethylolethane; pentaerythritol; Polyether triols and glycerol, trimesic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid and pyromellitic dianhydride. Preference is given to polyols such as trimethylolpropane, pentaerythritol and in particular glycerol. By means of the components d and d ', biodegradable polyesters with a structural viscosity can be built up. The rheological behavior of the melts improves; The biodegradable polyesters are easier to process. The compounds d are shear-thinning, i. the viscosity at higher shear rates becomes lower.
Die Polyester i weisen in der Regel ein zahlenmittleres Molekulargewicht (Mn) im Bereich von 10000 bis 100000, insbesondere im Bereich von 15000 bis 75000 g/mol, bevorzugt im Bereich von 20000 bis 38000 g/mol, ein gewichtmittleres Molekulargewicht (Mw) von 30000 bis 300000, vorzugsweise 60000 bis 200000 g/mol und ein Mw/Mn-Verhältnis von 1 bis 6, vorzugsweise 2 bis 4 auf. Die Viskositätszahl liegt zwischen 150 und 320, vorzugsweise von 180 bis 250 g/mL (gemessen in o-Dichlorbenzol/Phenol (Gewichtsverhältnis 50/50). Der Schmelzpunkt liegt im Bereich von 85 bis 150, bevorzugt im Bereich von 95 bis 140°C. Die genannten Polyester können Hydroxy- und/oder Carboxylend-gruppen in jedem beliebigen Verhältnis aufweisen. Die genannten teilaromatischen Polyester können auch endgruppenmodi- fiziert werden. So können beispielsweise OH-Endgruppen durch Umsetzung mit Phthalsäure, Phthalsäureanhydrid, Trimellithsäure, Trimellithsäureanhydrid, Pyromellithsäure oder Pyromel- lithsäureanhydrid säuremodifiziert werden. Bevorzugt sind Polyester mit Säurezahlen kleiner als 1 ,5 mg KOH/g. The polyesters i generally have a number average molecular weight (Mn) in the range from 10,000 to 100,000, in particular in the range from 15,000 to 75,000 g / mol, preferably in the range from 20,000 to 38,000 g / mol, a weight-average molecular weight (Mw) of 30,000 to 300,000, preferably 60000 to 200,000 g / mol and a Mw / Mn ratio of 1 to 6, preferably 2 up to 4. The viscosity number is between 150 and 320, preferably from 180 to 250 g / ml (measured in o-dichlorobenzene / phenol (weight ratio 50/50).) The melting point is in the range of 85 to 150, preferably in the range of 95 to 140 ° C. The abovementioned polyesters can have hydroxyl and / or carboxyl end groups in any desired ratio. [Te Die] The semiaromatic polyesters can also be end-group-modified, for example OH end groups can be obtained by reaction with phthalic acid, phthalic anhydride, trimellitic acid, trimellitic anhydride, pyromellitic acid or pyromel polyesters with acid numbers of less than 1.5 mg KOH / g are preferred.
Die biologisch abbaubaren Polyester i können weitere dem Fachmann bekannte, aber nicht erfindungswesentliche Inhaltsstoffe enthalten. Beispielsweise die in der Kunststofftechnik üblichen Zusatzstoffe wie Stabilisatoren; Nukleierungsmittel; Gleit- und Trennmittel wie Stearate (insbesondere Calziumstearat); Weichmacher (Plastifizierer) wie beispielsweise Zitronensäureester (insbesondere Acetyl-tributylcitrat), Glycerinsäureester wie Triacetylglycerin oder Ethyl- englykolderivate, Tenside wie Polysorbate, Palmitate oder Laurate; Wachse wie beispielsweise Bienenwachs oder Bienenwachsester; Antistatikum, UV-Absorbers; UV-Stabilisators; Antifog- Mittel oder Farbstoffe. Die Additive werden in Konzentrationen von 0 bis 5 Gew.-%, insbesonde- re 0,1 bis 2 Gew.-% bezogen auf die erfindungsgemäßen Polyester eingesetzt. The biodegradable polyesters i may contain further ingredients known to the person skilled in the art but not essential to the invention. For example, the usual additives in plastics technology such as stabilizers; nucleating agents; Lubricants and release agents such as stearates (especially calcium stearate); Plasticizers such as citric acid esters (especially acetyl tributyl citrate), glyceric acid esters such as triacetylglycerol or ethylglycol derivatives, surfactants such as polysorbates, palmitates or laurates; Waxes such as beeswax or beeswax esters; Antistatic, UV absorber; UV-stabilizer; Antifog agents or dyes. The additives are used in concentrations of from 0 to 5% by weight, in particular from 0.1 to 2% by weight, based on the polyesters according to the invention.
Als Komponente ii) wird Polymilchsäure mit dem folgenden Eigenschaftsprofil bevorzugt eingesetzt: · einer Schmelzvolumenrate (MVR bei 190° C und 2.16 kg nach ISO 1 133 von 0.5 bis 15 bevorzugt 1 bis 9, besonders bevorzugt 2 bis 8 ml/10 Minuten ) As component ii), polylactic acid having the following property profile is preferably used: a melt volume rate (MVR at 190 ° C. and 2.16 kg according to ISO 1 133 of 0.5 to 15, preferably 1 to 9, particularly preferably 2 to 8 ml / 10 minutes)
• einem Schmelzpunkt unter 180° C;  • a melting point below 180 ° C;
• einem Glaspunkt (Tg) größer 40°C  • a glass point (Tg) greater than 40 ° C
• einem Wassergehalt von kleiner 1000 ppm  • a water content of less than 1000 ppm
· einem Monomeren-Restgehalt (Lactid) von kleiner 0.3%.  · A residual monomer content (lactide) of less than 0.3%.
• einem Molekulargewicht von größer 50 000 Dalton.  • a molecular weight greater than 50,000 daltons.
Bevorzugte Polymilchsäuren sind beispielsweise von NatureWorks® das Ingeo® 2002 D, 4032 D, 4042 D und 4043 D, 8251 D, 3251 D und insbesondere 8051 D sowie 8052D. NatureWorks Ingeo® 8051 D und 8052 D sind Polymilchsäuren der Fa. NatureWorks, mit den folgenden Produkteigenschaften: Tg: 65,3°C, Tm: 153,9°C, MVR: 6,9 [ml/10 Minuten], Mw:186000, Examples of preferred polylactic acids of NatureWorks® are Ingeo® 2002 D, 4032 D, 4042 D and 4043 D, 8251 D, 3251 D and in particular 8051 D and 8052D. NatureWorks Ingeo® 8051 D and 8052 D are polylactic acids from NatureWorks, with the following product properties: Tg: 65.3 ° C, Tm: 153.9 ° C, MVR: 6.9 [ml / 10 minutes], M w : 186000,
Mn:107000. Weiterhin weisen diese Produkte eine etwas höhere Säurezahl auf. Mn: 107,000th Furthermore, these products have a slightly higher acid number.
Für die Herstellung der erfindungsgemäßen expandierbaren Granulate haben sich insbesondere Polymilchsäuren mit einer MVR nach ISO 1 133 [190°C/2,16 kg] von 5 bis 8 ml/10 Minuten als vorteilhaft erweisen. Komponente iii) wird im Folgenden näher beschrieben. For the production of the expandable granules according to the invention, in particular polylactic acids having an MVR according to ISO 1 133 [190 ° C./2.16 kg] of 5 to 8 ml / 10 minutes have proven to be advantageous. Component iii) is described in more detail below.
Unter Epoxiden wird insbesondere Epoxidgruppen-haltiges Copolymer auf Basis Styrol, Acryl- säureester und/oder Methacrylsaureester verstanden. Die Epoxidgruppen tragenden Einheiten sind vorzugsweise Glycidyl(meth)acrylate. Als vorteilhaft haben sich Copolymere mit einem Glycidylmethacrylat-Anteil von größer 20, besonders bevorzugt von größer 30 und insbesondere bevorzugt von größer 50 Gew.-% des Copolymers erwiesen. Das Epoxid-Äquivalentgewicht (EEW) in diesen Polymeren beträgt vorzugsweise 150 bis 3000 und insbesondere bevorzugt 200 bis 500 g/Äquivalent. Das mittlere Molekulargewicht (Gewichtsmittel) Mw der Polymere beträgt vorzugsweise 2000 bis 25.000, insbesondere 3000 bis 8.000. Das mittlere Molekularge- wicht (Zahlenmittel) Mn der Polymere beträgt vorzugsweise 400 bis 6.000, insbesondere 1000 bis 4.000. Die Polydispersität (Q) liegt im Allgemeinen zwischen 1 .5 und 5. Epoxidgruppen- haltige Copolymere des obengenannten Typs werden beispielsweise von der BASF Resins B.V. unter der Marke Joncryl® ADR vertrieben. Als Kettenverlängerer besonders geeignet ist Jonc- ryl® ADR 4368. Epoxides are understood as meaning, in particular, epoxide-group-containing copolymer based on styrene, acrylic acid ester and / or methacrylic acid ester. The epoxy groups bearing units are preferably glycidyl (meth) acrylates. Copolymers having a glycidyl methacrylate content of greater than 20, particularly preferably greater than 30 and especially preferably greater than 50% by weight, of the copolymer have proven to be advantageous. The epoxy equivalent weight (EEW) in these polymers is preferably 150 to 3000, and more preferably 200 to 500 g / equivalent. The weight average molecular weight Mw of the polymers is preferably from 2,000 to 25,000, in particular from 3,000 to 8,000. The number average molecular weight M n of the polymers is preferably from 400 to 6,000, in particular from 1,000 to 4,000. The polydispersity (Q) is generally between 1 .5 and 5 epoxide groups-containing copolymers of the above type are sold for example by BASF Resins BV under the trademark Joncryl ® ADR. Particularly suitable as a chain is Jonc- ryl ® ADR 4368th
Unter Komponente iv wird insbesondere eines oder mehrere der folgenden Zusatzstoffe verstanden: Stabilisator, Nukleierungsmittel, Gleit- und Trennmittel, Tensid, Wachs, Antistatikum, Antifog-Mittel, Farbstoff, Pigment, UV-Absorber, UV-Stabilisator oder sonstigen Kunststoffadditiv. Komponente iv wird vorzugsweise in einer Menge von 0,5 bis 1 Gew.-% bezogen auf die Komponenten i und iv eingesetzt. In particular, component iv is understood as meaning one or more of the following additives: stabilizer, nucleating agent, lubricant and release agent, surfactant, wax, antistatic agent, antifogging agent, dye, pigment, UV absorber, UV stabilizer or other plastic additive. Component iv is preferably used in an amount of from 0.5 to 1% by weight, based on components i and iv.
Die erfindungsgemäßen Formmassen enthalten 69 bis 98 Gew.-%, vorzugsweise 75 bis 92 Gew.-%, und insbesondere bevorzugt 80 bis 90 Gew.-% des Thermoplasten A und dementsprechend 2 bis 31 Gew.-%, vorzugsweise 8 bis 25 Gew.-%, und insbesondere bevorzugt 10 bis 20 Gew.-% der Polymermischung B. Die Kerbschagzähigkeit steigt in der Regel mit wachsendem Anteil der Polymermischung B an. The molding compositions of the invention contain 69 to 98 wt .-%, preferably 75 to 92 wt .-%, and particularly preferably 80 to 90 wt .-% of the thermoplastic A and, accordingly, 2 to 31 wt .-%, preferably 8 to 25 wt. %, and more preferably 10 to 20 wt .-% of the polymer mixture B. The notch toughness increases as a rule with increasing proportion of the polymer mixture B.
Die Zusatzstoffe C werden in Mengen von 0 bis 40 Gew.-%, insbesondere 0,5 bis 30 Gew.-%, bezogen auf die Komponenten A bis C eingesetzt. Die hohen Gewichtsanteile kommen insbe- sondere für Füllstoffe in Frage. The additives C are used in amounts of 0 to 40 wt .-%, in particular 0.5 to 30 wt .-%, based on the components A to C. The high weight fractions are particularly suitable for fillers.
Als bevorzugte faserförmige Füllstoffe C seien Kohlenstofffasern, Aramid-Fasern, Glasfasern und Kaliumtitanat-Fasern genannt, wobei Glasfasern als E-Glas besonders bevorzugt sind. Diese werden als Rovings in den handelsüblichen Formen eingesetzt. Preferred fibrous fillers C are carbon fibers, aramid fibers, glass fibers and potassium titanate fibers, glass fibers being particularly preferred as E glass. These are used as rovings in the commercial forms.
Die erfindungsgemäß als Roving eingesetzten Glasfasern weisen einen Durchmesser von 6 bis 20 μηη, bevorzugt von 10 bis 18 μηη auf, wobei der Querschnitt der Glasfasern rund, oval oder eckig ist. Insbesondere werden erfindungsgemäß E-Glasfasern verwendet. Es können aber auch alle anderen Glasfasersorten, wie z.B. A-, C-, D-, M-, S-, R-Glasfasern oder beliebige Mi- schungen davon oder Mischungen mit E-Glasfasern eingesetzt werden. Die faserförmigen Füllstoffe können zur besseren Verträglichkeit mit den Thermoplasten mit einer Silanverbindung oberflächlich vorbehandelt sein. The glass fibers used according to the invention as a roving have a diameter of 6 to 20 μm, preferably of 10 to 18 μm, the cross section of the glass fibers being round, oval or angular. In particular, E-glass fibers are used according to the invention. However, it is also possible to use all other types of glass fiber, such as A, C, D, M, S, R glass fibers or any mixtures thereof or mixtures with E glass fibers. The fibrous fillers can be surface-pretreated for better compatibility with the thermoplastics with a silane compound.
Geeignete Silanverbindungen sind solche der allgemeinen Formel (X-(CH2)n)k-Si-(0-CmH2m+l )4-k in der die Substituenten folgende Bedeutung haben: n eine ganze Zahl von 2 bis 10, bevorzugt 3 bis 4 Suitable silane compounds are those of the general formula (X- (CH 2) n) k -Si (O-C m H 2 m + 1) 4-k in which the substituents have the following meanings: n is an integer from 2 to 10, preferably 3 to 4
m eine ganze Zahl von 1 bis 5, bevorzugt 1 bis 2 m is an integer from 1 to 5, preferably 1 to 2
k eine ganze Zahl von 1 bis 3, bevorzugt 1 Bevorzugte Silanverbindungen sind Aminopropyltrimethoxysilan, Aminobutyltrimeth-oxysilan, Aminopropyltriethoxysilan, Aminobutyltriethoxysilan sowie die entsprechenden Silane, welche als Substituent X eine Glycidylgruppe enthalten. k is an integer from 1 to 3, preferably 1 Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl group as substituent X.
Die Silanverbindungen werden im Allgemeinen in Mengen von 0,01 bis 2, vorzugsweise 0,025 bis 1 ,0 und insbesondere 0,05 bis 0,5 Gew.-% (bezogen auf C)) zur Oberflächenbeschichtung eingesetzt. The silane compounds are generally used in amounts of 0.01 to 2, preferably 0.025 to 1, 0 and in particular 0.05 to 0.5 wt .-% (based on C)) for surface coating.
Andere geeignete Beschichtungsmittel (auch Schlichte genannt) basieren auf Isocyanaten. Bevorzugt beträgt das L/D (Länge/Durchmesser)-Verhältnis 100 bis 4000, insbesondere 350 bis 2000 und ganz besonders 350 bis 700. Other suitable coating agents (also called sizing agents) are based on isocyanates. Preferably, the L / D (length / diameter) ratio is 100 to 4000, in particular 350 to 2000 and very particularly 350 to 700.
Die thermoplastischen Formmassen enthalten weiterhin vorteilhafterweise ein Schmiermittel C. Als Komponente C können die erfindungsgemäßen Formmassen von 0 bis 3, bevorzugt von 0,05 bis 3, vorzugsweise von 0,1 bis 1 ,5 und insbesondere von 0,1 bis 1 Gew.-% eines The thermoplastic molding compositions furthermore advantageously contain a lubricant C. As component C, the molding compositions of the invention may be from 0 to 3, preferably from 0.05 to 3, preferably from 0.1 to 1.5 and in particular from 0.1 to 1,% by weight. % one
Schmiermittels bezogen auf die Gesamtmenge der Komponenten A bis C enthalten. Lubricant based on the total amount of components A to C included.
Bevorzugt sind Aluminium-, Alkali-, Erdalkalisalze oder Ester- oder Amide von Fettsäuren mit 10 bis 44 C-Atomen, vorzugsweise mit 14 bis 44 C-Atomen. Die Metallionen sind vorzugsweise Erdalkali und Aluminium (AI), wobei Calzium (Ca) oder Magnesium besonders bevorzugt sind. Bevorzugte Metallsalze sind Ca-Stearat und Ca-Montanat sowie Al-Stearat. Es können auch Mischungen verschiedener Salze eingesetzt werden, wobei das Mischungsverhältnis beliebig ist. Preference is given to aluminum, alkali metal, alkaline earth metal salts or ester or amides of fatty acids having 10 to 44 C atoms, preferably having 14 to 44 C atoms. The metal ions are preferably alkaline earth and aluminum (Al), with calcium (Ca) or magnesium being particularly preferred. Preferred metal salts are Ca-stearate and Ca-montanate as well as Al-stearate. It is also possible to use mixtures of different salts, the mixing ratio being arbitrary.
Die Carbonsäuren können 1 - oder 2-wertig sein. Als Beispiele seien Pelargonsäure, Palmitinsäure, Laurinsäure, Margarinsäure, Dodecandisäure, Behensäure und besonders bevorzugt Stearinsäure, Caprinsäure sowie Montansäure (Mischung von Fettsäuren mit 30 bis 40 C- Atomen) genannt. The carboxylic acids can be 1- or 2-valent. Examples which may be mentioned are pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid and particularly preferred Stearic acid, capric acid and montanic acid (mixture of fatty acids having 30 to 40 carbon atoms) called.
Die aliphatischen Alkohole können 1 - bis 4-wertig sein. Beispiele für Alkohole sind n-Butanol, n- Octanol, Stearylalkohol, Ethylenglykol, Propylenglykol, Neopentylglykol, Pentaerythrit, wobei Glycerin und Pentaerythrit bevorzugt sind.  The aliphatic alcohols can be 1 - to 4-valent. Examples of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, with glycerol and pentaerythritol being preferred.
Die aliphatischen Amine können 1 - bis 3-wertig sein. Beispiele hierfür sind Stearylamin, Ethyl- endiamin, Propylendiamin, Hexamethylendiamin, Di(6-Aminohexyl)amin, wobei Ethylendiamin und Hexamethylendiamin besonders bevorzugt sind. Bevorzugte Ester oder Amide sind ent- sprechend Glycerindistearat, Glycerintristearat, Ethylendiamindistearat, Glycerinmonopalmitrat, Glycerintrilaurat, Glycerinmonobehenat und Penta-erythrittetrastearat. The aliphatic amines can be 1 - to 3-valent. Examples of these are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di (6-aminohexyl) amine, with ethylenediamine and hexamethylenediamine being particularly preferred. Preferred esters or amides are correspondingly glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate and pentaerythritol tetrastearate.
Es können auch Mischungen verschiedener Ester oder Amide oder Ester mit Amiden in Kombination eingesetzt werden, wobei das Mischungsverhältnis beliebig ist. It is also possible to use mixtures of different esters or amides or esters with amides in combination, the mixing ratio being arbitrary.
Als weitere Komponente C können die erfindungsgemäßen thermoplastischen Formmassen übliche Verarbeitungshilfsmittel wie Stabilisatoren, Oxidationsverzögerer, weitere Mittel gegen Wärmezersetzung und Zersetzung durch ultraviolettes Licht, Gleit- und Entformungsmittel, Färbemittel wie Farbstoffe und Pigmente, Keimbildungsmittel, Weichmacher, Flammschutzmittel usw. enthalten. As a further component C thermoplastic molding compositions according to the invention conventional processing aids such as stabilizers, oxidation retardants, other agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, flame retardants, etc. included.
Als Beispiele für Oxidationsverzögerer und Wärmestabilisatoren seien Phosphite und weitere Amine (z. B. TAD), Hydrochinone, verschiedene substituierte Vertreter dieser Gruppen und deren Mischungen in Konzentrationen bis zu 1 Gew.-%, bezogen auf das Gewicht der thermoplas- tischen Formmassen genannt. Examples of oxidation inhibitors and heat stabilizers are phosphites and further amines (eg TAD), hydroquinones, various substituted representatives of these groups and mixtures thereof in concentrations of up to 1% by weight, based on the weight of the thermoplastic molding compositions.
Als UV-Stabilisatoren, die im Allgemeinen in Mengen bis zu 2 Gew.-%, bezogen auf die Formmasse, verwendet werden, seien verschiedene substituierte Resorcine, Salicylate, Benzotriazo- le und Benzophenone genannt. As UV stabilizers, which are generally used in amounts of up to 2 wt .-%, based on the molding composition, various substituted resorcinols, salicylates, Benzotriazo- le and benzophenones may be mentioned.
Es können anorganische Pigmente, wie Titandioxid, Ultramarinblau, Eisenoxid und Ruß und/oder Grafit, weiterhin organische Pigmente, wie Phthalocyanine, Chinacridone, Perylene sowie Farbstoffe, wie Nigrosin und Anthrachinone als Farbmittel zugesetzt werden. Als Keimbildungsmittel können Natriumphenylphosphinat, Aluminiumoxid, Siliziumdioxid sowie bevorzugt Talkum eingesetzt werden. It is possible to add inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide and carbon black and / or graphite, furthermore organic pigments such as phthalocyanines, quinacridones, perylenes and also dyes such as nigrosine and anthraquinones as colorants. As nucleating agents, sodium phenylphosphinate, alumina, silica and preferably talc may be used.
Als Flammschutzmittel seien roter Phosphor, P- und N-haltige Flammschutzmittel sowie halo- genierte Flammschutzmittelsysteme und deren Synergisten genannt. Flame retardants include red phosphorus, flame retardants containing P and N, and halogenated flame retardant systems and their synergists.
Beispiele Messmethoden und Eigenschaften Examples Measurement methods and properties
Die Bestimmung der Viskositätszahl erfolgte nach DIN 53728 Teil 3, 3. Januar 1985. Als Lösungsmittel wurde das Gemisch: Phenol/Dichlorbenzol im Gewichtsverhältnis 50/50 verwendet. The determination of the viscosity number was carried out according to DIN 53728 Part 3, January 3, 1985. The solvent used was the mixture: phenol / dichlorobenzene in a weight ratio of 50/50.
Die Charpy-Kerbschlagzähigkeit wurde bei 23°C respektive -30°C gemäß ISO 179-2/1 eA ermittelt. Die Streckspannung, E-Modul und Bruchdehnung wurde nach ISO 527-2:1993 ermittelt. Die Zuggeschwindigkeit betrug 5 mm/min. The Charpy notched impact strength was determined at 23 ° C or -30 ° C according to ISO 179-2 / 1 eA. The yield stress, Young's modulus and elongation at break were determined according to ISO 527-2: 1993. The pulling speed was 5 mm / min.
Einsatzstoffe Es wurden folgende Komponenten verwendet: Komponente A: Starting materials The following components were used: Component A:
Ai: PVC 250 SB der Firma Solvin SA (CAS:9002-86-2 , Dichte: 590 g/l, Restmonomergehalt: Ai: PVC 250 SB from Solvin SA (CAS: 9002-86-2, density: 590 g / l, residual monomer content:
< 1 ppm, Schmelzpunkt: 75-85 °C)  <1 ppm, melting point: 75-85 ° C)
Aii: Ultramid® B27E der Firma BASF SE (CAS:25038-54-4, Dichte: 1 120-1 150 g/l, Schmelzpunkt: 220 °C, Relative Viskosität (1 % in 96% H2S04): 2,7± 0,03) Komponente B: Aii: Ultramid ® B27E BASF SE (CAS: 25038-54-4, density: 1120-1150 g / l, melting point: 220 ° C, Relative viscosity (1% in 96% H2S04): 2.7 ± 0.03) Component B:
Bi: 67,9 Gew.-% Ecoflex® C1200 (alte Produktbezeichnung: Ecoflex® FBX 701 1 )- ein Polyb- utylenadipat-coterephthalat der Fa. BASF SE, 32 Gew.-% Polymilchsäure (PLA) Ingeo® 4043D der Firma Natureworks LLC; 0,1 Gew.-% Joncryl® ADR 4368 - ein epoxidgrup- pen-haltiges Copolymer auf Basis Styrol, Acrylsäureester und/oder Methacrylsäureester der Firma BASF Resins B.V. Bi: 67.9 wt .-% Ecoflex ® C1200 (old product name: Ecoflex FBX ® 701 1) - a Polyb- utylenadipat-co-terephthalate from BASF SE, 32 wt .-% of polylactic acid (PLA) Ingeo ® 4043D of NatureWorks. LLC; 0.1% by weight of Joncryl® ADR 4368 - an epoxide group-containing copolymer based on styrene, acrylic ester and / or methacrylic ester from BASF Resins BV
Bii: 54,9 Gew.-% Ecoflex® C1200 (alte Produktbezeichnung: Ecoflex® FBX 701 1 )- ein Polyb- utylenadipat-coterephthalat der Fa. BASF SE, 45 Gew.-% Polymilchsäure (PLA) Ingeo® 4043D der Firma Natureworks LLC; 0,1 Gew.-% Joncryl® ADR 4368 - ein epoxidgrup- pen-haltiges Copolymer auf Basis Styrol, Acrylsäureester und/oder Methacrylsäureester der Firma BASF Resins B.V. Bii: 54.9 wt .-% Ecoflex ® C1200 (old product name: Ecoflex FBX ® 701 1) -. A Polyb- utylenadipat-co-terephthalate from BASF SE 45 wt .-% of polylactic acid (PLA), Ingeo ® 4043D of NatureWorks LLC; 0.1% by weight of Joncryl® ADR 4368 - an epoxide group-containing copolymer based on styrene, acrylic ester and / or methacrylic ester from BASF Resins BV
Komponente C: Component C:
Ci: Baerostab M25-85 der Firma Baerlocher GmbH (Baerostab M25-85 ist ein modifiziertes Butyl-Zinn-mercaptid. Dieses Produkt enthält ein nicht migrierendes Gleitmittel, and wur- de als PVC Stabilisator entwickelt. Dichte bei 20 °C: 1080 g/l, Viskosität bei 20 °C: 80 mPa.s) Baerostab M25-85 from Baerlocher GmbH (Baerostab M25-85 is a modified butyl-tin-mercaptide.) This product contains a non-migrating lubricant, and de developed as a PVC stabilizer. Density at 20 ° C: 1080 g / l, viscosity at 20 ° C: 80 mPa.s)
Cii: Acrawax C der Firma Lonza AG (besteht aus Ν,Ν'-Ethylenbisstearamid (CAS: 1 10-30-5), N,N'-Ethan-1 ,2-diylbishexadecan-1 -amid (CAS: 5518-18-3), Ci4-18-Fettsäuren (CAS: 67701 -02-4), Schmelzpunkt: 140-145 °C) Cii: Acrawax C from Lonza AG (consists of Ν, Ν'-ethylenebisstearamide (CAS: 1 10-30-5), N, N'-ethane-1,2-diylbishexadecane-1-amide (CAS: 5518-18 -3), C 4 -18 fatty acids (CAS: 67701 -02-4), melting point: 140-145 ° C)
Ciii: Irganox 98 der Firma BASF SE (N,N'-Hexane-1 ,6-diylbis[3-(3,5-di-tert-butyl-4- hydroxyphenylpropionamide)], CAS Number: 23128-74-7, Schmelzpunkt: 156-165 °C) Ciii: Irganox 98 from BASF SE (N, N'-hexane-1, 6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide)], CAS Number: 23128-74-7, Melting point: 156-165 ° C)
Civ: Talkum IT der Firma Mondo Minerals (CAS: 14807-96-6, Dichte:2750 g/l) Beispiel 1 Civ: Talc IT from Mondo Minerals (CAS: 14807-96-6, density: 2750 g / l) Example 1
Die Formmassen des Vergleichsbeispiels 1 und Beispiels 1 wurden auf einem DSM Miniextruder mit einer Drehzahl von 80 1/min bei 180°C hergestellt: The molding compositions of Comparative Example 1 and Example 1 were prepared on a DSM mini-extruder at a speed of 80 1 / min at 180 ° C:
Herstellung der Probekörper Preparation of the specimens
Die zur Bestimmung der Eigenschaften verwendeten Prüfkörper wurden mittels einer DSM Spritzgussmaschine hergestellt. Die 180°C heiße im DSM Miniextruder hergestellte Schmelzemischung wurde mit 15bar in das 70°C heiße Werkzeug gepresst. Die Kerbe wurde in den Charpystab nach ISO 179-2/1 eA(F) gefräst und geprüft. The specimens used to determine the properties were produced by means of a DSM injection molding machine. The 180 ° C hot melt mixture produced in the DSM Mini Extruder was pressed at 15 bar into the 70 ° C hot tool. The notch was milled into the Charpystab according to ISO 179-2 / 1 eA (F) and tested.
Tabelle 1 : Einfluss von Komponente B auf die Kerbschlagzähigkeit von PVC Table 1: Influence of component B on the notched impact strength of PVC
Die Zusammensetzungen der Formmassen und die Ergebnisse der Messungen sind der Tabelle 1 zu entnehmen. Beispiel 1 mit der erfindungsgemäßen Polymermischung B wies eine um 42 % höhere Kerbschlagzähigkeit als Vergleichsbeispiel 1 auf. Beispiel 2 The compositions of the molding compositions and the results of the measurements are shown in Table 1. Example 1 with the polymer mixture B according to the invention had a notched impact strength 42% higher than Comparative Example 1. Example 2
Die Formmassen des Vergleichsbeispiels 2 und der Beispiele 2 und 3 wurden auf einer ZSK 30 mit einer Drehzahl von 250 1/min bei 260°C hergestellt: The molding compositions of Comparative Example 2 and Examples 2 and 3 were prepared on a ZSK 30 at a speed of 250 1 / min at 260 ° C:
Herstellung der Probekörper Preparation of the specimens
Die zur Bestimmung der Eigenschaften verwendeten Prüfkörper wurden mittels einer Battenfeld 50 Spritzgussmachine hergestellt. Die unter 2) und 3) hergestellten Granulate wurden aufge- schmolzen und mit Umdrehungszahl der Schnecke 100 U/min und Verweilzeit 50 s in das Werkzeug eingepresst. Die Prüfkörper für die Spannungstests wurden nach ISO 527-2/1 A 50 und die Prüfkörper für die Schlagzähigkeitsmessungen nach ISO 179-2/1 eA(F) hergestellt. Die Einspritztemperatur betrug 260°C, die Werkzeugtemperatur 80°C. Tabelle 2: Einfluss von Komponente B auf die Kerbschlagzähigkeit von Polyamid  The test specimens used to determine the properties were prepared by means of a Battenfeld 50 injection molding machine. The granules produced under 2) and 3) were melted and pressed into the mold at a speed of rotation of the screw at 100 rpm and a residence time of 50 s. The test specimens for the stress tests were produced according to ISO 527-2 / 1 A 50 and the test specimens for the impact measurements according to ISO 179-2 / 1 eA (F). The injection temperature was 260 ° C, the mold temperature 80 ° C. Table 2: Influence of component B on the notched impact strength of polyamide
Die Zusammensetzungen der Formmassen und die Ergebnisse der Messungen sind der Tabelle 2 zu entnehmen. Beispiel 2 mit 10 Gew.-% der erfindungsgemäßen Polymermischung B wies bei 23 °C (-30 °C) eine um 45 % (19 %) höhere Kerbschlagzähigkeit als Vergleichsbeispiel 2 auf. Beispiel 3 mit 30 Gew.-% der erfindungsgemäßen Polymermischung B wies bei 23 °C (-30 °C) eine um 141 % (85 %) höhere Kerbschlagzähigkeit als Vergleichsbeispiel 2 auf. The compositions of the molding compositions and the results of the measurements are shown in Table 2. Example 2 with 10% by weight of the polymer mixture B according to the invention had a notched impact strength of 45% (19%) at 23 ° C. (-30 ° C.) compared to Comparative Example 2. Example 3 with 30 wt .-% of the polymer mixture B according to the invention had at 23 ° C (-30 ° C) by 141% (85%) higher notched impact strength than Comparative Example 2 on.
Die Zugeigenschaften: Bruchdehnung, Zugfestigkeit und E-Modul waren im erfindungsgemäßen Beispiel 3 gegenüber Beispiel 2 verbessert und auf einem ähnlichen Niveau wie in Vergleichsbeispiel 2V. The tensile properties: elongation at break, tensile strength and modulus of elasticity were improved in Example 3 according to the invention compared with Example 2 and at a level similar to Comparative Example 2V.

Claims

Patentansprüche claims
1 . Thermoplastische Formmasse, enthaltend 1 . Thermoplastic molding composition containing
A) 69 bis 98 Gew.-%, bezogen auf die Komponenten A und B, eines Thermoplasten ausgewählt aus der Gruppe bestehend aus: Polyvinylchlorid, Polystyrol, Polyme- thylmethacrylat, Polyamid, Polybutylenterephthalat und Polyoxymethylen; A) 69 to 98 wt .-%, based on the components A and B, of a thermoplastic selected from the group consisting of: polyvinyl chloride, polystyrene, polymethyl methacrylate, polyamide, polybutylene terephthalate and polyoxymethylene;
B) 2 bis 31 Gew.-%, bezogen auf die Komponenten A und B, einer Polymermischung enthaltend: B) 2 to 31 wt .-%, based on the components A and B, of a polymer mixture comprising:
i) 30 bis 70 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten i bis ii, mindestens eines Polyesters auf Basis von aliphatischen und/oder aromatischen Dicarbonsäuren und einer aliphatischen Dihydroxyverbindung; ii) 70 bis 30 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten i bis ii, Polymilchsäure; iii) 0 bis 10 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten i bis iv, eines Epoxidgruppen-haltigen Copolymers auf Basis Styrol, Acrylsäu- reester und/oder Methacrylsäureester; iv) 0 - 15 % Gew.-%, bezogen auf das Gesamtgewicht der Komponenten i bis iv, Nukleierungsmittel, Gleit- und Antiblockmittel, Wachse, Antistatika, Anti- fog-Mittel oder Farbstoffe; und  i) 30 to 70 wt .-%, based on the total weight of components i to ii, of at least one polyester based on aliphatic and / or aromatic dicarboxylic acids and an aliphatic dihydroxy compound; ii) from 70 to 30% by weight, based on the total weight of components i to ii, of polylactic acid; iii) 0 to 10% by weight, based on the total weight of components i to iv, of an epoxide group-containing copolymer based on styrene, acrylic acid esters and / or methacrylic acid esters; iv) 0-15% by weight, based on the total weight of components i to iv, of nucleating agents, lubricants and antiblocking agents, waxes, antistatic agents, antifogging agents or dyes; and
C) 0 bis 40 Gew.-%, bezogen auf die Komponenten A bis C, weiterer Zusatzstoffe. C) 0 to 40 wt .-%, based on the components A to C, other additives.
2. Thermoplastische Formmasse nach Anspruch 1 , wobei der Thermoplast A ein amorphes Polymer ausgewählt aus der Gruppe bestehend aus: Polyvinylchlorid, Polystyrol und Po- lymethylmethacrylat ist. 2. The thermoplastic molding composition according to claim 1, wherein the thermoplastic A is an amorphous polymer selected from the group consisting of: polyvinyl chloride, polystyrene and polymethyl methacrylate.
3. Thermoplastische Formmasse nach Anspruch 1 , wobei der Thermoplast A ein teilkristallines Polymer ausgewählt aus der Gruppe bestehend aus: Polyamid, Polybutylenterephthalat und Polyoxymethylen ist. 3. A thermoplastic molding composition according to claim 1, wherein the thermoplastic A is a semi-crystalline polymer selected from the group consisting of: polyamide, polybutylene terephthalate and polyoxymethylene.
4. Verfahren zur Erhöhung der Kerbschlagzähigkeit eines Thermoplasten A ausgewählt aus der Gruppe bestehend aus: Polyvinylchlorid, Polystyrol, Polymethylmethacrylat, Polyamid, Polybutylenterephthalat und Polyoxymethylen durch Mischen von 4. A method for increasing the impact strength of a thermoplastic selected from the group consisting of: polyvinyl chloride, polystyrene, polymethyl methacrylate, polyamide, polybutylene terephthalate and polyoxymethylene by mixing
A) 69 bis 98 Gew.-%, bezogen auf die Komponenten A und B, eines Thermoplasten A und B) 2 bis 31 Gew.-%, bezogen auf die Komponenten A und B, einer Polymermischung B enthaltend: A) 69 to 98 wt .-%, based on the components A and B, of a thermoplastic A and B) 2 to 31% by weight, based on the components A and B, of a polymer mixture B comprising:
i) 30 bis 70 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten i bis ii, mindestens eines Polyesters auf Basis von aliphatischen und/oder aromatischen Dicarbonsäuren und einer aliphatischen Dihydroxyverbindung; ii) 70 bis 30 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten i bis ii, Polymilchsäure; iv) 0 bis 10 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten i bis iv, eines Epoxidgruppen-haltigen Copolymers auf Basis Styrol, Acrylsäu- reester und/oder Methacrylsäureester; iv) 0 - 15 % Gew.-%, bezogen auf das Gesamtgewicht der Komponenten i bis iv, Nukleierungsmittel, Gleit- und Antiblockmittel, Wachse, Antistatika, Anti- fog-Mittel oder Farbstoffe; und  i) 30 to 70 wt .-%, based on the total weight of components i to ii, of at least one polyester based on aliphatic and / or aromatic dicarboxylic acids and an aliphatic dihydroxy compound; ii) from 70 to 30% by weight, based on the total weight of components i to ii, of polylactic acid; iv) 0 to 10% by weight, based on the total weight of components i to iv, of an epoxide group-containing copolymer based on styrene, acrylic acid ester and / or methacrylic acid ester; iv) 0-15% by weight, based on the total weight of components i to iv, of nucleating agents, lubricants and antiblocking agents, waxes, antistatic agents, antifogging agents or dyes; and
C) 0 bis 40 Gew.-%, bezogen auf die Komponenten A bis C, weiterer Zusatzstoffe. C) 0 to 40 wt .-%, based on the components A to C, other additives.
Verfahren nach Anspruch 4, dadurch gekennzeichnet, dass der Thermoplast A ein amorphes Polymer ausgewählt aus der Gruppe bestehend aus Polyvinylchlorid, Polystyrol und Polymethylmethacrylat ist. A method according to claim 4, characterized in that the thermoplastic A is an amorphous polymer selected from the group consisting of polyvinyl chloride, polystyrene and polymethyl methacrylate.
Verfahren nach Anspruch 4, dadurch gekennzeichnet, dass der Thermoplast A ein teilkristallines Polymer ausgewählt aus der Gruppe bestehend aus Polyamid, Polybutylen- terephthalat und Polyoxymethylen ist. A method according to claim 4, characterized in that the thermoplastic A is a partially crystalline polymer selected from the group consisting of polyamide, polybutylene terephthalate and polyoxymethylene.
EP12756512.5A 2011-09-21 2012-09-12 Thermoplastic molding compound having improved notch impact strength Withdrawn EP2758474A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP12756512.5A EP2758474A1 (en) 2011-09-21 2012-09-12 Thermoplastic molding compound having improved notch impact strength

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP11182189A EP2573142A1 (en) 2011-09-21 2011-09-21 Thermoplastic moulding composition with improved notched impact resistance
PCT/EP2012/067798 WO2013041423A1 (en) 2011-09-21 2012-09-12 Thermoplastic molding compound having improved notch impact strength
EP12756512.5A EP2758474A1 (en) 2011-09-21 2012-09-12 Thermoplastic molding compound having improved notch impact strength

Publications (1)

Publication Number Publication Date
EP2758474A1 true EP2758474A1 (en) 2014-07-30

Family

ID=46826550

Family Applications (2)

Application Number Title Priority Date Filing Date
EP11182189A Withdrawn EP2573142A1 (en) 2011-09-21 2011-09-21 Thermoplastic moulding composition with improved notched impact resistance
EP12756512.5A Withdrawn EP2758474A1 (en) 2011-09-21 2012-09-12 Thermoplastic molding compound having improved notch impact strength

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP11182189A Withdrawn EP2573142A1 (en) 2011-09-21 2011-09-21 Thermoplastic moulding composition with improved notched impact resistance

Country Status (5)

Country Link
US (1) US20140357764A1 (en)
EP (2) EP2573142A1 (en)
JP (1) JP2014526591A (en)
CN (1) CN103827222A (en)
WO (1) WO2013041423A1 (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6512097B2 (en) * 2013-08-06 2019-05-15 株式会社カネカ Soft thermoplastic resin composition
CN108070225B (en) * 2016-11-17 2022-02-08 普立万聚合体（上海）有限公司 Polyester articles having a simulated metallic or pearlescent appearance
CN107474503A (en) * 2017-08-29 2017-12-15 宁波家联科技股份有限公司 A kind of rapid crystallization high impact properties polylactic acid alloy material and preparation method thereof
EP3670578B1 (en) * 2018-12-19 2021-05-19 Ems-Chemie Ag Polyamide moulding material for extrusion blow molding
CN111334015A (en) * 2020-03-18 2020-06-26 温州华邦安全封条股份有限公司 Novel environment-friendly high-performance plastic and preparation method thereof
CN112080089A (en) * 2020-09-15 2020-12-15 中工恒盛科技有限公司 Preparation method of high-thermal-conductivity polyvinyl chloride cable protection pipe
CN116376209A (en) * 2023-04-28 2023-07-04 金发科技股份有限公司 HIPS/POM alloy material and preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2053091A1 (en) * 2006-07-28 2009-04-29 Teijin Limited Resin composition, method for producing the same and molded article

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69127676T2 (en) 1990-11-26 1998-04-02 Showa Highpolymer A method of making saturated polyester
ATE150058T1 (en) 1990-11-30 1997-03-15 Eastman Chem Co MIXTURES OF ALIPHATIC-AROMATIC COPOLYESTERS WITH CELLULOSE ESTER POLYMERS
DE4440858A1 (en) 1994-11-15 1996-05-23 Basf Ag Biodegradable polymers, processes for their production and their use for the production of biodegradable moldings
DE19638488A1 (en) 1996-09-20 1998-03-26 Basf Ag Biodegradable polyester
US7368511B2 (en) * 2003-12-22 2008-05-06 Eastman Chemical Company Polymer blends with improved rheology and improved unnotched impact strength
SI1838784T1 (en) * 2005-01-12 2008-10-31 Basf Se Biologically-degradable polyester mixture
ITMI20050452A1 (en) 2005-03-18 2006-09-19 Novamont Spa ALYPATIC-AROMATIC BIODEGRADABLE POLYESTER
ES2372988T3 (en) * 2006-12-14 2012-01-30 Pactiv Corporation EXPANDED AND EXTRUDED BIODEGRADABLE FOAMS AND REDUCED EMISSIONS MADE WITH BLOWING AGENTS BASED ON METHYR FORMAT.
KR20100049538A (en) * 2007-09-03 2010-05-12 유니띠까 가부시키가이샤 Resin composition and molded body using the same
KR20110007186A (en) 2008-04-15 2011-01-21 바스프 에스이 Method for the continuous production of biodegradable polyesters
ES2397765T3 (en) 2008-04-15 2013-03-11 Basf Se Process for the continuous production of biodegradable polyesters
AU2009295999B2 (en) * 2008-09-29 2013-12-19 Basf Se Biodegradable polymer mixture
CN105218794A (en) 2008-09-29 2016-01-06 巴斯夫欧洲公司 Aliphatic polyester
BRPI0921678A2 (en) * 2008-11-06 2016-02-16 Tristano Pty Ltd biodegradable polymer composition, film sheet, method for preparing a biodegradable polymer composition, and standard blend
KR101049058B1 (en) * 2008-12-11 2011-07-15 제일모직주식회사 Aliphatic polyester copolymer, its manufacturing method and polylactic acid resin composition using the same
KR20140108731A (en) * 2009-06-19 2014-09-12 로디아 오퍼레이션스 Composition of a blend of polyamide and polyester resins
KR20120093843A (en) * 2009-09-03 2012-08-23 씨오투스타치 피티와이 리미티드 Polymer/thermoplastic starch compositions
IT1399031B1 (en) * 2009-11-05 2013-04-05 Novamont Spa BIODEGRADABLE ALIPHATIC-AROMATIC COPOLIESTERE

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2053091A1 (en) * 2006-07-28 2009-04-29 Teijin Limited Resin composition, method for producing the same and molded article

Also Published As

Publication number Publication date
JP2014526591A (en) 2014-10-06
US20140357764A1 (en) 2014-12-04
WO2013041423A1 (en) 2013-03-28
CN103827222A (en) 2014-05-28
EP2573142A1 (en) 2013-03-27

Similar Documents

Publication Publication Date Title
WO2013041423A1 (en) Thermoplastic molding compound having improved notch impact strength
EP3135731B1 (en) Polyamide moulding material and molded bodies made therefrom
EP2350162B1 (en) Aliphatic polyesters
EP2553021B1 (en) Use of polyamides that are resistant to corrosion and stress cracking
BR112012010358B1 (en) Mixture, combination, articles comprising said mixture and use of the mixture
EP2778190A1 (en) Polyamide moulding material and moulded body produced from the same
US9920198B2 (en) Durable high performance heat resistant polycarbonate (PC) and polylactide (PLA) blends and compositions and methods of making those
EP3126446B1 (en) Polyester composition
EP3636406B1 (en) Toughened polyamide moulding masses
EP2310453B1 (en) Increasing the hydrolysis resistance of biodegradable polyesters
US20150361258A1 (en) Poly (lactic acid)-based biocomposite materials having improved toughness and heat distortion temperature and methods of making and using thereof
WO2013041422A1 (en) Polyamide molding compounds
WO2011043187A1 (en) Eyeglasses molded article, process for production of same, and eyeglasses
Phetwarotai et al. Influence of compatibilizer and multifunctional additive loadings on flame retardation, plasticization, and impact modification of polylactide and poly (butylene adipate‐co‐terephthalate) biodegradable blends
DE2849593C2 (en) Polyester molding compound
DE3040999A1 (en) THERMOPLASTIC MOLDS
JP2960149B2 (en) Polyester molding
JP2006348159A (en) Polylactic acid-based resin composition, molded product thereof, and method for producing the same
DE2233143C3 (en) Thermoplastic molding compounds based on poly (oxymethylene)
WO2012019868A2 (en) Method for increasing the molecular weight of polyesters
EP2826817A1 (en) Biodegradable polyester mixture
JP6621960B2 (en) Masterbatch, resin composition, and resin molded product
JP6902688B1 (en) Colored resin compositions for agricultural films, and agricultural films
WO2012163822A1 (en) Polyester with styrene copolymers
DE69917344T2 (en) POLYESTER MOLDING MATERIAL

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20140422

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20150618

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20151029