EP2652023A1 - Compositions de polyester - Google Patents
Compositions de polyesterInfo
- Publication number
- EP2652023A1 EP2652023A1 EP11794775.4A EP11794775A EP2652023A1 EP 2652023 A1 EP2652023 A1 EP 2652023A1 EP 11794775 A EP11794775 A EP 11794775A EP 2652023 A1 EP2652023 A1 EP 2652023A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- parts
- products
- compositions
- titanium dioxide
- 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.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0005—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor using fibre reinforcements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/40—Glass
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Definitions
- the invention relates to compositions based on polyester, titanium dioxide and glass fibers, the use of these compositions for the production of short-time thermoforming products and a process for the production of short-term heat-resistant polyester-based products, in particular polyester-based optoelectronic products.
- Many electronic and electrical assemblies and components include temperature sensitive electrical and / or electronic products, such as electrical and electronic products. heat sensitive integrated circuits, lithium batteries, oscillator crystals, optoelectronic products.
- electrical contacts must be reliably connected to tracks of a board and / or electrical contacts with other products.
- This assembly is often done with the aid of a soldering process, in which provided on the product solder terminals are soldered to the board. For each product, this results in a safe range for the soldering and soldering temperature, can be made in the good solder joints.
- the temperature sensitive electrical and electronic products should not be overheated to avoid permanent damage.
- soldering heat-sensitive products there are the conflicting requirements of ensuring a sufficiently high soldering temperature for soldering in the area of the solder terminals, but keeping the temperature sufficiently low in the temperature-sensitive areas of the products that no damage to the products occurs.
- the products for producing LEDs have to be exposed to elevated temperatures during soldering for a long time. For example, when wave soldering, the product placed on the board is first slowly warmed to about 100 C degrees. This is followed by the actual soldering, typically at about 260 C degrees and lasting at least 5 seconds, followed by the solidification phase as the product slowly cools.
- JP-A-55027335 discloses a composition containing as polyester PET (polyethylene terephthalate), titanium dioxide with a particle size of 10 - 10000 nm and glass fibers for use in the field of optoelectronic products.
- WO 2007/033129 A2 describes a temperature-resistant composition for LED sockets based on the polyester cyclohexanedimethanol terephthalate, as well as titanium dioxide and glass fibers. From WO 2010/049531 Al so-called power LEDs based on aromatic polyester or completely aromatic polyester are known, whereby the degradation of the thermoplastic material is to be prevented by heat or radiation.
- polyesters of WO 2010/049531 AI are the high processing temperature in the melt due to the high melting points of the polymers described at temperatures of 355 ° C and higher, as well as the high mold temperatures of 175 ° C and higher.
- the polyesters mentioned in the prior art may be sufficiently stable with regard to their short-time heat distortion resistance or solder bath resistance, they may be disadvantageous, in particular when they are processed in the melt.
- the object of the present invention is therefore to provide compositions with optimized properties in terms of short-term heat distortion resistance, reflection, high surface quality with simultaneously low processing temperatures in the melt.
- compositions which have a sufficiently high short term heat distortion resistance (which is a prerequisite for obtaining good soldering results in subsequent processing steps) and at the same time low processing temperatures in the melt (this leads to considerable improvements in the processing of the compositions), is a special one technical challenge, since both properties are contrary in nature. In combination with the demand for optimized properties in terms of reflection and surface quality, the challenge of the task is all the more important.
- compositions comprising a) 5 to 50 parts by weight, preferably 10 to 40 parts by weight, particularly preferably 13 to 33 parts by weight of glass fibers, b) 10 to 40 parts by weight, preferably 13 to 33 parts by weight, more preferably 18 to 28 parts by weight of titanium dioxide having an average particle size between 90 nm and 2000 nm and c) 20 to 80 parts by weight, preferably 30 to 70 parts by weight, more preferably 40-60 parts by weight of polyethylene terephthalate (PET).
- PET polyethylene terephthalate
- the present invention relates to compositions comprising a) 5 to 50 parts by weight, preferably 10 to 40 parts by weight, particularly preferably 13 to 33 parts by weight of glass fibers,
- compositions according to the invention contain, in addition to a) to d), also e) 0.01 to 15 parts by weight, preferably 0.01 to 10 parts by weight, particularly preferably 0.01 to 5 parts by weight Additives which are different from the components mentioned under a) and b).
- the sum of all parts by weight is 100% and corresponds to the total composition of the molding compositions according to the invention.
- the glass fibers to be used according to the invention as component a) generally have a fiber diameter between 7 and 18 ⁇ m, preferably between 9 and 15 ⁇ m, and are added as continuous fibers or as cut or ground glass fibers.
- the fibers may be provided with a suitable sizing system and a primer or adhesion promoter system, preferably based on silane.
- silane-based adhesion promoters for pretreatment are silane compounds of the general formula (I)
- Preferred adhesion promoters are silane compounds from the group of 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 from 0.05 to 2% by weight, preferably from 0.25 to 1.5% by weight and in particular from 0.5 to 1% by weight, based on the glass fibers used for surface coating.
- the glass fibers may have a smaller d97 or d50 value than the glass fibers originally used.
- the glass fibers may have shorter length distributions than originally used due to the processing of the molding compound or molding in the molding compound or in the molding.
- titanium dioxide pigments are suitable whose basic bodies can be prepared by the sulfate (SP) or chloride (CP) process and which have anatase and / or rutile structure, preferably rutile structure.
- the main body need not be stabilized, but a special stabilization is preferred: in the case of the CP base body by an Al doping of 0.3-3.0 wt .-% (calculated as A1 2 0 3 ) and an excess of oxygen in the gas phase at the oxidation of titanium tetrachloride to titanium dioxide of at least 2%; in the SP base body by doping z.
- Al, Sb, Nb or Zn is particularly preferred.
- titanium dioxide as a white pigment in paints and varnishes, plastics, etc.
- unwanted photocatalytic reactions produced by UV absorption lead to the decomposition of the pigmented material.
- Titanium dioxide pigments absorb light in the near ultraviolet range, creating electron-hole pairs that generate highly reactive radicals on the titanium dioxide surface.
- the radicals formed in organic media result in a binder degradation.
- the surface of pigmentary titanium dioxide is preferably covered with amorphous precipitates of oxide hydrates of the compounds Si0 2 and / or A1 2 0 3 and / or zirconium oxide.
- the Al 2 O 3 sheath facilitates pigment dispersion in the polymer matrix, the Si0 2 sheath impedes the charge exchange on the pigment surface and thus prevents polymer degradation.
- the titanium dioxide is preferably provided with hydrophilic and / or hydrophobic organic coatings, in particular with siloxanes or polyalcohols. Titanium dioxide to be used according to the invention has an average particle size between 90 nm and
- 2000 nm preferably between 200 nm and 800 nm.
- the PET or PBT to be used as components c) or component d) are reaction substances of aromatic dicarboxylic acids or their reactive derivatives, preferably dimethyl esters or anhydrides, and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reaction products.
- Preferred polyethylene terephthalates (PET) or polybutylene terephthalates (PBT) contain at least 80 mol%, preferably 90 mol%, based on the dicarboxylic acid, terephthalic acid residues and at least 80 mol%, preferably at least 90 mol%, based on the diol component , Ethylene glycol or butanediol 1, 4-radicals.
- the preferred polyethylene terephthalates or polybutylene terephthalates may contain, in addition to terephthalic acid residues, up to 20 mol% of radicals of other aromatic dicarboxylic acids having 8 to 14 C atoms or radicals of aliphatic dicarboxylic acids having 4 to 12 C atoms, such as radicals of phthalic acid, isophthalic acid, naphthalene-2, 6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid, or cyclohexanedicarboxylic acid.
- radicals of other aromatic dicarboxylic acids having 8 to 14 C atoms or radicals of aliphatic dicarboxylic acids having 4 to 12 C atoms such as radicals of phthalic acid, isophthalic acid, naphthalene-2, 6-dicarboxylic acid,
- the preferred polyethylene terephthalates or polybutylene terephthalates may in addition to ethylene or butanediol-l, 4-glycol radicals contain up to 20 mol% of other aliphatic diols having 3 to 12 carbon atoms or cycloaliphatic diols having 6 to 21 carbon atoms, preferably radicals of 1,3-propanediol, 2-ethylpropane-1,3-diol, neopentyl glycol, pentanediol-1,5, hexanediol-1,6, cyclohexane-dimethanol-1,4, 3-methylpentanediol-2,4, 2-methylpentanediol-2, 4, 2,2,4-trimethylpentanediol-1, 3 or -1,6,2-
- Preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and trimethylolpropane and pentaerythritol.
- the PET or PBT to be used according to the invention preferably has an intrinsic viscosity of about 0.3 cm / g to 1.5 cm / g, particularly preferably 0.4 cm / g to 1.3 cm / g, especially preferably 0.5 cm / g to 1.0 cm / g each measured in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C.
- polyesters of component c) PET and component d) PBT may also be used in admixture with other polyesters and / or further polymers.
- compositions according to the invention may also contain additives.
- Typical additives of component e) are preferably stabilizers, in particular UV stabilizers, heat stabilizers, gamma ray stabilizers, antistatic agents, flow aids, flame retardants, mold release agents, elastomer modifiers, fire protection additives, emulsifiers, nucleating agents, plasticizers, lubricants, dyes and pigments.
- stabilizers in particular UV stabilizers, heat stabilizers, gamma ray stabilizers, antistatic agents, flow aids, flame retardants, mold release agents, elastomer modifiers, fire protection additives, emulsifiers, nucleating agents, plasticizers, lubricants, dyes and pigments.
- suitable additives are described for example in Gumbleter, Müller, plastic additives, 3rd edition, Hanser Verlag, Kunststoff, Vienna, 1989 and in the Plastics Additives Handbook, 5th Edition, Hanser Verlag, Kunststoff, 2001.
- the Additives can be used alone or in mixture or in the form of master
- stabilizers are preferably sterically hindered phenols, hydroquinones, aromatic secondary amines such as diphenylamines, substituted resorcinols, salicylates, benzotriazoles and Benzophenones, as well as various substituted representatives of these groups and mixtures thereof used.
- dyes or pigments regardless of the titanium dioxide of component b), further dyes or pigments are used in order to give a color to the light to be emitted by the latter in the case of an optoelectronic product or to improve the light to be emitted by means of an optical brightener.
- the nucleating agents used are preferably sodium or calcium phenylphosphinate, aluminum oxide, silicon dioxide and preferably talc.
- Preferred lubricants and mold release agents are ester waxes, pentaerythritol tetrastearate (PETS), long-chain fatty acids, in particular stearic acid or behenic acid, their salts, in particular Ca or Zn stearate, and also amide derivatives, in particular ethylene-bis-stearylamide, or montan waxes, in particular mixtures of straight-chain ones , saturated carboxylic acids having chain lengths of 28 to 32 carbon atoms, and low molecular weight polyethylene or polypropylene waxes used.
- PETS pentaerythritol tetrastearate
- long-chain fatty acids in particular stearic acid or behenic acid
- their salts in particular Ca or Zn stearate
- amide derivatives in particular ethylene-bis-stearylamide, or montan waxes, in particular mixtures of straight-chain ones , saturated carboxylic acids having chain lengths of 28 to 32 carbon atoms,
- the plasticizers used are preferably dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils or N- (n-butyl) benzenesulfonamide.
- Additives to be used as elastomer modifiers are preferably one or more graft polymers E of
- E.2 95 to 5 wt .-%, preferably 70 to 10 wt .-% of one or more graft bases with glass transition temperatures ⁇ 10 ° C, preferably ⁇ 0 ° C, particularly preferably ⁇ -20 ° C used.
- the graft base E.2 generally has an average particle size (d 50 value) of 0.05 to 10 ⁇ , preferably 0, 1 to 5 ⁇ , more preferably 0.2 to 1 ⁇ .
- Monomers E.I are preferably mixtures of E.I. from 50 to 99% by weight of vinylaromatics and / or ring-substituted vinylaromatics (such as, for example, styrene, ⁇ -methylstyrene, p-methylstyrene, p-chlorostyrene) and / or methacrylic acid (C 1 -C 8 ) -alkyl esters (for example methyl methacrylate , Ethyl methacrylate) and
- E.1.2 1 to 50% by weight of vinyl cyanides (unsaturated nitriles such as acrylonitrile and methacrylonitrile) and / or (meth) acrylic acid (C 1 -C 8 ) -alkyl esters (such as, for example, methyl methacrylate, n-butyl acrylate, t-butyl acrylate) and / or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids (eg, maleic anhydride and N-phenyl-maleimide).
- vinyl cyanides unsaturated nitriles such as acrylonitrile and methacrylonitrile
- acrylic acid (C 1 -C 8 ) -alkyl esters such as, for example, methyl methacrylate, n-butyl acrylate, t-butyl acrylate
- derivatives such as anhydrides and imides
- unsaturated carboxylic acids eg, maleic anhydride and N
- Preferred monomers E. l. l are selected from at least one of the monomers styrene, ot-methylstyrene and methyl methacrylate
- preferred monomers E.1.2 are selected from at least one of the monomers acrylonitrile, maleic anhydride and methyl methacrylate.
- Particularly preferred monomers are E.I. l styrene and E.1.2 acrylonitrile.
- Suitable graft bases E.2 for the graft polymers to be employed in the elastomer modifiers are diene rubbers, EP (D) M rubbers, ie those based on ethylene / propylene and optionally diene, acrylate, polyurethane, silicone, chloroprene and ethylene-1-yl-inyl acetate. rubbers.
- Preferred grafting principles E.2 are diene rubbers (for example based on butadiene, isoprene, etc.) or mixtures of diene rubbers or copolymers of diene rubbers or mixtures thereof with other copolymerizable monomers (for example according to E.I.1 and E.1.2), with the proviso that the glass transition temperature of component E.2 is below ⁇ 10 ° C., preferably ⁇ 0 ° C., more preferably ⁇ -10 ° C.
- grafting E.2. pure polybutadiene rubber.
- Particularly preferred polymers E are ABS polymers (emulsion, bulk and suspension ABS), as z.
- DE-A 2 035 390 US Pat. No. 3,644,574
- DE-A 2 248 242 DE-A 1 409 275
- the gel content of the grafting base E.2 is at least
- ABS means acrylonitrile-butadiene-styrene copolymer with the CAS number 9003-56-9 and is a synthetic terpolymer of the three different monomer types acrylonitrile, 1,3-butadiene and styrene. It belongs to the amorphous thermoplastics. The proportions can vary from 15-35% acrylonitrile, 5-30% butadiene and 40-60% styrene.
- the elastomer modifiers or graft copolymers E are obtained by free radical polymerization, e.g. by emulsion, suspension, solution or bulk polymerization, preferably by emulsion or bulk polymerization.
- Particularly suitable graft rubbers are also ABS polymers which are prepared by redox initiation with an initiator system of organic hydroperoxide and ascorbic acid according to US Pat. No. 4,937,285. Since, in the grafting reaction, the grafting monomers are not necessarily grafted completely onto the grafting base, graft polymers E according to the invention are also those products which are obtained by (co) polymerization of the grafting monomers in the presence of the grafting base and are obtained during workup.
- Suitable acrylate rubbers are based on graft bases E.2 which are preferably polymers of alkyl acrylates, optionally with up to 40% by weight, based on E.2, of other polymerizable, ethylenically unsaturated monomers.
- the preferred polymerisable acrylic acid esters include C 1 -C 6 -alkyl esters, preferably methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Haloalkyl esters, preferably halogen-Ci-Cg-alkyl esters, particularly preferably chloroethyl acrylate and mixtures of these monomers.
- crosslinking monomers having more than one polymerizable double bond can be copolymerized.
- Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids having 3 to 8 carbon atoms and unsaturated monohydric alcohols having 3 to 12 carbon atoms, or saturated polyols having 2 to 4 OH groups and 2 to 20 carbon atoms, such as. Ethylene glycol dimethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds, such as e.g. Trivinyl and triallyl cyanurate; polyfunctional vinyl compounds such as di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate.
- Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds having at least 3 ethylenically unsaturated groups.
- crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine, triallylbenzenes.
- the amount of crosslinked monomers is preferably 0.02 to 5, in particular 0.05 to 2 wt .-%, based on the grafting E.2.
- cyclic crosslinking monomers having at least 3 ethylenically unsaturated groups it is advantageous to limit the amount to less than 1% by weight of the graft base E.2.
- Preferred "other" polymerizable, ethylenically unsaturated monomers which may optionally be used in addition to the acrylic acid esters for the preparation of the graft base E.2 are, for example, acrylonitrile, styrene, ot-methylstyrene, acrylamides, vinyl-C 1 -C 6 -alkyl ethers, methyl methacrylate, butadiene.
- Preferred acrylate rubbers as the graft base E.2 are emulsion polymers which have a gel content of at least 60% by weight.
- organic halogen compounds with synergists or commercial organic nitrogen compounds or organic / inorganic phosphorus compounds used individually or in admixture are used as flame retardants.
- halogen-containing, in particular brominated and chlorinated compounds are preferably ethylene-l, 2-bistetrabromophthalimide, epoxidized tetrabromobisphenol A resin, tetrabromobisphenol A oligocarbonate,
- TPP triphenyl phosphate
- RDP resorcinol bis
- BDP bisphenol A bis-diphenyl phosphate including oligomers
- BDP bisphenol A bis-diphenyl phosphate including oligomers
- Suitable nitrogen compounds are, in particular, melamine and melamine cyanurate.
- Preferred synergists are antimony compounds, especially antimony trioxide and antimony pentoxide, zinc compounds, tin compounds, e.g. Tin stannate and borates suitable.
- the flame retardant so-called carbon formers and tetrafluoroethylene polymers can be added.
- additional fillers and / or reinforcing agents may be present as additives in the compositions according to the invention.
- a mixture of two or more different fillers and / or reinforcing substances in particular based on talc, mica, silicate, quartz, titanium dioxide, wollastonite, kaolin, amorphous silicas, magnesium carbonate, chalk, feldspar, barium sulfate, glass spheres and / or fibrous fillers and / or reinforcing materials based on carbon fibers used.
- Mineral particulate fillers based on talc, wollastonite or kaolin are particularly preferably used according to the invention.
- needle-shaped mineral fillers are also used with particular preference as an additive.
- acicular wollastonites are mentioned.
- the mineral has a length: diameter ratio of from 2: 1 to 35: 1, more preferably from 3: 1 to 19: 1, most preferably from 4: 1 to 12: 1.
- the mean particle size of the acicular minerals according to the invention is preferably less than 20 ⁇ m, particularly preferably less than 15 ⁇ m, particularly preferably less than 10 ⁇ m determined with a CILAS GRANULOMETER.
- the filler and / or reinforcing material may be surface-modified, particularly preferably with a primer or adhesion promoter system, particularly preferably based on silane.
- pretreatment is not essential.
- the silane compounds are generally purchased in amounts of from 0.05 to 2% by weight, preferably from 0.25 to 1.5% by weight and in particular from 0.5 to 1% by weight used on the mineral filler for surface coating.
- the particulate fillers may be due to the processing of the molding material or
- Shaped body in the molding material or in the molding have a smaller d97 or d50 value than the fillers originally used.
- the present invention also relates to the use of the compositions of the invention for the production of short-time heat-resistant products, preferably electronic and electronic assemblies and components, particularly preferably optoelectronic
- the present invention also relates to a process for the production of products, preferably short-time heat-resistant products for the electrical or electronics industry, more preferably electronic or electrical assemblies and components, wherein the matrix material is obtained by injection molding or extrusion, preferably by injection molding.
- the present invention also relates to a process for improving the short-time heat distortion resistance of polyester-based products, characterized in that by injection molding or extrusion glass fiber-reinforced, on a mixture of polybutylene terephthalate and polyethylene terephthalate-based compositions with titanium dioxide having an average particle size between 90 nm and 2000 nm processed.
- Processes according to the invention for producing articles by extrusion or injection molding operate at melt temperatures in the range from 230 to 330 ° C., preferably from 250 to 300 ° C. and optionally additionally at pressures of not more than 2500 bar, preferably at pressures of not more than 2000 bar, more preferably at Pressing a maximum of 1500 bar and most preferably at pressures of a maximum of 750 bar.
- the method of injection molding is characterized in that the raw material, preferably in granular form, is melted (plasticized) in a heated cylindrical cavity and injected as a spray mass under pressure into a tempered cavity. After cooling
- An injection molding machine consists of a clamping unit, the injection unit, the drive and the controller.
- the clamping unit includes fixed and movable platens for the tool, a face plate and columns and drive of the moving platen. (Toggle joint or hydraulic clamping unit).
- An injection unit comprises the electrically heatable cylinder, the drive of the worm (motor, gearbox) and the hydraulic system for moving the worm and injection unit.
- the task of the injection unit is to melt the powder or the granules, to dose, to inject and to press (because of contraction).
- the problem of melt backflow within the screw (leakage flow) is solved by backflow stops.
- the inflowing melt is dissolved, cooled and thus manufactured the product to be manufactured. Necessary are always two tool halves. In injection molding, the following functional complexes are distinguished:
- Polyamide used in the extruder, wherein the extruder is a machine for the production of thermoplastic fittings.
- Extrusion lines consist of extruder, tool, follower, extrusion blow molding. Extrusion lines for the production of profiles consist of: extruder, profile tool, calibration, cooling section, caterpillar and roller take-off, separating device and tilting channel.
- the present invention accordingly also relates to products, in particular short-term dimensionally stable products, obtainable by extrusion, profile extrusion or injection molding of the invention
- the present invention also relates to a process for the preparation of short-time thermoforming products, characterized in that glass fiber-reinforced, on a mixture of polybutylene terephthalate and polyethylene terephthalate-based compositions with titanium dioxide having an average particle size between 90 nm and 2000 nm im
- the present invention preferably relates to a process for the preparation of short-time thermoforming products, characterized in that mixtures containing a) 5 to 50 parts by weight of glass fibers, b) 10 to 40 parts by weight of titanium dioxide having an average particle size between 90 nm and 2000 nm and c) 40-50 parts by weight of polyethylene terephthalate (PET) and. d) 8 to 12 parts by weight of polybutylene terephthalate are processed.
- PET polyethylene terephthalate
- the products obtainable by the processes mentioned surprisingly show excellent short-term heat resistance / soldering tape resistance, show optimized properties in the reflection at 450 nm and a low loss of this property over a longer period of time, optimized processability by a sufficiently stable melt at low melting temperatures Range from 250 to 275 ° C compared to products obtained according to the prior art compositions.
- the present invention also relates to the use of the compositions according to the invention for increasing the short-time heat distortion resistance of products, in particular optoelectronic products.
- a light-emitting diode also luminescence diode, English light-emitting diode, German light-emitting diode, LED
- a light-emitting diode is an electronic semiconductor device. If current flows through the diode in the forward direction, it emits light, infrared radiation (as an infrared light-emitting diode) or else ultraviolet radiation with a wavelength dependent on the semiconductor material and the doping.
- OLED organic light emitting diode
- LEDs inorganic light-emitting diodes
- compositions according to the invention are mixed in a twin-screw extruder (ZSK 26 Mega Compounder from Coperion Werner & Pfleiderer (Stuttgart, Germany) at temperatures between 260 and 290 ° C in the melt, discharged as a strand, until granulation capability cooled and granulated, before further
- Steps the granules are dried at 120 ° C in a vacuum oven for about 2h.
- the specimens (color sample plates 60 ⁇ 40 ⁇ 4 mm) for the tests listed in Table 1 were sprayed on a commercial injection molding machine at a melt temperature of 260-270 ° C. and a mold temperature of 80-120 ° C.
- Test for determining the short-time heat distortion resistance In this test a cylindrical soldering iron tip having a tip diameter of 1 mm is heated at a rate of 20 ° C / minute from 25 ° C to 360 ° C. The soldering iron tip acts with a weight of 1.0 kg on the 60x40x4 mm test specimen. The temperature at which the soldering iron tip 1.5 mm has penetrated into the test specimen is called the penetration temperature. In the range between 350 ° C and 360 ° C a meaningful evaluation by the temperature gradient described during the measurement is no longer possible, so that it results in a maximum evaluable temperature of 350 ° C. Everything beyond that is marked with> 350 ° C.
- the gloss value is determined at 450 nm, according to DIN 5033-4 on a colorimeter from Minolta (CM2600D) under D65 light on test specimens of dimensions 60 mm ⁇ 40 mm ⁇ 4 mm.
- Loss of reflection after hot air aging For hot air aging, the test specimens of the
- Processability and releasability The processability and releasability of the polyesters used according to the invention can be read on two parameters, the filling pressure at injection molding casting process and the mold release. The better the flowability of the molding compound, the lower the required filling pressure during the injection molding process and the better the processability. For demolding rapid crystallization is advantageous in order to eject the product from the tool as quickly as possible and without deformation. + means a better result over o.
- PET polyethylene terephthalate (polyester chips PET V004, Invista, Wichita, USA)
- GF Glass fibers with a diameter of 10 ⁇ m, coated with silane-containing compounds (CS 7967, commercial product of Lanxess N.V., Antwerp, Belgium)
- TiO 2 inorganic titanium dioxide commonly used in polyesters (eg Kronos® 2230 from Kronos, Dallas, USA)
- polyesters such as, for example, mold release agents (eg pentaerythritol tetrastearate (PETS)), heat stabilizers (eg based on phenyl phosphites) and nucleating agents (eg talcum [CAS No. 14807-96-6]).
- PETS pentaerythritol tetrastearate
- heat stabilizers eg based on phenyl phosphites
- nucleating agents eg talcum [CAS No. 14807-96-6]
- compositions according to the invention additionally have a short-time heat distortion resistance of more than 300 ° C. And all this while maintaining low processing temperatures in the melt (260 to 270 ° C).
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP11794775.4A EP2652023A1 (fr) | 2010-12-14 | 2011-12-14 | Compositions de polyester |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10194965A EP2465896A1 (fr) | 2010-12-14 | 2010-12-14 | Compositions de polyester |
PCT/EP2011/072807 WO2012080361A1 (fr) | 2010-12-14 | 2011-12-14 | Compositions de polyester |
EP11794775.4A EP2652023A1 (fr) | 2010-12-14 | 2011-12-14 | Compositions de polyester |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2652023A1 true EP2652023A1 (fr) | 2013-10-23 |
Family
ID=43498530
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP10194965A Withdrawn EP2465896A1 (fr) | 2010-12-14 | 2010-12-14 | Compositions de polyester |
EP11794775.4A Ceased EP2652023A1 (fr) | 2010-12-14 | 2011-12-14 | Compositions de polyester |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP10194965A Withdrawn EP2465896A1 (fr) | 2010-12-14 | 2010-12-14 | Compositions de polyester |
Country Status (6)
Country | Link |
---|---|
US (1) | US9163140B2 (fr) |
EP (2) | EP2465896A1 (fr) |
JP (1) | JP5723022B2 (fr) |
KR (1) | KR101586549B1 (fr) |
CN (1) | CN103347946B (fr) |
WO (1) | WO2012080361A1 (fr) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4336287B2 (ja) * | 2004-10-13 | 2009-09-30 | 株式会社島精機製作所 | 横編機で編まれたvネックニットウエアおよびその編成方法 |
DE102011018921B4 (de) * | 2011-04-28 | 2023-05-11 | OSRAM Opto Semiconductors Gesellschaft mit beschränkter Haftung | Träger, optoelektronisches Bauelement mit Träger und Verfahren zur Herstellung dieser |
IN2014DE03298A (fr) * | 2013-11-27 | 2015-09-25 | Lanxess Deutschland Gmbh | |
DE102014000612A1 (de) | 2014-01-18 | 2015-07-23 | Lanxess Deutschland Gmbh | Polyester Zusammensetzungen |
EP2878625A1 (fr) * | 2013-11-27 | 2015-06-03 | LANXESS Deutschland GmbH | Compositions de polyester |
ES2616282T3 (es) | 2013-11-27 | 2017-06-12 | Lanxess Deutschland Gmbh | Composiciones de poliéster |
HUE039596T2 (hu) * | 2014-05-05 | 2019-01-28 | Lanxess Deutschland Gmbh | Poliészter vegyületek |
KR102626934B1 (ko) * | 2018-09-21 | 2024-01-19 | 신동수 | 고비중, 항균 및 자외선 차단 성능을 갖는 pet 다기능성 마스터 배치 및, 그의 제조방법, 그를 이용한 폴리에스테르 섬유 |
WO2020116209A1 (fr) * | 2018-12-03 | 2020-06-11 | 三菱ケミカル株式会社 | Film multicouche pour impression laser, corps multicouche pour passeports électroniques, corps multicouche pour cartes plastiques, film pour cartes plastiques, carte plastique, feuille de données pour passeports électroniques et passeport électronique |
KR102036284B1 (ko) * | 2019-06-21 | 2019-10-24 | 이규득 | 폴리에틸렌 테레프탈레이트 필름의 제조방법 |
KR102038694B1 (ko) * | 2019-08-12 | 2019-10-31 | 금강기업 주식회사 | 비결정성 폴리에틸렌 테레프탈레이트 필름의 제조방법 |
TWI754922B (zh) | 2020-04-28 | 2022-02-11 | 財團法人紡織產業綜合研究所 | 紅外線反射纖維及其製備方法 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102004029303A1 (de) * | 2004-06-17 | 2006-01-12 | Ems-Chemie Ag | Nanoskalige Titandioxid-Sole, Verfahren zu dessen Herstellung und seine Verwendung |
Family Cites Families (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1580834A (fr) | 1968-01-04 | 1969-09-12 | ||
US3644574A (en) | 1969-07-17 | 1972-02-22 | Eastman Kodak Co | Shaped articles of blends of polyesters and polyvinyls |
US4013613A (en) | 1971-10-01 | 1977-03-22 | General Electric Company | Reinforced intercrystalline thermoplastic polyester compositions |
JPS5039599B2 (fr) | 1973-03-30 | 1975-12-18 | ||
US4035958A (en) | 1973-03-30 | 1977-07-19 | Tokyo Kosei Kaken Co. Ltd. | Mobile floor cleaning and polishing device |
DE2407776A1 (de) | 1974-02-19 | 1975-09-04 | Licentia Gmbh | Schaltung zur regelung der betriebsspannung fuer die transistor-zeilenendstufe eines fernsehempfaengers |
US4122061A (en) | 1976-12-23 | 1978-10-24 | General Electric Company | Impact modified polyester compositions |
DE2715932A1 (de) | 1977-04-09 | 1978-10-19 | Bayer Ag | Schnellkristallisierende poly(aethylen/alkylen)-terephthalate |
JPS5527335A (en) * | 1978-08-18 | 1980-02-27 | Teijin Ltd | Polyester resin composition |
US4370438A (en) * | 1981-04-09 | 1983-01-25 | Celanese Corporation | Polyester blend compositions exhibiting suppression of transesterification |
US4436860A (en) * | 1981-10-30 | 1984-03-13 | General Electric Company | Reinforced thermoplastic composition |
JPH0696769B2 (ja) | 1985-08-23 | 1994-11-30 | 東レ株式会社 | 表面金属化ポリプチレンテレフタレ−ト樹脂成形品の製造方法 |
DE3631539A1 (de) | 1986-09-17 | 1988-03-24 | Bayer Ag | Alterungsbestaendige thermoplastische formmassen mit guter zaehigkeit |
DE3631540A1 (de) | 1986-09-17 | 1988-03-24 | Bayer Ag | Thermoplastische formmassen mit hoher alterungsbestaendigkeit und guter tieftemperaturzaehigkeit |
DE3704657A1 (de) | 1987-02-14 | 1988-08-25 | Bayer Ag | Teilchenfoermige mehrphasenpolymerisate |
DE3704655A1 (de) | 1987-02-14 | 1988-08-25 | Bayer Ag | Teilchenfoermige mehrphasenpolymerisate |
DE3738143A1 (de) | 1987-11-10 | 1989-05-18 | Bayer Ag | Verwendung von redoxpfropfpolymerisaten zur verbesserung der benzinbestaendigkeit von thermoplastischen, aromatischen polycarbonat- und/oder polyestercarbonat-formmassen |
DE4236122A1 (de) | 1992-10-27 | 1994-04-28 | Bayer Ag | Flammgeschützte, mineralgefüllte, thermoplastische Formmassen mit hoher Kriechstromfestigkeit |
JPH1087968A (ja) | 1996-09-09 | 1998-04-07 | Nippon G Ii Plast Kk | 樹脂組成物およびそれによる成形品 |
DE19643280A1 (de) | 1996-10-21 | 1998-04-23 | Basf Ag | Flammgeschützte Formmassen |
JP2000198912A (ja) | 1998-10-29 | 2000-07-18 | Toray Ind Inc | 難燃性樹脂組成物および成形品 |
WO2000047202A1 (fr) | 1999-02-09 | 2000-08-17 | University Of Virginia Patent Foundation | Composes derives du felbamate |
JP2001011292A (ja) | 1999-06-30 | 2001-01-16 | Kanegafuchi Chem Ind Co Ltd | 淡色系耐光性ポリエステル樹脂組成物およびそれから成形された照明器具部品 |
DE10112355C1 (de) | 2001-03-13 | 2002-06-13 | Daimler Chrysler Ag | Verfahren und Schutzvorrichtung zur Montage eines temperaturempfindlichen elektronischen Bauteils |
ATE425225T1 (de) * | 2002-09-25 | 2009-03-15 | Toray Industries | Flammhemmende polybutylenterephthalat-harz- zusammensetzung und -formkörper |
US8007885B2 (en) * | 2005-09-14 | 2011-08-30 | Georgios Topoulos | Light-emitting diode assembly housing comprising poly(cyclohexanedimethanol terephthalate) compositions |
US20090130451A1 (en) * | 2007-11-19 | 2009-05-21 | Tony Farrell | Laser-weldable thermoplastics, methods of manufacture, and articles thereof |
TWI444427B (zh) * | 2008-03-28 | 2014-07-11 | Nippon Oil Corp | Camera module with liquid crystal polyester resin composition |
TW201022327A (en) | 2008-10-30 | 2010-06-16 | Solvay Advanced Polymers Llc | Hydroquinone-containing polyesters having improved whiteness |
EP2546628A1 (fr) * | 2011-07-13 | 2013-01-16 | Koninklijke Philips Electronics N.V. | Support de filtre avec support de changement de phase |
-
2010
- 2010-12-14 EP EP10194965A patent/EP2465896A1/fr not_active Withdrawn
-
2011
- 2011-12-14 CN CN201180064164.5A patent/CN103347946B/zh active Active
- 2011-12-14 KR KR1020137018279A patent/KR101586549B1/ko active IP Right Grant
- 2011-12-14 US US13/993,708 patent/US9163140B2/en active Active
- 2011-12-14 WO PCT/EP2011/072807 patent/WO2012080361A1/fr active Application Filing
- 2011-12-14 JP JP2013543771A patent/JP5723022B2/ja active Active
- 2011-12-14 EP EP11794775.4A patent/EP2652023A1/fr not_active Ceased
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102004029303A1 (de) * | 2004-06-17 | 2006-01-12 | Ems-Chemie Ag | Nanoskalige Titandioxid-Sole, Verfahren zu dessen Herstellung und seine Verwendung |
Non-Patent Citations (12)
Title |
---|
"Partikelgrösse und ISO 13320", PARTIKELWELT, no. 9, 2008 * |
"Partikelgrössenverteilung", December 2011 (2011-12-01), Retrieved from the Internet <URL:http://www.roempp.com/prod3/roempp.php> * |
AGNIESZKA DUDKIEWICZ ET AL: "A uniform measurement expression for cross method comparison of nanoparticle aggregate size distributions", THE ANALYST, vol. 140, no. 15, 1 January 2015 (2015-01-01), GB, pages 5257 - 5267, XP055351095, ISSN: 0003-2654, DOI: 10.1039/C5AN00561B * |
ALAN RAWLE: "BASIC PRINCIPLES OF PARTICLE SIZE ANALYSIS", 1 January 2000 (2000-01-01), XP055009141, Retrieved from the Internet <URL:http://www.rci.rutgers.edu/~moghe/PSD Basics.pdf> [retrieved on 20111011] * |
ANONYMOUS: "Horiba Scientific, A Guidebook to Particle Size Analysis", 1 January 2012 (2012-01-01), Irvine, CA 92618, USA, pages 1 - 32, XP055060732, Retrieved from the Internet <URL:http://www.horiba.com/fileadmin/uploads/Scientific/eMag/PSA/Guidebook/pdf/PSA_Guidebook.pdf> [retrieved on 20130423] * |
Datenblatt Kronos 2225 * |
Datenblatt Kronos 2230 * |
Produktbroschüre "Kronos TiO2 Grades and Applications" * |
Produktbroschüre "Kronos vlp 7" * |
See also references of WO2012080361A1 * |
T. A. EGERTON ET AL: "Physical characterization of titanium dioxide nanoparticles", INTERNATIONAL JOURNAL OF COSMETIC SCIENCE., vol. 36, no. 3, 1 June 2014 (2014-06-01), NL, pages 195 - 206, XP055351101, ISSN: 0142-5463, DOI: 10.1111/ics.12113 * |
WIESE H: "Lichtstreuung und Teilchengrössenmessung; 2. Statische Lichtstreuung", GIT FACHZ. LAB., vol. 7, 1992 * |
Also Published As
Publication number | Publication date |
---|---|
CN103347946B (zh) | 2015-10-07 |
KR101586549B1 (ko) | 2016-01-18 |
CN103347946A (zh) | 2013-10-09 |
US20140088241A1 (en) | 2014-03-27 |
JP5723022B2 (ja) | 2015-05-27 |
WO2012080361A1 (fr) | 2012-06-21 |
EP2465896A1 (fr) | 2012-06-20 |
JP2014500368A (ja) | 2014-01-09 |
US9163140B2 (en) | 2015-10-20 |
KR20130113498A (ko) | 2013-10-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2652023A1 (fr) | Compositions de polyester | |
EP2878629B1 (fr) | Compositions de polyester | |
EP2942367B1 (fr) | Compositions de polyester | |
EP2468810B1 (fr) | Compositions de polyamide non inflammables remplies de verre moulu | |
EP2878630B1 (fr) | Compositions en polyamide | |
EP2878628B1 (fr) | Compositions de polyester | |
EP3020753A1 (fr) | Semi-produit a matrice de fibres ignifuge | |
EP2463338B1 (fr) | Procédé d'optimisation du comportement de cristallisation de masses moulées à base de polyester | |
EP2878619A1 (fr) | Compositions de polyester | |
EP3133104B1 (fr) | Compositions de polyamide | |
EP2924062B1 (fr) | Compositions de polyamide ininflammables | |
EP2365030B1 (fr) | Composés contenant du -N=C=N- utilisé pour éviter la décomposition thermique durant la fusion de polyalkylène térépthalaltes contenant des dialkylphosphinates de metaux | |
EP2878626B1 (fr) | Utilisation des compositions de polyester | |
DE102014000613A1 (de) | Polyester Zusammensetzungen | |
DE102010053483A1 (de) | =N=C=N- enthaltende Verbindung zur Verhinderung des thermischen Abbaus in Schmelzen | |
EP2365028B1 (fr) | Liaisons contenant du -N=C=N- destinées à éviter la perte thermique pendant la fonte | |
EP2915841A1 (fr) | Composition de polyester | |
EP2878625A1 (fr) | Compositions de polyester | |
DE102014000612A1 (de) | Polyester Zusammensetzungen | |
WO2022218593A1 (fr) | Stabilisants pour polymères | |
EP4177311A1 (fr) | Utilisation de polyamide 6 |
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: 20130715 |
|
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) | ||
17Q | First examination report despatched |
Effective date: 20140415 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R003 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED |
|
18R | Application refused |
Effective date: 20181123 |