WO2006042714A1 - Lasermarkierbare formmassen und daraus erhältliche produkte und verfahren zur lasermarkierung - Google Patents
Lasermarkierbare formmassen und daraus erhältliche produkte und verfahren zur lasermarkierung Download PDFInfo
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- WO2006042714A1 WO2006042714A1 PCT/EP2005/011098 EP2005011098W WO2006042714A1 WO 2006042714 A1 WO2006042714 A1 WO 2006042714A1 EP 2005011098 W EP2005011098 W EP 2005011098W WO 2006042714 A1 WO2006042714 A1 WO 2006042714A1
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- WIPO (PCT)
- Prior art keywords
- laser
- molding compound
- compound according
- component
- markable
- Prior art date
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- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- AQRDGTBNWBTFKJ-UHFFFAOYSA-N molybdenum;dihydrate Chemical compound O.O.[Mo] AQRDGTBNWBTFKJ-UHFFFAOYSA-N 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 description 1
- FTWUXYZHDFCGSV-UHFFFAOYSA-N n,n'-diphenyloxamide Chemical class C=1C=CC=CC=1NC(=O)C(=O)NC1=CC=CC=C1 FTWUXYZHDFCGSV-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical class C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- HYBLFDUGSBOMPI-UHFFFAOYSA-N octa-1,4-diene Chemical compound CCCC=CCC=C HYBLFDUGSBOMPI-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 235000013873 oxidized polyethylene wax Nutrition 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 150000008379 phenol ethers Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical class OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 229920001639 plastic brand Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HHJJPFYGIRKQOM-UHFFFAOYSA-N sodium;oxido-oxo-phenylphosphanium Chemical compound [Na+].[O-][P+](=O)C1=CC=CC=C1 HHJJPFYGIRKQOM-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 125000004354 sulfur functional group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000004557 technical material Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- FSBZGYYPMXSIEE-UHFFFAOYSA-H tin(2+);diphosphate Chemical compound [Sn+2].[Sn+2].[Sn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O FSBZGYYPMXSIEE-UHFFFAOYSA-H 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 235000013337 tricalcium citrate Nutrition 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000010981 turquoise Substances 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- BHTBHKFULNTCHQ-UHFFFAOYSA-H zinc;tin(4+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Sn+4] BHTBHKFULNTCHQ-UHFFFAOYSA-H 0.000 description 1
- JLYXXMFPNIAWKQ-UHFFFAOYSA-N γ Benzene hexachloride Chemical compound ClC1C(Cl)C(Cl)C(Cl)C(Cl)C1Cl JLYXXMFPNIAWKQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/267—Marking of plastic artifacts, e.g. with laser
-
- 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
- C08K3/24—Acids; Salts thereof
-
- 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
- C08L67/06—Unsaturated polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Definitions
- the present invention relates to novel molding compositions based on semi-crystalline engineering thermoplastics, the result of laser marking moldings with increased marking quality. Furthermore, the invention relates to molded parts, which are produced from such laser-markable molding compositions, a method for laser marking and the use of selected additives for laser marking.
- Semicrystalline thermoplastics have long been used as materials. In addition to their mechanical, thermal, electrical and chemical properties, functionalities such as laser marking become increasingly important. By way of example, applications in the household goods sector, in keyboards and in the electronics sector are mentioned. Here, a high contrast between the laser-written marking and the polymer matrix as background is required for the application. Furthermore, a targeted adjustment of the marking and matrix color as well as the surface quality of the marking is advantageous for the aesthetics. In particular, if the laser-marked surfaces are usually visible during use or regularly exposed to mechanical or chemical stress, the durability should be ensured with high perceived value. This represents in many cases a hurdle for the use of semi-crystalline engineering thermoplastics.
- Laser-markable molding compounds are known per se.
- One way of marking these molding compositions with laser light is to irradiate the plastic at selected locations with laser light and to bring about a mechanical change or a local discoloration of the plastic by the introduced energy.
- Another way of marking this Molding compositions with laser light is to use discolourable fillers that change their color by irradiation of laser light at selected locations.
- TiO 2 white pigment is known from EP-A-330,869.
- EP-A-400,305 and EP-A-542,115 describe the use of copper hydroxide phosphate and molybdenum (IV) oxide, respectively.
- EP-A-797,511 describes the use of platelet-shaped pigments with a layer of doped tin oxide.
- EP-A-764,683 discloses the use of copper pyrophosphate hydrate and / or manganese sulfate hydrate.
- WO-A-98/58805 discloses a series of copper phosphates.
- WO-A-99/55773 describes inter alia the use of zinc hydroxystannate and stannous oxa!
- WO-A-01/78994 proposes the use of copper fumarate, copper maleate and mixtures thereof.
- DE-A-100 53 639 proposes the use of selected salts, including various cobalt and iron phosphates.
- DE-A-100 34472 describes the use of particles surface-modified with certain silicon compounds.
- EP-A-753,536 describes the use of at least two types of metal oxides.
- EP-A-105,451 describes polyphenylene sulfide molding compositions which have been modified for laser marking with selected additives, for example with the combination of lead chromate and lead molybdate, with nickel antimony titanate or with cobalt zinc silicon.
- the previously available laser-markable plastic molding compounds can be improved in many respects.
- pigments For laser inscribability used pigments often result in an insufficient color difference between the marked site and the unformed plastic matrix and thus a poor color contrast and poor legibility of the label. In other cases, the initially acceptable color contrast changes with time, so that the label more or less disappears. With the addition of increasing amounts of pigment there is also the risk of an undesirable change in the plastic properties. If a light-scattering particle which acts as a white pigment is used as the laser-sensitive additive, this approach is limited by the fact that the photosensitivity increases with increasing content of the additive but the marking contrast as well as the penetration depth of the marking can decrease.
- a metal compound e.g., oxide or salt
- the inherent color tends to contribute to discoloration of the matrix and is generally detrimental to aesthetics.
- the present invention has the object to provide molding compositions based on semi-crystalline engineering thermoplastics, which can be marked with conventional lasers, and those with good marking contrast, the color of the matrix, the color of the marking and the surface topology
- the marking can be optimized without causing the rest of the property profile of engineering thermoplastics inappropriate.
- the present invention relates to laser-markable molding compositions containing
- Particulate light-sensitive salt-like compounds or mixtures containing a plurality of cations are used according to the invention as component B).
- the cations are selected in a particular case so that the salt-like compound B) when mixed into the component A) does not change the color of the molding composition or in a desired manner.
- the mass ratios of the cations to one another are chosen such that, after the irradiation of the molding composition at the irradiated sites, their brightness changes, but not the color of the matrix.
- the mean particle size (d 50 ) of component B is preferably less than 10 ⁇ m. Suitable primary particles can range from a few nanometers to a few
- Component B must contain at least two different cations from the groups described above.
- other cations may e.g. from elements of the 2.-5. Period of the I main group of the periodic table.
- particulate additives which on the one hand increase the laser light sensitivity of the molding composition but on the other hand hardly scatter light are used as component C).
- Inorganic oxides which have a different refractive index from the matrix but primary particles with a mean diameter (dso) below the wavelength of light, usually meet this criterion.
- the formulation components of the molding composition according to the invention are therefore the same
- Matrix (A) comprising partially crystalline engineering thermoplastics, and the additives (B) in the form of particulate light-sensitive compounds or mixtures with the above-defined combination of cations and / or additives (C) in the form of nanoparticulate inorganic oxides, and optionally further conventional additives (D).
- both types of particulate additives complement each other in a nontrivial way.
- Both component B and component C increase in the
- Component B optionally influences the intrinsic color of the matrix and the color of the marking with further coloring additives or pigments.
- Laser-writable molding compositions in the context of this application are characterized in that when exposed to intense light, preferably from a conventional
- Laser light source at the exposed location a color change compared to unexposed matrix occurs.
- This color difference can be considered locally different luminance, as locally different color values, e.g. in the ClELab system or as locally different color values in the RGB system. These effects can occur with different light sources.
- the selection of the components B) and / or C) is generally carried out so that they have the strongest possible absorption in the wavelength range of the available laser light.
- Suitable lasers generally have a wavelength in the range of 157 nm to 10.6 ⁇ m, preferably in the range of 532 nm to 10.6 ⁇ m.
- CO 2 lasers (10.6 ⁇ m) and Nd: YAG lasers (1064 nm) or pulsed UV lasers.
- Typical excimer lasers have the following wavelengths: F 2 excimer laser (157 nm), ArF excimer laser (193 nm), KrCl excimer laser (222 nm), KrF excimer laser (248 nm), XeCl excimer laser (308 nm), XeF excimer laser (351 nm), frequency-multiplied Nd: YAG lasers with wavelengths of 532 nm
- Nd YAG lasers (1064 or 532 nm) and CO 2 lasers.
- the energy densities of the lasers used according to the invention are generally in the range from 0.3 mJ / cm 2 to 50 J / cm 2 , preferably 0.3 mJ / cm 2 to 10 J / cm 2 .
- the pulse frequency is generally in the range of 1 to 30 kHz.
- the molding composition according to the invention contains from 50 to 99.95% by weight, preferably from 80 to 99.5% by weight, particularly preferably from 95 to 99% by weight, of matrix component (A) which contains one or more of the technical semicrystalline thermoplastics , Since, by definition, the matrix is semicrystalline and thus not transparent at domains differing in the refractive index, it is primarily near-surface components that contribute to laser marking.
- Degree of polymerization of the present invention can be used semi-crystalline thermoplastics are not particularly limited and are of the same order of magnitude as the comparable non-lichtbeschriftbarer molding compositions.
- the matrix component (A) used according to the invention must be partially crystalline, ie the thermoplastics in question have a melting range in the DSC diagram.
- the matrix component (A) used according to the invention is not subject to any particular restrictions, as long as it is a thermoplastic and partially crystalline polymer.
- thermoplastics examples include polyacetals (A1), polyesters (A2), polyamides (A3), polyarylene ethers and polyarylene sulfides (A4), polyethersulfones and polysulfones (A5), polyaryletherketones (A6), polyolefins (A7), liquid crystalline polymers (A8) and optionally further thermoplastic polymers as blend partners (AX).
- Polyacetals (A1) in the sense of this description are polymers which have oxymethylene groups (CH 2 O-) as their main repeat. They include polyoxymethylene homopolymers, copolymers, terpolymers and block copolymers.
- polyesters (A2) are thermoplastic polymers having repeating ester groups in the main chain. Examples are polycondensation products of naphthalenedicarboxylic acids, terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid,
- Cyclohexanedicarboxylic acids mixtures of these carboxylic acids and ester-forming derivatives with dihydric alcohols such as ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 4-butenediol and 1, 6-hexanediol, 1, 4-hexanediol, 1, 4-cyclohexanediol, 1, 4-di- (hydroxymethyl) cyclohexane, bisphenol A, neopentyl glycol, oligo- or polyethylene glycols, oligo- or polypropylene glycols, oligo- or
- Particularly preferred matrix components (A) are polyethylene terephthalate, polybutylene terephthalate and polyether ester block copolymers.
- Polyamides (A3) in the sense of this description are thermoplastic polymers having repeating acid amide groups in the main chain. They include both homopolymers of the amine carboxylic acid type and of the diamine-dicarboxylic acid type, as well as copolymers with other possible AA, BB and AB comonomers.
- the useful polyamides are known and, for example, in the Encyclopedia of
- polyamides (A3) are polyhexamethylene adipamide, polyhexamethylene azelaic acid amide, polyhexamethylene sebacamide,
- lactams e.g. Polycaprolactam or Polylaurinlactam obtained products.
- Diamine component and basic polyamide resins prepared by copolymerizing two or more of the foregoing polymers or their components are suitable.
- An example of this is a copolycondensate of terephthalic acid, isophthalic acid, hexamethylenediamine and caprolactam.
- Polyarylene sulfides (A4) in the sense of this description are thermoplastic polymers having repeating sulfur groups in the largely aromatic main chain. They include both homopolymers and copolymers.
- Liquid-crystalline polymers (A8) in the sense of this description are especially liquid-crystalline copolyesters and copolyesteramides based on p-hydroxybenzoic acid and / or 6-hydroxy-2-naphthoic acid.
- Very particularly advantageous to use as liquid-crystalline plastics are generally wholly aromatic polyesters which form anisotropic melts and average molecular weights
- Thermoplastic polymers as blend partners (AX) in the sense of this description can be any further semicrystalline, liquid-crystalline and amorphous polymers.
- Light-sensitive compounds (B) in the sense of this description are organic or inorganic salt-like compounds having the above-defined combinations of different cations or mixtures of salt-like compounds with the above-defined combinations of different cations which change their color under the influence of a laser light source at the exposed position or lead to a color change in the plastic.
- the compounds (B) may be classical salts of defined stoichiometry of one or more anions having a plurality, but at least two cations derived from different elements, but may also be non-stoichiometric compounds having at least two cations derived from different elements ,
- a mixture of compounds each having a cation is used, which is convertible on heating to at least one compound having two cations.
- the additives used for the molding composition of the invention as such at least two have different cations, for example by reaction of at least two simple salts (each having a cation) are formed and as mixed salts (B) in the polymer matrix (A) represent the molding composition of the invention.
- the other embodiment uses the same selection of cations as the first embodiment, but consists of a not yet reacted mixture of simple salts. This embodiment is possible if, at elevated temperatures and other customary conditions (eg residual moisture), the salts present in the mixture react to form mixed salts, ie new reaction products (B), and thus the molding composition according to the invention becomes accessible.
- the simple salt-like compounds contained in the mixture can be reacted with each other before addition to the plastic matrix (A) to form a salt-like compound with cations according to the selection rules of the invention, after which the reaction product can be used as additive (B) for the molding composition according to the invention ,
- the mixture of simple salts is mixed to the plastic matrix (A) to be laser-marked. Subsequently, upon heating the matrix, the simple salt-like compounds react with each other to give identical or similar multiple salts, which are the same or at least similar to those in the first part of this example.
- Elements whose cations can be used for light-induced color changes are Ti, Cr, Mn, Fe, Co 1 Ni, Cu, Zn, Y, Zr, Nb, Mo, Ag, Sn, Sb, La, Pr, Ta, W and Ce.
- cations of elements of the 2nd-5th period of the first main group of the Periodic Table may still be present as a third component.
- the anions of component (B) are in principle not limited, as long as the construction of compounds with cations of at least two different elements is possible.
- Anions which contain at least two different elements are preferably used in component (B).
- Particularly preferred components (B) have as inorganic anions inorganic oxoanions and anions of the organic carboxylic acids and the
- Carbonic acid provided that they can be mixed compounds with multiple cations realized.
- Particularly preferred components (B) have, as anions, phosphorus-containing oxoanions.
- Preference is furthermore given to those combinations in which the intrinsic color of the unexposed compound (B) can be adjusted by varying the molar ratios of the cations.
- the unexposed molding composition has any desired inherent color and the exposed molding compound has a color difference that is as distinct as possible. If this is a difference in color, this can mean a change from one hue to another, such as from yellow to red.
- this term also means a change in brightness, for example from white to gray, from gray to black or from light brown to dark brown.
- a change in opacity for example from transparent to white or black or brown, should be understood as a difference in color.
- the difference in color can be perceived by the human eye.
- Also according to the invention should be colored differences, so they are detected by optical measuring devices or are perceived at a wavelength outside the sensitivity range of the human eye by means of a detector. An example of this is the use of readers that use diode lasers in the NIR range.
- a high color contrast means the occurrence of a high value for dE *, where
- Index 1 stands for the unexposed, Index 2 for the exposed molding compound.
- the unexposed molding compound has the highest possible brightness (ie the highest possible brightness value L * in the ClELab color space) and the lowest possible intrinsic color (ie the smallest possible deviation from the black-white axis: the smallest possible a *, as small as possible b *).
- the exposed molding compound is to have the lowest possible brightness (lowest possible brightness value L *) and nevertheless the lowest possible intrinsic color (as small as possible in terms of absolute value a *, as small as possible b *).
- the exposed molding compound should have a color that is as clear as possible (absolute maximum a * and / or b * ).
- Tungsten a, o, and z independently denote integers having values of 1-20, and y is an integer of values between 0 and 10.
- the component (B) as cations comprises at least one combination of two different elements of the group consisting of copper, tin, antimony and iron.
- component (B) comprises anions of phosphoric (V) and / or phosphoric (III) acid, their condensation products and optionally further hydroxide ions and as cations Cu and Fe or Cu and Sn or Cu and Sb or Sn and Fe.
- component (B) In addition to the chemical composition, physical parameters such as the particle size of component (B) also have a significant influence on the quality of laser inscribability. Their scattering behavior influences both the color and brightness values of the unexposed matrix and the optical uniformity in the image exposed and unexposed area. Furthermore, the average particle size is an important measure of the dispersibility in the polymer matrix and thereby also affects the photosensitivity of the molding composition.
- Components (B) with a middle one are suitable
- Component (B) preferably has an average particle diameter of less than 5 ⁇ m.
- Quantitative data on the particle size refer in this application throughout the average particle size (d 50 ) and on the particle size of
- the particle diameter for the purposes of this invention is determined by conventional methods such as light scattering (optionally with polarized light), microscopy or electron microscopy, counting flow measurements on thin columns, sedimentation methods or other commercially available methods.
- the components B) are advantageously used in proportions of 0.01 to 2.0 wt .-%. Particular preference is given to contents of 0.02 to 1.0% by weight.
- Light-sensitizing inorganic oxides (C) in the sense of this description are oxides which, under the influence of light radiation, cause the formation of coloring matter
- Promote connections This may be, on the one hand, a change in their intrinsic color of these oxides or a catalytic contribution to the fact that correspondingly absorbent compounds are formed in their spatial proximity.
- oxides also includes compounds in which part of the oxygen atoms is present in the form of hydroxyl groups. Again, these may be stoichiometric and non-stoichiometric compounds.
- Suitable inorganic oxides of component (C) may be used on elements of the 3-6.
- oxides (C) are Al 2 O 3 , SiO 2 , silicate and alumosilicate minerals, silicate glasses, TiO 2 , ZnO, ZrO 2 , SnO 2 , Sb 2 O 3 ,
- Sb 2 O 5 Sb 2 O 5 , Bi 2 Os and possibly mixed oxides with further doping elements.
- Particularly preferred is TiO 2 in anatase and rutile form.
- the oxidic additive acts as a permanent white pigment due to its scattering behavior, the brightness values of the unexposed and exposed areas are increased and thus the marking contrast is limited. Furthermore, the average particle size is an important measure of the maximum particle-matrix interface, which can be achieved with good dispersion and thereby also affects the photosensitivity of the molding composition.
- Components (C) having an average particle diameter of less than 250 nm have been found to be suitable.
- the particle diameter is used for the purposes of this invention, e.g. determined by electron or X-ray methods.
- Component (C) preferably has an average particle diameter of less than or equal to 200, in particular less than or equal to 100 nm, particularly preferably from 10 to 100 nm.
- the stated particle sizes are based on the primary particles of the additive used. Depending on the quality of the dispersion, agglomerates of these primary particles can form in the matrix, which naturally can have larger diameters.
- the components C) are advantageously used in proportions of 0.01 to 2.0 wt .-%. Particular preference is given to contents of 0.02 to 1.0% by weight.
- thermoplastic molding compositions according to the invention are further customary additives (D).
- D customary additives
- D1 stabilizers to improve the resistance to light, UV radiation and weathering
- D2 stabilizers to improve the thermal and thermal oxidative resistance
- D3 stabilizers to improve the hydrolytic resistance
- the molding composition according to the invention may contain one or more substances from the group of (D1A) benzotriazole derivatives, (D1B) benzophenone derivatives, (D1C) oxanilide derivatives, (D1D) aromatic benzoates, such as salicylates, (D1E) cyanoacrylates,
- the molding composition of the invention contains both at least one of the stabilizers of the groups D1 A to D1 F and sterically hindered amines of the group D1G.
- the molding composition according to the invention contains a benzotriazole derivative D1A together with a hindered amine D1G.
- Examples of (D1A) benzotriazole derivatives are 2- [2'-hydroxy-3 ', 5'-bis (1, 1-dimethylbenzyl) phenyl] benzotriazole, 2 ⁇ [2'-hydroxy-3'-tert. buty! -5'-methylphenyl) ⁇ 5-chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenzyl) benzotriazole.
- Examples of benzophenone derivatives (D1 B) are 2-hydroxy-4-n-octoxybenzophenone and 2-hydroxy-4-n-dodecyloxybenzophenone.
- Examples of sterically hindered amines (D1G) are 2,2,6,6-tetramethyl-4-piperidyl compounds, such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebazate or the Polymer of succinic acid dimethyl ester and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethyl-4-piperidine.
- the weathering stabilizers mentioned (D 1) are advantageously used in proportions of 0.01 to 2.0 wt .-%. Levels of 0.02 to 1.0% by weight in total of D1A to D1G are particularly preferred.
- the molding composition according to the invention may contain antioxidants, for example one or more substances from the group of (D2A) sterically hindered phenols, (D2B) phenol ethers, (D2C) phenol esters, organic or phosphorus-containing acids such as pentaerythrityl tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], triethylene glycol bis [3 ⁇ [3-tert-butyl-4-hydroxy-5- methylphenyl) propionate], 3,3'-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionohydrazide), hexamethylene-glycol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionohydrazide).
- antioxidants for example one or more substances from the group of (D2A) sterically hindered phenols, (D
- Pentaerythrityl tetrakis [3- (3 J 5-di-tert-butyl-4-hydroxyphenyl) - propionate] are preferred, hydroquinones (D2D) and aromatic secondary amines (D2E).
- a sterically hindered phenol in a particularly preferred embodiment, a sterically hindered phenol
- the antioxidants mentioned (D2) can be used in proportions of 0.01 to 10 wt .-%. Preference is given to contents of up to 2% by weight in total.
- the molding composition according to the invention may comprise hydrolysis stabilizers (D3), ie one or more substances from the group of the (D3A) glycidyl ethers or (D3B) carbodiimides.
- D3A hydrolysis stabilizers
- D3B hydrolysis stabilizers
- Examples are mono-, di- or optionally Mehrfachglycidylether of ethylene glycol, propanediol, 1,4-butanediol, 1, 3-butanediol, glycerol and
- Trimethylolpropantrisglycidylether Trimethylolpropantrisglycidylether.
- the stabilizers (D3) mentioned can be used in proportions of 0 to 3% by weight. Preference is given to contents of up to 1.0% by weight in total. Particularly preferred are polymeric or monomeric carbodiimides.
- the molding composition according to the invention may contain acid-emitting substances, ie one or more substances from the group of nitrogen-containing compounds (D4A), alkaline earth compounds (D4B) or bases (D4C).
- acid-emitting substances ie one or more substances from the group of nitrogen-containing compounds (D4A), alkaline earth compounds (D4B) or bases (D4C).
- both nitrogen-containing compounds (D4A) and alkaline earth compounds (D4B) are used.
- Examples of nitrogen-containing compounds (D4A) are melamine,
- alkaline earth compounds examples are calcium propionate, tricalcium citrate and magnesium stearate.
- Examples of bases are Na 2 CO 3 and NaHCO 3 .
- the cited acid scavengers (D4) are preferably used in proportions of 0.001 to 1, 0 wt .-%. Acid scavengers can also be used as mixtures.
- a lubricant (D5) or mold release agents (D6) the molding composition according to the invention waxes, such as polyethylene waxes and / or oxidized polyethylene waxes may contain their esters and amides and fatty acid esters or fatty acid amides.
- Lubricants (D5) and mold release agents (D6) are preferably used in proportions of from 0.01 to 10% by weight. Levels of 0.05 to 3 wt .-% in total are particularly preferred. As a rule, lubricants can also act as mold release aids and vice versa.
- the molding composition according to the invention can contain coloring substances, so-called colorants. These can be both organic and inorganic pigments as well as dyes.
- the pigments and dyes are not particularly limited. However, pigments should be used which distribute themselves uniformly in the molding composition and do not accumulate at interfaces or individual domains, so that excellent color uniformity, color constancy and mechanical properties
- Examples include anthraquinone dyes and various pigments such as carbon black, azo pigments, phthalocyanine pigments, perylene pigments, quinacridone pigments, anthraquinone pigments, indoline pigments, titanium dioxide pigments,
- Iron oxide pigments and cobalt pigments Any suitable combinations of colorants may also be used within the present invention. When carbon blacks are used, in addition to the coloring effect, a contribution to weathering stabilization is often observed.
- the content of colorants is preferably from 0.05 to 10% by weight, particularly preferably up to 5% by weight in total. If the contents are too low, the desired color depth is often not reached; Higher levels are usually not necessary, economically unattractive and possibly degrade other properties such as the mechanics of the molding compound.
- the molding composition according to the invention may contain homogeneous or heterogeneous nucleating agents, ie one or more substances from the group of solid inorganics and crosslinked polymers.
- (D8) nucleating agents are pyrogenic
- the molding composition according to the invention contains talc or branched or partially crosslinked polymers as nucleating agents.
- Nucleating agents are preferably used in amounts of 0.0001 to 5 wt .-%. Preference is given to contents of from 0.001 to 2.0% by weight in total.
- the molding composition according to the invention may contain additives (D9) which favorably influence the fire behavior.
- additives (D9) which favorably influence the fire behavior.
- flame retardants There are all known flame retardants into consideration, both halogen-containing and halogen-free.
- flame retardants are (D9A) nitrogen-containing, (D9B) phosphorus-containing
- D9A or D9B are melamine polyphosphate, melamine cyanurate, resorcinol diphosphate, polyhalodiphenyl, polyhalodiphenyl ether,
- substituted phosphines such as triphenylphosphine, substituted phosphine oxides, melamine phosphate esters, phosphinic acid esters and corresponding salts, elemental phosphorus, hypophosphite esters and corresponding salts, phosphite esters and corresponding salts, phosphate esters and corresponding salts.
- the molding composition according to the invention may contain additives (D10) which, as impact modifiers, favorably influence mechanical properties.
- Levels of 0 to 20 wt .-% in total are preferred.
- particulate polymers which are often elastomeric or contain elastomeric components.
- EPM ethylene-propylene
- EPDM ethylene-propylene-diene
- diene monomers for EPDM rubbers for example, conjugated dienes such as isoprene and butadiene, non-conjugated dienes having 5 to 25 carbon atoms such as penta-1, 4-diene, hexa-1, 4-diene, hexa-1, 5 -diene, 2,5-dimethylhexa-1, 5-diene and octa-1, 4-diene, cyclic dienes such as cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadiene, and also alkenylnorbornenes such as 5-ethylidene-2-norbornene, 5-butylidene-2 norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5-norbornene and Tricyclodienes such as 3-methyl-tricyclo (5.2.1.0.2.6) -3,8-decadiene or mixtures thereof called.
- the diene content of the EPDM rubbers is preferably 0.5 to 50, in particular 1 to 8 wt .-%, based on the total weight of the rubber.
- EPM or EPDM rubbers may preferably also be grafted with reactive carboxylic acids or their derivatives.
- reactive carboxylic acids or their derivatives e.g. Acrylic acid,
- Methacrylic acid and its derivatives e.g. Glycidyl (meth) acrylate, and called maleic anhydride.
- Another group of preferred rubbers are copolymers of ethylene with acrylic acid and / or methacrylic acid and / or the esters of these acids.
- the rubbers may still contain dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids, e.g. Esters and anhydrides, and / or monomers containing epoxy groups.
- dicarboxylic acid derivatives or monomers containing epoxy groups are preferably incorporated into the rubber by adding monomers containing dicarboxylic acid or epoxy groups.
- Preferred elastomers are also emulsion polymers, their preparation e.g. by Blackley in the monograph "Emulsion Polymerization".
- the emulsifiers and catalysts which can be used are known per se. Basically, homogeneously constructed elastomers or those with a
- Shell structure can be used.
- the shell-like structure is determined by the order of addition of the individual monomers; the morphology of the polymers is also influenced by this order of addition.
- monomers for the preparation of the rubber portion of the elastomers acrylates such as e.g. n-butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates,
- the soft or rubber phase (with a glass transition temperature below 0 0 C) of the elastomers may be the core, the outer shell or a middle shell (in elastomers with more than two-shell construction); in the case of multi-shell elastomers, it is also possible for a plurality of shells to consist of a rubber phase.
- one or more hard components (with glass transition temperatures of more than 20 0 C) to the structure of the elastomer involved, these generally prepared by polymerization of styrene, acrylonitrile, methacrylonitrile, alpha-methylstyrene, p-methylstyrene, Acrylklareestern and
- Methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate produced as the main monomers.
- Methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate produced as the main monomers.
- smaller proportions of other comonomers can also be used here.
- the particles of the rubber phase can also be crosslinked.
- Crosslinking monomers are, for example, buta-1,3-diene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate and the compounds described in EP-A 50 265.
- graft-linking monomers ie monomers having two or more polymerizable double bonds which react at different rates during the polymerization.
- the different polymerization rates entail a certain proportion of unsaturated double bonds in the rubber. If, subsequently, another phase is grafted onto such a rubber, the double bonds present in the rubber react at least partially with the graft monomers Formation of chemical bonds, ie the grafted phase is at least partially linked via chemical bonds with the graft.
- graft-linking monomers examples include allyl-containing monomers, in particular allyl esters of ethylenically unsaturated carboxylic acids, such as
- graft polymers having a multi-shell structure instead of graft polymers having a multi-shell structure, homogeneous, i. single-shell elastomers of buta-1,3-diene, isoprene and n-butyl acrylate or copolymers thereof are used. These products can also be prepared by concomitant use of crosslinking monomers or monomers having reactive groups.
- emulsion polymers examples include n-butyl acrylate / (meth) acrylic acid copolymers, n-butyl acrylate / glycidyl acrylate or n-butyl acrylate / glycidyl methacrylate copolymers, graft polymers having an inner core of n-butyl acrylate or butadiene-based and an outer shell of the above-mentioned copolymers and copolymers of ethylene with comonomers providing reactive groups.
- the described elastomers may also be prepared by other conventional methods, e.g. by suspension polymerization.
- Further preferred rubbers are polyurethanes, polyether esters and silicone rubbers.
- the novel thermoplastic molding compositions may contain fibrous, platelet or particulate fillers and reinforcing agents.
- Examples are carbon fibers, aramid fibers, glass fibers, glass beads, amorphous
- Silicic acid asbestos, calcium silicate (wollastonite), aluminum silicate, magnesium carbonate, kaolin, chalk, lime, marble, powdered quartz, mica, barite, feldspar, layer and aluminosilicates, bentonite, montmorillonite and talc.
- the fillers may be modified by organic components or silanization.
- the proportion of such fillers is generally up to 50 wt .-%, preferably up to 35 wt .-%.
- the molding composition according to the invention may contain additives (D 12) which influence the mobility of the chain in the amorphous phases or which
- Examples are dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils, N - (n-butyl) benzenesulfonamide and o- and p-tolylethylsulfonamide.
- the molding composition according to the invention may comprise additives which according to the respective prior art ensure or improve functional properties of the molding composition (for example electrical conductivity and / or antistatic properties).
- a method of preparation of the molding composition or of a suitable intermediate according to the invention is, for example, mixing all components at elevated temperature, ie above the melting point of, some or all of the matrix polymers (A) in well-mixing aggregates such as Brabender, extruders, preferably twin-screw extruders, or on mixing rolls.
- Another method of preparation is the mixing of components at room temperature and the subsequent melting of the matrix polymers in an extruder, preferably twin-screw extruders.
- the matrix A contains a polymer which is built up via a polycondensation reaction:
- additives for better dispersion can already be added during the molecular weight build-up.
- nanoscale additives C this variant offers advantages. If the matrix contains a polyester, such and other components can be added at the end of the transesterification or at the beginning of the polycondensation.
- the components individually or in combination, can first be processed into more highly concentrated masterbatches and these can then be processed further with other components to give the mixture according to the invention.
- the additives mentioned in this description can be added in any suitable steps.
- the final formulation of the molding composition can also be produced so that one or more additives are added only shortly before the formation of the molding.
- the mixture of granules with an additive paste or the mixture of two or more types of granules, wherein at least one of the molding composition according to the invention or they ultimately together give the composition of the invention are suitable.
- the molding composition according to the invention is thermoplastic and thus accessible to the usual processing methods.
- the processing is usually carried out by using a granulate which is further processed in a known manner, for example by extrusion, injection molding, vacuum forming, blow molding or foaming to Formkörpem.
- the molding composition according to the invention is suitable as a technical material for
- molded parts in irradiated and unirradiated form which are produced from the molding composition according to the invention by means of conventional processing techniques, in particular by injection molding, are the subject of the present invention.
- the molded parts according to the invention can be used in the computer, electrical, electronic,
- the marking and labeling of molded parts according to the invention e.g. Keyboards, cables, lines, trim or functional parts in the heating, ventilation and cooling area or switches, plugs, levers and handles that contain the molding compound according to the invention can be achieved with the aid of laser light.
- the moldings according to the invention can be used as packaging.
- the present invention furthermore relates to a method for the laser marking of thermoplastic molded parts, comprising the steps of: i) producing a molding from a molding composition containing at least one semicrystalline thermoplastic A) and components B) and / or C) and D) as defined above, and ii ) Irradiating predetermined parts of at least one surface of the molding with laser light to cause a change in the visual appearance at the irradiated sites.
- the present invention likewise relates to the use of the above-defined components B) and / or C) for the laser marking of molded parts.
- the markings thus obtained are characterized by the fact that they wipe and scratch resistant, stable in subsequent sterilization processes and hygienically pure
- Another field of application for laser marking are plastic brands for the individual identification of animals, so-called poultry rings, cattle tags or ear tags.
- the label must be very durable, since the mark sometimes remain on the animals for several years.
- Samples were prepared and tested which contained polyoxymethylene (POM) or polybutylene terephthalate (PBT) as semi-crystalline engineering thermoplastics (A).
- POM polyoxymethylene
- PBT polybutylene terephthalate
- the examples according to the invention contained, in addition to component A, either light-sensitive compounds with a plurality of cations (B) or nanoscale particles of light-sensitizing oxides (C) or a combination of both.
- the samples used as comparative examples contained either light-sensitive compounds with one cation or microscale particles of light-sensitizing oxides or served as a reference without a photosensitive additive.
- Tinuvin® 234 and Tinuvin® 770 are Ciba Spezialitatenchemie GmbH, as a flow aid and mold release Licowachs® C (Clariant GmbH), as acid repellents melamine and calcium propionate used.
- D P BT as an antioxidant were Irganox® 1010 and Irgafos® 126 (both Ciba Specialty Chemicals GmbH), as a nucleating agent talc as flow aids and mold-release Licolub® WD4 (Clariant GmbH) and as
- copper (II) hydroxide phosphate was used, obtained from Aldrich or Fa. Chemische Fabrik Budenheim KG.
- FeP as component B
- an additive powder containing both Fe (II) and Fe (III) as cations was used. It was obtained as iron (II) phosphite with small amounts of iron (III) and small amounts of phosphate from. Chemische Fabrik Budenheim KG and used.
- additive powders containing both Cu (II) and Fe (II) and Fe (III) as cations were purchased from Chemische Fabrik Budenheim KG. The additives were used both as an unreacted mixture of the individual salts (about 50%).
- additive powders containing both Sn (II) and Cu (II) as cations and obtained from Messrs. Chemische Fabrik Budenheim KG were used. The additives were used both as an unreacted mixture of the individual salts (about 80% tin (II) phosphate with about 20% copper (II) hydroxide) and as reacted mixed salts for the preparation of the molding compositions.
- Molding compounds showed significant differences to those of the simple starting salts.
- an additive powder which contained both Cu (II) and Sb (III) as cations and was purchased from Chemische Fabrik Budenheim KG.
- the additives were used as an unreacted mixture of the individual salts (about 80% antimony (III) phosphate with about 20% copper (II) hydroxide) for the preparation of the molding compositions. Diffraction spectra obtained with X-ray radiation on the molding composition showed marked differences to those of the simple starting salts.
- the example contains the entry nano-TiO 2 (n-TiO 2 ) as component C, titanium dioxides with particle diameters of a few nanometers, such as P25 from Degussa or Hombitec RM 130F from Sachtleben, were used.
- Titanium dioxide white pigment with d 5 o of 0.3 ⁇ m used as the types 2078 or 2220 from Kronos.
- the molding compounds were compounded in a twin-screw extruder with two kneading zones (Berstorff ZE-25).
- the nano-additives were already added during the polycondensation.
- the molding compounds were then injection molded into 90 mm x 65 mm x 1 mm plates.
- the results are based on the compilation of the table.
- the PBT matrix had brightness values greater than 222 and the POM matrix greater than 220, respectively.
- the PBT matrix had brightness values less than 220 and the POM matrix less than 216.
- red-green-blue components were largely the same, with “turquoise” somewhat stronger intensities in the green-blue range, while reddish had slightly stronger intensities in red.
- the Mark Darkness indicator was less than 50.
- the ratio of matrix brightness / marker brightness was greater than 1.25.
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Abstract
Description
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Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
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DE502005010730T DE502005010730D1 (de) | 2004-10-15 | 2005-10-15 | Lasermarkierbare formmassen und daraus erhältliche produkte und verfahren zur lasermarkierung |
CN2005800412481A CN101068686B (zh) | 2004-10-15 | 2005-10-15 | 可激光标记的模塑组合物、由其获得的产品和激光标记方法 |
AT05797680T ATE492406T1 (de) | 2004-10-15 | 2005-10-15 | Lasermarkierbare formmassen und daraus erhältliche produkte und verfahren zur lasermarkierung |
AU2005296732A AU2005296732B2 (en) | 2004-10-15 | 2005-10-15 | Laser-markable molding masses and products obtained therefrom and method for laser marking |
US11/665,550 US7771646B2 (en) | 2004-10-15 | 2005-10-15 | Laser-markable molding compositions, moldings prepared using the same and methods of marking such moldings |
JP2007536108A JP5133060B2 (ja) | 2004-10-15 | 2005-10-15 | レーザー標識可能な成形材及びそれより得られる製品並びにレーザー標識するための方法 |
EP05797680A EP1827858B1 (de) | 2004-10-15 | 2005-10-15 | Lasermarkierbare formmassen und daraus erhältliche produkte und verfahren zur lasermarkierung |
HK08103618.8A HK1113476A1 (en) | 2004-10-15 | 2008-04-02 | Laser-markable molding masses and products obtained therefrom and method for laser marking |
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DE102004050557.8 | 2004-10-15 | ||
DE102004050557A DE102004050557B4 (de) | 2004-10-15 | 2004-10-15 | Lasermarkierbare Formmassen und daraus erhältliche Produkte und Verfahren zur Lasermarkierung |
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US (1) | US7771646B2 (de) |
EP (2) | EP2269833B1 (de) |
JP (1) | JP5133060B2 (de) |
KR (1) | KR20070091112A (de) |
CN (1) | CN101068686B (de) |
AT (1) | ATE492406T1 (de) |
AU (1) | AU2005296732B2 (de) |
DE (2) | DE102004050557B4 (de) |
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EP4119344A1 (de) | 2021-07-14 | 2023-01-18 | Covestro Deutschland AG | Spezielle polymerschichten zur schnelleren laminierbarkeit von mehrschichtaufbauten |
WO2023285356A1 (de) | 2021-07-14 | 2023-01-19 | Covestro Deutschland Ag | Spezielle polymerschichten zur schnelleren laminierbarkeit von mehrschichtaufbauten |
WO2023285358A1 (de) | 2021-07-14 | 2023-01-19 | Covestro Deutschland Ag | Folienaufbau geeignet zur schnellen lamination |
Also Published As
Publication number | Publication date |
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EP1827858A1 (de) | 2007-09-05 |
EP2269833B1 (de) | 2013-04-24 |
CN101068686B (zh) | 2010-12-29 |
US7771646B2 (en) | 2010-08-10 |
AU2005296732B2 (en) | 2011-02-17 |
CN101068686A (zh) | 2007-11-07 |
DE102004050557A1 (de) | 2006-04-27 |
DE102004050557B4 (de) | 2010-08-12 |
KR20070091112A (ko) | 2007-09-07 |
AU2005296732A1 (en) | 2006-04-27 |
DE502005010730D1 (de) | 2011-02-03 |
ATE492406T1 (de) | 2011-01-15 |
EP2269833A1 (de) | 2011-01-05 |
HK1113476A1 (en) | 2008-10-03 |
JP2008517081A (ja) | 2008-05-22 |
JP5133060B2 (ja) | 2013-01-30 |
US20070295689A1 (en) | 2007-12-27 |
EP1827858B1 (de) | 2010-12-22 |
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