US20100310787A1 - Use of zero-order diffractive pigments - Google Patents

Use of zero-order diffractive pigments Download PDF

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Publication number
US20100310787A1
US20100310787A1 US12/740,114 US74011408A US2010310787A1 US 20100310787 A1 US20100310787 A1 US 20100310787A1 US 74011408 A US74011408 A US 74011408A US 2010310787 A1 US2010310787 A1 US 2010310787A1
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Prior art keywords
tungsten
tungstate
process according
nir
coating
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US12/740,114
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English (en)
Inventor
Urs Lehmann
Urs Leo Stadler
Marc Mamak
Ralf Knischka
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BASF SE
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BASF SE
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Assigned to BASF SE reassignment BASF SE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LEHMANN, URS, KNISCHKA, RALF, MAMAK, MARC, STADLER, URS LEO
Publication of US20100310787A1 publication Critical patent/US20100310787A1/en
Abandoned legal-status Critical Current

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    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10—Polymers of propylene
    • B29K2023/12—PP, i.e. polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2055/00—Use of specific polymers obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of main groups B29K2023/00 - B29K2049/00, e.g. having a vinyl group, as moulding material
    • B29K2055/02—ABS polymers, i.e. acrylonitrile-butadiene-styrene polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/04—Polyesters derived from hydroxycarboxylic acids
    • B29K2067/046—PLA, i.e. polylactic acid or polylactide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2069/00—Use of PC, i.e. polycarbonates or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B29K2995/0026—Transparent
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/38—Particle morphology extending in three dimensions cube-like

Definitions

  • the invention relates to the use of tungsten oxide or of tungstate to increase the heat-input amount of near infrared radiation.
  • EP 1 847 635 discloses, for example a particle dispersion of Cs 033 WO 3 as heat absorbing material.
  • the tungsten oxide material of the present invention comes quite near to this target profile—although it is slightly bluish to grayish.
  • this tungsten oxide material can be applied at such a low concentrations that its own colour is acceptable for most applications.
  • Tungsten oxides and tungstates are known as infrared shielding material.
  • the publications EP 1 676 890 and US 2007/0187653 disclose an infrared shielding nanoparticle dispersion comprising tungsten trioxide having reduced oxygen.
  • the invention relates to the use of tungsten oxide of the formula WO3-x wherein W is tungsten, O is oxygen, and x is 0.1-1 and/or the use of tungstate of the formula MxWyOz wherein M is one or more element selected from NH 4 , H, Li, Na, K, Rb, Cs, Ca, Ba, Sr, Fe, Sn, Mo, Nb, Ta, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, TI; W is tungsten, O is oxygen, 0.001 ⁇ x/y ⁇ 1, and 2.0 ⁇ z/y ⁇ 3.0, to increase the heat-input amount of near infrared radiation in the process of NIR curing of coatings and NIR drying of coatings.
  • the heat-input amount is the thermal energy supplied by near infrared radiation and corresponds to the temperature reached after NIR-curing and drying of coatings.
  • y is 1.
  • Examples are: H 0.53 WO 3 Na 0.33 WO 3 , K 0.33 WO 3 , Cs 0.33 WO 3 , Ba 0.33 WO 3 , Rb 0.33 WO 3
  • tungsten suboxides e.g. WO 2,7
  • tungsten bronzes e.g. H 0.53 WO 3 Na 0.33 WO 3 , Cs 0.33 WO 3 .
  • Cs 0.2-0.5 WO 3 are especially preferred.
  • the tungsten bronzes can be prepared according to EP 1676890, wherein it is said that tungsten bronzes as expressed by the formula M x WO 3 can be prepared by heating an aqueous solution of ammonium meta tungstate with metal salts to about 300-700° C. and drying the aqueous mixture to obtain a solid product.
  • Tungsten oxides powders are commercially available e.g. from Osram Sylvania.
  • WO 2,7 may also be prepared by reducing ammonium tungstate in a plasma reactor. The commercially available WO 2,7 may be dispersed and then this dispersion is milled e.g. in a Dynomill mill with 0.4- ⁇ m zirconium balls to obtain particles having a particle size between 10 nm and 1 ⁇ m, preferably between 10 nm and 500 nm, more preferably between 10 nm and 200 nm.
  • the amount of tungsten oxide or of tungstate applied is between 0.01 and 2.0 wt %. In this amount the slight blue color of tungsten oxide is not relevant.
  • the NIR radiation used in the process according to the invention is short-wave infrared radiation in the wavelength range from about 700 nm to about 3000 nm.
  • Radiation sources for NIR radiation include, for example, conventional NIR radiation emitters, which are available commercially (for example, from Adphos) with the main emission in the range from 800 to 1500 nm, diode lasers, fibre lasers or a Nd:YAG laser.
  • coatings can be used for all type of coatings including both pigmented and unpigmented coating materials.
  • coatings may comprise solvent and/or water or may be solventless or water-free. They may also comprise fillers and other additives in addition to the pigments.
  • Any kind of coating is suitable in the method according to the invention, for example, powder coatings, clearcoats, high-solids coatings, effect coatings, high-gloss coatings, silk-finish coatings, matt-finish coatings, spray coatings, dip-coatings, pour-coatings etc.
  • Corresponding raw materials and compositions are known to the person skilled in the art and are described, for example, in “Lehrbuch der Lacktechnologie”, Vincentz Verlag, 1998.
  • NIR Curing of coatings is state of the art in the field of coil coatings. As coating formulations per se do not absorb NIR-radiation, the heating rate of the coating during drying and/or curing is therefore strongly dependent from several factors:
  • one aspect of the invention is the use in pigmented coatings.
  • Minatec 230 A-IR consists of a specific antimony tin composition (Merck), Lazerflair 825 is a mica based platelet type pigment (Merck) and Lumogen IR 765 and IR 788 are organic quaterrylene-bisimides (BASF). LaB 6 can be purchased from Aldrich.
  • Ammonium paratungstate powder (NH 4 ) 10 W 12 H 2O O 42 .4H 2 O, Osram Sylvania ) was entrained into an argon carrier gas by a vibratory-type powder feeder operating at 10 g/min.
  • the fluidized powder was fed into a plasma reactor with a Tekna PL-50 plasma torch operated at a power of 65 kW.
  • the temperature range typically reached in the plasma hot zone of the reactor is between 5000-10,000 K.
  • a mixture of 140 slpm argon, 0.5 slpm hydrogen, and 5 slpm helium [slpm standard liters per minute; standard conditions for the calculation of slpm are defined as: Tn 0° C.
  • Particle size is between 30 and 200 nm. This material exhibits very good dispersibility in coatings or plastics etc.
  • the different NIR-Absorbers were tested in a 2P-PU formulation concerning there temperature uptake during NIR-curing as well as the final coating properties.
  • the NIR-Absorbers were incorporated into the millbase using glass beads and a scandex shaker for 16 h according to the following table (values are in g).
  • Millbase Laropal A 81 (urea-aldehyde resin available from BASF) 15.7 g 60% in 1-methoxy-2propylacetate/xylene 3:1 EFKA 4401 (polymeric dispersant, available from Ciba Inc) 0.08 g 1-methoxy-2propylacetate (solvent) 4.62 g Butylglycolacetate (solvent) 1.16 g NIR-A 0.19 g
  • the millbase was mixed with the letdown formulation and the crosslinker was added according to the following table.
  • the coating was applied by a wire bar using a WFT (wet film thickness) of 80 ⁇ m.
  • the coatings were dried in an NIR-dryer using different lamp settings (6 Adphos high-burn NIR-lamps, output from 50-100%) and belt speeds (1-4 m/min).
  • the distribution of the NIR-A into the coating formulation was checked via the measurement of haze over black. The lower the value the better the distribution in the formulation and the less impact on the visual film properties is observed.
  • the temperature of the coating surface was measured directly after cure.
  • the Table below shows the results using a belt speed of 2 m/min, a 6 Adphos high-burn NIR-lamps, output 70%, a distance to the lamp of 100 mm
  • the millbase was prepared according to a standard process using a dispermat for pre-mixing and additional milling for 1 h using a Disperser DAS 200 from Lau.
  • the coatings were applied onto pre-primed white aluminium panels using a slit coater leading to DFT's of around 80 ⁇ m.
  • Formulations with TiO 2 and mixtures of TiO 2 and NIR-A′ s were tested. Curing was done at different belt speeds using 6 HB-NIR emitters from the company Adphos.
  • RAL 9010 being the most critical concerning the efficient absorption of the emitted energy.
  • NIR-A Example 2
  • the NIR-A can be added either directly in the milling step or alternatively via a resin free pigment paste based on Ciba EFKA® 4310 for solvent based applications.
  • the addition of the NIR-A leads to a strong reduction of the curing time (see Tab. 1). This allows to either increase the belt speed leading to a higher throughput of the coating line or to reduce the lamp output leading to a reduction of electricity costs.
  • the belt speed to cure was determined via the stability of the cured coating against 100 MEK doublerubs.
  • Example 3.2 The same formulation was used as in Example 3.2.
  • the formulation with 45 w % TiO 2 on solids was used as reference.
  • the belt speed to cure was determined via the stability of the cured coating against 100 MEK doublerubs.
  • the invention relates to the use of tungsten oxide of the formula WO3-x wherein W is tungsten, O is oxygen, and x is 0.1-1 and/or the use of tungstate of the formula MxWyOz wherein M is one or more element selected from NH 4 , H, Li, Na, K, Rb, Cs, Ca, Ba, Sr, Fe, Sn, Mo, Nb, Ta, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, TI; W is tungsten, O is oxygen, 0.001 ⁇ x/y ⁇ 1, and 2.0 ⁇ z/y ⁇ 3.0, to increase the heat-input amount of near infrared radiation in the process of laser marking of plastics.
  • tungsten suboxides e.g. WO 2,72
  • tungsten bronzes e.g. H 0.53 WO 3 Na 0.33 WO 3 , Cs 0.33 WO 3 .
  • Cs 0.2-0.5 WO 3 are especially preferred.
  • the invention relates to the use of tungsten oxide of the formula WO3-x wherein W is tungsten, O is oxygen, and x is 0.1-1 and/or the use of tungstate of the formula MxWyOz wherein M is one or more element selected from NH 4 , H, Li, Na, K, Rb, Cs, Ca, Ba, Sr, Fe, Sn, Mo, Nb, Ta, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, TI; W is tungsten, O is oxygen, 0.001 ⁇ x/y ⁇ 1, and 2.0 ⁇ z/y ⁇ 3.0, to increase the heat-input amount of near infrared radiation in the process of laser welding of plastics.
  • tungsten suboxides e.g. WO 2,72
  • tungsten bronzes e.g. H 0.53 WO 3 Na 0.33 WO 3 , Cs 0.33 WO 3 .
  • Cs 0.2-0.5 WO 3 are especially preferred.
  • Laser radiation is used in welding processes for producing fusion bonded plastics. Typical laser wavelengths used are: 808 nm, 850 nm, 940 nm, 980 nm or 1064 nm.
  • Typical laser wavelengths used are: 808 nm, 850 nm, 940 nm, 980 nm or 1064 nm.
  • An IR absorber is carbon black. Due to the dark color welding of brightly colored or transparent parts is impossible.
  • the concentration of the tungsten oxide or of the tungstate is 10-800 ppm, preferably 100-300 ppm.
  • the tungsten oxide or of the tungstate may be incorporated directly into the plastics parts by known processes like injection molding, extrusion, and the like.
  • plastics used in a laser welding process are polypropylene, polyvinylbutyrale, polyamide, polycarbonate, polycarbonate-polyethylene terephthalate-blends, polycarbonate-polybutylene terephthalate-blends, polycarbonate-acrylnitrile/styrene/acrylnitrile-copolymer-blends, polycarbonate-acrylnitrile/butadiene/styrene-copolymer-blends, polymethylmethacrylate-acrylnitrile/butadiene/styrene-copolymer-blends (MABS), polyethylene terephthalate, polybutylene terephthalate, polymethylmethacrylate, polybutylacrylate, polymethylmeth-acrylate-polyvinylidenedifluoride-blends, acrylnitrile/butadiene/styrene-copolymere (ABS), styrene/acrylnitrile-
  • the IR absorber according to Example 2 is incorporated by means of an injection molding machine into a polycarbonate sheet (thickness 2 mm) at a concentration of 500 ppm.
  • the resulting transparent slightly bluish sheet is welded together with a polycarbonate sheet (thickness 1 mm) using a 250 watt Nd:YAG-laser.
  • the surface was scanned by laser beam at a speed of 20 mm/sec.
  • the resulting welding has an excellent connection, is highly transparent, does not show any localized plastic deformation, does not evolve bubbles during welding. No fracture of the welding seam is induced due to mechanical stress.
  • IR absorbers for laser welding of plastics like Lumogen IR 765 or Lumogen IR 788 no welding takes place under these conditions. This is also true for diode lasers at e.g. 980 nm, 940 nm or 850 nm instead of a Nd:YAG laser (1064 nm). Only at 808 nm welding with these IR absorbers takes place.
  • the invention relates to the use of tungsten oxide of the formula WO3-x wherein W is tungsten, O is oxygen, and x is 0.1-1 and/or the use of tungstate of the formula MxWyOz wherein M is one or more element selected from NH 4 , H, Li, Na, K, Rb, Cs, Ca, Ba, Sr, Fe, Sn, Mo, Nb, Ta, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, TI; W is tungsten, O is oxygen, 0.001 ⁇ x/y ⁇ 1, and 2.0 ⁇ z/y ⁇ 3.0, to increase the heat-input amount of near infrared radiation in the process of NIR curing of adhesives and sealants and NIR drying of adhesives and sealants.
  • tungsten suboxides e.g. WO 2,72
  • tungsten bronzes e.g. H 0.53 WO 3 Na 0.33 WO 3 , Cs 0.33 WO 3 .
  • Cs 0.2-0.5 WO 3 are especially preferred.
  • NIR absorbing additive to a liquid adhesive in particular water based adhesives but also solvent based adhesives can improve drying performance of the liquid adhesive by the concentrated absorption of the emitted NIR radiation.
  • NIR radiation and NIR absorbing additive for drying liquid adhesives can be used in addition to conventional drying processes like hot air or IR radiation drying or as independent drying step.
  • NIR absorbing additive to a liquid adhesive and subsequent irradiation with NIR under given constant conditions, result in a lower content of residual liquid (water) compared to the same adhesive without the NIR absorbing additive.
  • This is especially interesting in web coating applications of liquid adhesives for example in the manufacture of label laminates or tapes. Further in web laminating processes of non porous materials like films or foils were the liquid adhesive needs to be completely dry before the lamination step. Also with porous substrates like paper or fabric, the complete adhesive drying before lamination gives advantages with regards to flatness of moisture or water sensitive substrates.
  • a further advantage is provided with the addition of NIR absorbing additives, that the induced energy is mainly absorbed within the adhesive layer itself which leads to lower substrate temperatures compared to conventional drying operations. This opens interesting possibilities to dry liquid adhesive coatings on temperature sensitive substrates like low melting or shrinkable films and fabrics.
  • the NIR absorbing additive according to Example 2 was, with the help of an acrylic copolymer dispersant EFKA 4585 from Ciba, mixed in a speed mixer. With a stainless steel coating bar a 50 micron adhesives layer was applied to a glass plate. The weight of the adhesive was determined before and after multiple passes under the NIR emitter.
  • NIR absorbing additives can be added to 100% solid, thermoplastic heat activated adhesive systems.
  • a heat activated adhesive layer is created by coating or extruding the corresponding adhesive system to one of the substrates to be bonded or to a suitable intermediate carrier.
  • a heat activated adhesive layer can be created by coating and drying a corresponding adhesive from an aqueous or solvent carrier.
  • the so prepared adhesive layer may be sticky to the touch but is typically non-sticky and can be converted into smaller units e.g. slit rolls or sheets, for later activation and bonding to the second substrate.
  • Heat activated adhesives can also be manufactured and provided as self supporting films (adhesive film), webs (web adhesive) or powders (powder adhesives).
  • the so prepared heat activable adhesive layer or the self-supporting adhesive structure has to be heated above its activation temperature and then joined with the bonding substrate(s).
  • Typical adhesive activation methods are: flame activation, hot air activation, IR activation, activation via heated rolls or a heat calendar heated plates, wedges or presses.
  • NIR absorbing additives to heat activated adhesives the activation can conveniently be done with an NIR emitter.
  • the suitably modified adhesive absorbs the NIR radiation; heats up above it required activation temperature and the bond can be established.
  • NIR absorbing additives brings the further advantage, that the energy is mainly absorbed by the adhesive and not the substrates and therefore also temperature sensitive materials are accessible to this bonding method.
  • Typical chemistries for heat activated adhesives involve: polyolefines, amorphous alpha polyolefins, modified polyolefines like EVA, EAA, BAA, polypropylene, co-polyesters, co-polyamides, thermoplastic polyurethanes, polycaprolactones, styrene-blockcopolymer based hotmelt adhesives
  • a typical heat activated hotmelt adhesive based on amorphous poly-alpha-olefines was mixed in a sigma blade kneader at 170° C. for 1 hour.
  • APAP polymers were obtained from Evonik Industries, hydrocarbon resin and styrene blockcopolymer from Exxon Chemical, Antioxidant from Ciba Inc. and the rosin ester tackyfier from Eastman.
  • the adhesives were coated with a hot melt slot-die coater onto a siliconized paper and transferred to a steel plat carrier.
  • the adhesive samples were exposed to the NIR radiation and the temperature of the adhesive surface was observed via laser thermometer. The results show that the adhesive without NIR absorbing additive according to Example 2 only reaches the temperature as the blank steel carrier plate. Adding different amounts of NIR absorbing additive boosts the adhesive surface temperature to 99° C., 109° C. and 162° C. respectively.
  • the invention relates to the use of tungsten oxide of the formula WO3-x wherein W is tungsten, O is oxygen, and x is 0.1-1 and/or the use of tungstate of the formula MxWyOz wherein M is one or more element selected from NH 4 , H, Li, Na, K, Rb, Cs, Ca, Ba, Sr, Fe, Sn, Mo, Nb, Ta, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, TI; W is tungsten, O is oxygen, 0.001 ⁇ x/y ⁇ 1, and 2.0 ⁇ z/y ⁇ 3.0, to increase the heat-input amount of near infrared radiation and the efficiency in the process of laser marking of paper
  • tungsten suboxides e.g. WO 2,72
  • tungsten bronzes e.g. H 0.53 WO 3 Na 0.33 WO 3 Cs 0.33 WO 3 .
  • Cs 0.2-0.5 WO 3 are especially preferred.
  • Using lanthanum hexaboride instead of the material from example 2 requires more than 10 times as much of the IR-absorber (1.4 parts LaB6) in order to get the same laser marking performance.
  • the invention relates to the use of tungsten oxide of the formula WO3-x wherein W is tungsten, O is oxygen, and x is 0.1-1 and/or the use of tungstate of the formula MxWyOz wherein M is one or more element selected from NH 4 , H, Li, Na, K, Rb, Cs, Ca, Ba, Sr, Fe, Sn, Mo, Nb, Ta, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, TI; W is tungsten, O is oxygen, 0.001 ⁇ x/y ⁇ 1, and 2.0 ⁇ z/y ⁇ 3.0, to increase the heat-input amount of near infrared radiation in the process of drying of printings or fixing of ink toners to a substrate.
  • tungsten suboxides e.g. WO 2,72
  • tungsten bronzes e.g. H 0.53 WO 3 Na 0.33 WO 3 Cs 0.33 WO 3 .
  • Cs 0.2-0.5 WO 3 are especially preferred.
  • the invention relates to the use of tungsten oxide of the formula WO3-x wherein W is tungsten, O is oxygen, and x is 0.1-1 and/or the use of tungstate of the formula MxWyOz wherein M is one or more element selected from NH 4 , H, Li, Na, K, Rb, Cs, Ca, Ba, Sr, Fe, Sn, Mo, Nb, Ta, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, TI; W is tungsten, O is oxygen, 0.001 ⁇ x/y ⁇ 1, and 2.0 ⁇ z/y ⁇ 3.0, to increase the heat-input amount of near infrared radiation in the process of heating of plastic preforms.
  • tungsten suboxides e.g. WO 2,72
  • tungsten bronzes e.g. H 0.53 WO 3 Na 0.33 WO 3 , Cs 0.33 WO 3 .
  • Cs 0.2-0.5 WO 3 are especially preferred.
  • the invention relates to the use of a blend comprising tungsten oxide and/or tungstate as defined above and in addition a dithiolene metal complex of the formula I or II as disclosed in the International publication WO2008/086931 to increase the heat-input amount of near infrared radiation.
  • X 1 , X 2 and X 3 independently of one another are sulfur or oxygen;
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 independently of one another are hydrogen, NR 7 R 8 , C 1 -C 18 alkyl, aryl, aralkyl, heteroarylalkyl, wherein R 7 and R 8 independently of one another are C 1 -C 18 alkyl, aryl, aralkyl, heteroarylalkyl.
  • C 1 -C 18 alkyl examples are propyl, isopropyl, n-butyl, sec. butyl, tert. butyl, n-hexyl, cyclopentyl, cyclohexyl.
  • Aryl is phenyl, naphyl, anthryl or phenantryl.
  • Arylalkyl ist e.g. benzyl.
  • Heteroarylalkyl is understood as heteroaryl groups connected, as substituents, via a lower alkylene to a heteroaromatic ring selected from imidazolyl, pyridyl, thienyl, furyl, thiazolyl, indolyl, chinolinyl, pyrazolyl, pyrazyl, pyridazyl, pyrimidinyl.
  • the amount of dithiolen metal complex to tungsten oxide is in the range of 5 to 90 wt %
  • the invention relates to the use of a blend comprising tungsten oxide and/or tungstate as defined above and in addition at least one organic IR absorber selected from quinone-diimmonium salt, aminium salt, polymethines such as cyanine squaraine, croconaine; phthalocyanine, naphthalocyanine and quaterrylene-bisimide or in addition at least one anorganic IR absorber selected from lanthanum hexaboride, indium tin oxide (ITO) antimony tin oxide such as Minatec 230 A-IR available from Merck, or Lazerflair® pigments available from Merck.
  • organic IR absorber selected from quinone-diimmonium salt, aminium salt, polymethines such as cyanine squaraine, croconaine; phthalocyanine, naphthalocyanine and quaterrylene-bisimide or in addition at least one anorganic IR absorber selected from lan

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Cited By (14)

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EP2217533A2 (en) 2010-08-18
EP2682265A1 (en) 2014-01-08
TWI461368B (zh) 2014-11-21
KR101320750B1 (ko) 2013-10-21
WO2009059901A2 (en) 2009-05-14
CN102965049A (zh) 2013-03-13
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BRPI0818911A2 (pt) 2015-05-12
KR20120041266A (ko) 2012-04-30
CN102942818B (zh) 2014-09-17
WO2009059900A3 (en) 2009-10-22
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