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(12) Patent Application Publication (10) Pub. No.: US 2010/0139855A1 Edler Et Al

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(12) Patent Application Publication (10) Pub. No.: US 2010/0139855A1 Edler Et Al US 20100139855A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2010/0139855A1 Edler et al. (43) Pub. Date: Jun. 10, 2010 (54) POLYMERS HAVING A HIGH INFRARED (30) Foreign Application Priority Data ABSORPTION CAPACITY Aug. 15, 2005 (DE) ......................... 102005038774.8 (76) Inventors: Gerhard Edler, Trebur (DE); Rainer Linzmeier, Gross-Zimmern Publication Classification (DE) (51) Int. Cl. Correspondence Address: Sk 54 :08: MILLEN, WHITE, ZELANO & BRANGAN, P.C. CSK 9/02 (200 6. 01) 2200 CLARENDON BLVD., SUITE 1400 CSK 700 (2006.015 ARLINGTON, VA 22201 (US) (52) U.S. Cl. ....................... 156/272.2:523/200: 523/216 (21) Appl. No.: 12/063,817 (57) ABSTRACT (22) PCT Filed: Jul. 26, 2006 The present invention relates to polymers comprising absorp (86). PCT No.: PCT/EP06/07385 tion pigments, which are distinguished by the fact that they have high absorption in the near IR region, and to the use S371 (c)(1), thereof, in particular in thermoforming and in IR light weld (2), (4) Date: Feb. 14, 2008 1ng. Patent Application Publication Jun. 10, 2010 US 2010/O139855A1 Temperature behaviour of film under the influence of an IR emitter O 100 200 300 400 500 600 7OO Time in sec US 2010/O 139855A1 Jun. 10, 2010 POLYMERS HAVINGA HIGH INFRARED 0010 Surprisingly, it has now been found that the addition ABSORPTION CAPACITY of absorption pigments based on finely divided pale or trans parent semiconductor materials gives a polymer system which has high absorption in the near IR, in particular in the 0001. The present invention relates to polymers which are region from 750 to >2500 nm, very particularly preferably in distinguished by the fact that they have high absorption in the the region from 850 to 2500 nm, without changing the colour near IR region, and to the use thereof, in particular in ther in the visible region. Although the absorption pigment has moforming and in IR light welding. very high absorption in the near IR, the pigment is itself 0002 The heating of plastics using IR radiation is wide virtually white and thus only influences the properties of the spread in the area of thermoforming, Such as the deep drawing polymer, Such as colour and transparency, to an insignificant of plastic sheets and films, and the conditioning of preforms extent. Furthermore, the absorption pigment increases the for stretch blow moulding. However, this radiation is also thermal conductivity within the polymer matrix and acceler employed for accelerating polymerisation and curing pro ates polymerisation and curing processes. cesses and the welding of plastic parts. 0011. The invention therefore relates to polymers, prefer 0003. The IR source used here are hot bodies which emit ably thermoplastics, which comprise, as absorption pigment, IR radiation over a broad wavelength spectrum. The higher pale or transparent particulate semiconductor materials or the temperature of the radiating body, the higher also the particulate substrates coated with pale or transparent semi emitted energy and the shorter the wavelength. The electro conductor materials. magnetic spectrum of IR sources can be divided into three 0012 Suitable pale or transparent semiconductor materi regions in accordance with their wavelength: als are preferably those which absorb in the near IR region, in particular in the region from 750 to 2500 nm. The particulate semiconductor materials are preferably spherical, needle shaped or flake-form particles or flake-form, spherical or IR type Wavelength (nm) Temperature C. needle-shaped Substrates coated with semiconductor materi Short 1000-1500 1SOO-2700 als. Moderate 1500-2SOO 750-1500 0013 The semiconductor materials are built up homoge Long 3OOO-SOOO 200-7SO neously from pale or transparent semiconductor materials or applied as coating to a particulate Substrate. The semiconduc 0004 More recent developments in emitter technology tor materials are preferably based on oxides and/or sulfides, even reach wavelengths of up to 800 nm, i.e. as far as the Such as, for example, indium oxide, antimony oxide, tin region of visible light. oxide, zinc oxide, zinc sulfide, tin sulfide or mixtures thereof. 0005 Since high-temperature emitters emit more energy, 0014 Suitable semiconductor materials generally have they represent the best heat source. However, most polymer particle sizes of 0.01 to 2000 um, preferably 0.1 to 100 um, in groups only exhibit good absorption in a range from 2900 to particular 0.1 to 30 um. 3700 and above 5500 nm. This means that the energy of very 0015 The semiconductor materials either consist homo effective high-temperature emitters cannot be utilised suffi geneously of the said semiconductors or are particulate, pref ciently for heating polymeric systems. erably spherical, needle-shaped or flake-form substrates 0006. In the case of pigmented plastics, the situation is which are mono- or multicoated with the said semiconductor even more complex, since the absorption and reflection of the materials. The substrates are preferably coated with only one pigment are now added. Black pigments have high absorption layer. in the near infrared and therefore heat up very quickly in the 0016. The substrates can be spherical, flake-form or short-wave IR. White pigments, by contrast, reflect visible needle-shaped. The shape of the particles is not crucial perse. light very well, and this property is valid into the IR region. In In general, the particles have a diameter of 0.01-2000 um, the case of pale colours, this results in a significant delay in particularly 0.1-300 um and in particular 0.5-60 lum. The heating compared with black or dark colours. Owing to this particularly preferred substrates are spherical and flakeform delay, it not only takes much longer until, for example, a pale substrates. Suitable flake-form substrates have a thickness plastic sheet has reached the forming temperature necessary between 0.02 and 5um, in particular between 0.1 and 4.5um. for thermoforming, but the long dwell time may even result in The size in the two other dimensions is generally between 0.1 damage to the plastic Surface. and 1000 um, preferably between 1 and 500 um and in par 0007. However, the absorption pigments known from the ticular between 1 and 60 um. prior art, such as, for example, carbon black, all have the 0017. The substrates are preferably natural or synthetic disadvantage that they permanently colour the plastic. In mica flakes, SiO flakes, Al-O flakes, glass flakes, alu addition, they have to be added in comparatively high con minium flakes, BiOCl flakes, SiO, beads, silica gel, kiesel centrations and are frequently toxicologically unacceptable. guhr, glass beads, hollow glass beads, TiO, beads, polymer 0008. The object of the present invention was to find a pale beads, for example comprising polystyrene or polyamide, or or white plastic colouring which simultaneously has good TiO, needles, or mixtures of the said substrates. absorption in the near infrared region and can be carried out in 0018. The coating of the particulate substrates with the a simple manner. The absorber material must exhibit pro semiconductor materials is either known or can be carried out nounced absorption and an adequate reaction in this specific by processes known to the person skilled in the art. The NIR region. substrates are preferably coated by hydrolysis of the corre 0009. The absorber here should be easy to incorporate into sponding metal salts. Such as, for example, metal chlorides or the polymer system, have high transparency and only be metal Sulfates, metal alkoxides or carboxylic acid salts in employed in low concentrations. aqueous or conventional solvent solution. US 2010/O 139855A1 Jun. 10, 2010 0019. In the case of the semiconductors with a homoge mance, can be added to the plastics. Suitable colorants are, in neous structure and also in the case of the Substrates coated particular, coloured metal oxide pigments and organic pig with one or more semiconductor materials, the semiconduc ments and dyes. tor material preferably has a microcrystalline structure. 0031 All known polymer systems, in particular thermo 0020 Particularly preferred absorption pigments are plastics and thermoelastic plastics, as described, for example, flake-form or spherical tin oxide, antimony oxide, indium tin in Ullmann, Vol. 15, pp. 457 ff. Verlag VCH, can be doped oxide (ITO) and mica flakes coated with ITO, tin oxide or with the absorption pigments. Suitable plastics are thermo antimony oxide, and mixtures of the said oxides. plastics and thermoelastic plastics, such as, for example, 0021 Particularly preferred absorption pigments are polyethylene (PE, HDPE, LDPE), polypropylene (PP), transparent or pale semiconductor materials having a powder polyamides, polyesters, polyester-esters, polyether-esters, resistance of <20 S2 m, preferably <5 S2 m. polyphenylene ether, polyacetals, polyalkylene terephtha 0022. A particularly preferred absorption pigment is a tin lates, in particular polybutylene terephthalate (PBT) and oxide doped with antimony oxide or a substrate coated there polyethylene terephthalate (PET), polymethyl methacrylate with, such as, for example, a mica flake. Preference is fur (PMMA), polyvinyl acetal, polyvinyl chloride (PVC), thermore given to spherical SiO particles coated with anti polyphenylene oxide (PPO), polyoxymethylene (POM), mony oxide-doped tin oxide. The particle sizes of these polystyrene (PS), acrylonitrile-butadiene-styrene (ABS), preferred absorption pigments are preferably 1-2 um. acrylonitrile-styrene-acrylate
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