WO2012104006A1 - Polymères aptes au marquage par laser et au soudage par laser - Google Patents

Polymères aptes au marquage par laser et au soudage par laser Download PDF

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Publication number
WO2012104006A1
WO2012104006A1 PCT/EP2012/000066 EP2012000066W WO2012104006A1 WO 2012104006 A1 WO2012104006 A1 WO 2012104006A1 EP 2012000066 W EP2012000066 W EP 2012000066W WO 2012104006 A1 WO2012104006 A1 WO 2012104006A1
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WIPO (PCT)
Prior art keywords
laser
markable
polymers according
tpto
weldable
Prior art date
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PCT/EP2012/000066
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English (en)
Inventor
Tetsuji Honjo
Satoru Kobayashi
Masahiko Yazawa
Kazuhisa AZUMA
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Merck Patent Gmbh
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Publication of WO2012104006A1 publication Critical patent/WO2012104006A1/fr

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16—Laser beams
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16—Laser beams
    • B29C65/1629—Laser beams characterised by the way of heating the interface
    • B29C65/1635—Laser beams characterised by the way of heating the interface at least passing through one of the parts to be joined, i.e. laser transmission welding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16—Laser beams
    • B29C65/1677—Laser beams making use of an absorber or impact modifier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/05—Particular design of joint configurations
    • B29C66/10—Particular design of joint configurations particular design of the joint cross-sections
    • B29C66/11—Joint cross-sections comprising a single joint-segment, i.e. one of the parts to be joined comprising a single joint-segment in the joint cross-section
    • B29C66/112—Single lapped joints
    • B29C66/1122—Single lap to lap joints, i.e. overlap joints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/43—Joining a relatively small portion of the surface of said articles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16—Laser beams
    • B29C65/1629—Laser beams characterised by the way of heating the interface
    • B29C65/1674—Laser beams characterised by the way of heating the interface making use of laser diodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16—Laser beams
    • B29C65/1687—Laser beams making use of light guides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16—Laser beams
    • B29C65/1696—Laser beams making use of masks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/739—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/7392—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoplastic
    • B29C66/73921—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoplastic characterised by the materials of both parts being thermoplastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/739—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/7394—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoset
    • B29C66/73941—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoset characterised by the materials of both parts being thermosets

Definitions

  • the present invention relates to laser-markable and laser-weldable polymers which comprise, as absorber, a tungsten and/or phosphorus doped tin oxide or a substrate coated with tungsten and/or phosphorus doped tin oxide.
  • the identification marking of products is becoming increasingly important in almost every branch of industry. For example, it is frequently necessary to apply production dates, expiry dates, bar codes, company logos, serial numbers, etc. to plastics or plastic films. These markings are currently mostly executed using conventional techniques, such as printing, hot- stamping, other stamping methods or labelling. However, in particular for plastics, increasing importance is being attached to the contactless, very rapid and flexible method of marking with lasers. With this technique it is possible to apply graphic inscriptions, such as bar codes, at high speed, even to non-planar surfaces. Since the inscription is located within the plastics article itself, it is durably abrasion-resistant.
  • the resin compositions that contain phthalocyanine-based compounds, cyanine-based compounds, aminium-based compounds, imonium-based compounds, squalium-based compounds, polymethine-based compounds, anthraquinone-based compounds, azo-based compounds and carbon black are known in JP-A 2004-148800.
  • JP-A 2005-290087 in order to enhance sensitivity to the laser, a absorbent resin composition for laser is proposed in which copper phosphonate with an aromatic ring, metallic elements, salts, oxides, hydroxides, and the like are added.
  • these compounds have inadequate sensitivity to laser light, and a large quantity of them must be added to obtain a problem-free bonding.
  • the addition of a large quantity of the composition can alter the basic physical properties of the resin molding itself and can lead to reduced mechanical strength and other drawbacks.
  • Most of the above mentioned compositions also absorb light in the visible wavelength region, and severe coloration of the plastics is also cited as a drawback.
  • tin-doped indium oxide (ITO) and antimony-doped tin oxide (ATO) coated on platelet inorganic substrates described in JP 3591654 have relatively high transparency and absorption for laser.
  • a powder of mixed oxides of tin and a transition metal selected from group consisting of niobium, tungsten, vanadium and chromium has been published in U.S. 2009-060572.
  • the powder absorbs YAG laser energy and converts it into heat, carbonization in the surrounding material occurs and results in the formation of a dark mark that contrasts to the remainder of the surrounding area.
  • the color of powder become darker and can not result in the formation of dark markings that contrasts to the remainder of the surrounding area which is colored by addition of these powders. Consequently, the successful absorber should have high transparency or bright own color.
  • Transmission laser welding is an elegant technique which was developed for welding together materials such as polymers, like plastics. This is achieved by bringing two plastic elements into contact with one another, where one thereof is transparent to laser light and the other is opaque to laser light. The area of contact between the two plastic elements is then exposed to a laser beam. The laser beam passes through the transparent plastic element and is absorbed by the second, opaque plastic element. This causes the opaque plastic element to warm, so that the area of contact between the two plastic elements melts, resulting in the formation of a weld site.
  • the lasers used are usually diode lasers or Nd:YAG lasers having wavelengths between 808-1100 nm. Most polymers are more or less transparent at this wavelength, meaning that the absorption property can be achieved by the addition of additives.
  • the absorber used is usually carbon black. This exhibits very high absorption both in the visible and also in the IR region. Carbon black therefore only allows black as colour. Pale colours and transparent systems are impossible.
  • EP 1117502 B1 describes a method in which the absorber is applied in the interlayer. This method enables welding of polymers in all colours, even of transparent plastics. The disadvantage of this method is the additional application step of the absorber paste. The weld seam usually also tends to be on the surface.
  • the NIR absorbers used here are of an organic nature and exhibit no or virtually no light scattering.
  • the organic absorbent for laser welding described in JP-A 2004-148800 generally has a narrow wavelength range of absorbance, and a relatively large amount thereof must be added to obtain adequate heat generation.
  • the carbon black has high thermal stability and absorbance.
  • the plastic turned to black color due to the absorbance in the wavelength region of visible light. It is undesirable when a transparent plastic is required.
  • the additives used for laser marking such as, for example, antimony, antimony oxide, conductive pigments and TiO2, generally allow colouring in pale colours. They are added to the formulations of the laser-absorbent side and thus facilitate transmissive laser welding without the intermediate step of application of a laser additive to the site to be welded. Weldability is possible, but is not of commercial interest owing to the long process times. Besides the speed, a disadvantage is that the absorption of these additives is lower than that in the case of carbon black.
  • T1O2 is a surface absorber and thus does not allow a large penetration depth of the laser radiation.
  • the plastic may melt, but stable welding cannot be achieved.
  • Nd:YAG lasers are increasingly being used for the identification marking or welding of plastics by laser.
  • the YAG lasers usually used give a pulsed energy beam with a characteristic wavelength of 1064 nm or 532 nm.
  • the absorber material must have pronounced absorption in this specific NIR region in order to exhibit an adequate reaction during fast inscription procedures.
  • the object of the present invention is therefore to find laser-markable and laser-weldable polymers which when exposed to laser light can give a white marking with high contrast and at the same time enable good welding, even for pale colours, on exposure to laser light.
  • the successful absorbent should therefore have a very pale inherent colour and/or only have to be employed in very small amounts.
  • the objective of this invention is to find a laser marking and welding absorber which can be adapted to various industrial fields.
  • the laser-markability and laser- weldability of polymers in particular the contrast of marking can be improved by addition of an absorber selected from a tungsten and/or phosphorus doped tin oxide or a substrate coated with tungsten and/or phosphorus doped tin oxide, preferably a tungsten and phosphorus doped tin oxide (TPTO) or a substrate coated with tungsten and phosphorus doped tin oxide.
  • an absorber selected from a tungsten and/or phosphorus doped tin oxide or a substrate coated with tungsten and/or phosphorus doped tin oxide, preferably a tungsten and phosphorus doped tin oxide (TPTO) or a substrate coated with tungsten and phosphorus doped tin oxide.
  • TPTO tungsten and phosphorus doped tin oxide
  • the markings and laser-weldings achieved by the use of the transparent TPTO or TPTO coated on substrate are significantly paler, and at the same time the energy densities are lower.
  • the present invention therefore relates to laser-markable and laser- weldable polymers characterised in that the polymer contains, as absorber, a tungsten and/or phosphorus doped tin oxide or a tungsten and/or phosphorus doped tin oxide coated on substrate.
  • the laser-weldability of polymers consisting of a laser-absorbent part and a laser-transparent part can be improved by addition of TPTO or a TPTO coated on substrate into a laser-absorbent part.
  • the welding results achieved by the use of the TPTO powder are excellent compared to the absorbers known from the prior art.
  • TPTO and TPTO coated on substrates are characterized that they have the absorption at a certain wavelength corresponding to the YAG-laser. Additionally, TPTO is environment-friendly and harmless because it does not contain toxic elements and heavy metals. Thus, the application field is not limited.
  • TPTO powder in the range of 0.03 to 10 % by weight, based on the plastic resin, preferably from 0.05 to 2 % by weight, and in particular from 0.1 to 1 % by weight, a sharp laser-marking with high contrast and excellent laser-welding results can be achieved by the use of such small concentrations.
  • concentration of the laser absorber in the polymers is of course dependent on the polymer system used.
  • the small proportion of TPTO or TPTO coated on substrates does not substantially alter the polymer system, and has no effect on its processability.
  • colorants it is also possible for colorants to be added to the polymers, permitting any type of variation in colour and at the same time ensuring retention of the laser-marking.
  • Suitable colorants are colour pigments, white pigments, black pigments, effect pigments and in particular coloured metal oxide pigments, and also organic pigments and dyes.
  • the proportion of the laser absorber in plastic molding applications for laser-marking and laser-welding is preferably from 0.05 to 10 % by weight, based on plastic articles, more preferably from 0.1 to 1 % by weight.
  • the proportion of the laser absorber in the plastic printing and in coating applications for laser-marking and welding is preferably from 1 to 50 % by weight, based on plastic films, more preferably from 3 to 10 % by weight.
  • a scattering additive such as, for example, Ti0 2 , CaC03, MgC0 3 or other white pigments or fillers, etc., known to the person skilled in the art can optionally be added to the laser-transparent part.
  • the additive is used in amounts of ⁇ 2 % by weight, preferably ⁇ 0.5% by weight and particularly preferably ⁇ 0.3 % by weight.
  • an absorber can likewise be added in small amounts to the laser-transparent polymer part.
  • the addition of a scattering absorber in the laser-transparent part generally increases the strength of the weld seam and allows faster welding.
  • Suitable laser-scattering absorbers are conductive pigments, such as, for example, antimony, Sb 2 O3, (Sn,Sb)0 2 ,
  • Absorbers of this type are available, for example, from Merck KGaA under the trade name Lazerflair ® .
  • the absorber is preferably added to the laser-transparent polymer part in amounts of 0.001 - 2 % by weight, in particular 0.01 - % by weight and very particularly preferably 0.05 - 0.5 % by weight, based on the polymer part.
  • the proportion of absorber in the laser-transparent polymer part is always significantly smaller than in the laser-absorbent part.
  • the laser-absorbent part comprises a 2-20 times, preferably 5-10 times, larger amount of absorber than the laser-transparent part.
  • the laser-transparent part may comprise both a scattering absorber and a scattering additive. If the scattering absorber is copper hydroxide phosphate or copper phosphate, the absorber in the laser-transparent part and in the laser-absorbent part differs merely in the concentration. The total concentration of scattering absorber and scattering additive in the laser- transparent part preferably should not exceed 2 % by weight.
  • the concentration of the absorber(s) in the respective polymer part is, however, dependent on the plastic system employed.
  • the small proportion of absorber changes the plastic system insignificantly and does not affect its processability.
  • the suitable substrates are inorganic materials preferably selected from the group of from T1O2, ZnO, BaS0 4 , AI2O3, Si0 2 , ZrO 2 , glass, alkali titanate, natural or synthetic mica, phyllosilicates, such as talc, kaolin, wollastonite or sericite, and mixtures thereof.
  • a preferred substrate is T1O2 in view of the whitish hiding power due to high refractive index.
  • the crystal system of T1O2 can be selected from rutile, anatase, brookite or
  • the preferred crystal system is rutile which is the same crystal system of the tin oxide.
  • the shape of the base substrates can be selected from grains, spheres, plates, needles, fibers, columns, rods, and mixtures thereof. Especially preferred are grain or sphere-shaped substrates to obtain a good and smooth surface of the plastic films.
  • the mean diameter is in the range of 0.01 to 100 pm, in particular 0.01 - 30 pm, especially preferred 0.05 - 5 pm.
  • the grain or sphere-shaped substrates have preferably a mean radius of 0.01 - 10 pm, in particular 0.01 - 1 pm, especially preferred 10 - 500 nm. These mean diameters of substrates are desirable at the half of wavelength of visible light, since the whitish hiding power can be obtained on black base materials.
  • the ratio of its long axis and short axis ranges from 2 to 200, preferably 10 to 50.
  • the ratio of its long axis and short axis ranges from 1 to 10, preferably 1 to 5.
  • Preferred spherical base substrates are selected from the group of Ti0 2l ZnO, BaSO 4 , glass, alkali titanate, S1O2, Zr02 or mixtures thereof.
  • Especially preferred base substrates are ⁇ 1 ⁇ 2, alkali titanate and ZnO which have a whitish hiding power due to the high refractive index.
  • Preferred plate, needle, fiber, column and rod-shaped base substrates are selected from the group of natural or synthetic mica, talc, kaolin, sericite, glass, TiO 2 , ZnO, BaSO 4 , AI 2 O 3 , SiO 2 , ZrO 2 , alkali titanate, wollastonite or mixtures thereof.
  • Especially preferred base substrates are TiO 2> alkali titanate and ZnO which have a whitish hiding power due to high refractive index.
  • the amount of TPTO on the substrates is in the range of 20 - 80 wt.%, in particular 20 - 60 wt.%, and most preferably in the range of 40 - 50 wt.%, based on the weight of the final absorber.
  • the layer thickness of TPTO on the substrates is in the range of 10 - 200 nm, preferably 30 - 100 nm.
  • the atomic ratio of tungsten and phosphorus to tin is preferably 0.1 - 30 at.%, in particular, 1 - 10 at.%. If the doping content of tungsten and phosphorus is less or more, the darker markings cannot be achieved.
  • T1O2 particles spherical, grain-shaped having a mean radius of 150 - 500 nm which are coated with 30 - 50 wt.% of TPTO based on the weight of the final particles.
  • the layer thickness of the TPTO layer is preferably in the range of 10 - 100 nm.
  • a production process of TPTO powder or TPTO coated on substrates is not limited to a specific process.
  • the TPTO is deposited or coated on the substrates in the solution.
  • the deposited particles or coated substrates are filtered off, washed, dried and calcined at temperatures of 600 - 1000 °C, preferably 800 - 900 °C, in air or nitrogen atmosphere, preferably in nitrogen atmosphere. It is often advisable to add anionic and/or nonionic surfactants to improve properties.
  • Suitable water-soluble tin and tungsten salts are selected from chlorides, sodium salt, sulfates and nitrates, especially preferred are chlorides.
  • a suitable water-soluble phosphate is preferably phosphoric acid.
  • the layer thickness of TPTO coated on substrates is the range from 5 to 500 nm, preferably from 10 to 200 nm, in particular from 20 to 150 nm.
  • plastic resins can be used in the laser marking and welding application.
  • Suitable plastics are thermo and thermo setting plastics such as polyethylene (PE), polypropylene (PP), polyamide (PA), polyester, polyether, polyphenylene ether, polyacrylate, polyurethane (PU), polyoxymethylene (POM), polymethacrylate, polymethylmethacrylate (PMMA), polyvinyl acetate (PVAC), polyvinyl acetal (PVB), polystyrene (PS), acrylonitrile-butadiene-styrene (ABS), acrylonitrile-styrene-acrylate (ASA), ABS graft polymer, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polycarbonate (PC), polyether sulf
  • the incorporation of the absorber within the polymer like plastic takes place by mixing the plastics pellets with the absorber and optionally with further additives and/or dyes and/or colorants, followed by shaping with exposure to heat.
  • the plastics pellets may, if desired, be treated with adhesion promoters, organic polymer- compatible solvents, stabilizers, dispersants and/or surfactants resistant to the operating temperatures used.
  • the doped plastics pellets are usually produced by placing the plastics pellets in a suitable mixer, wetting these with any additives, and then adding and incorporating the dopant.
  • the plastics are generally pigmented by way of a colour concentrate
  • the laser absorber of the invention is coated on the surface of the resin molding and films by a printing and coating method.
  • a laser absorbent is dispersed in any solvent and additive by using a bead mill, a ball mill, a sand mill, ultrasonic dispersion, or another method, and mixed with a binder resin.
  • the obtained coating product is printed and coated on the surface of resin moldings and films.
  • the binder resin is cured by a prescribed method. Then, a thin plastic film contained a laser absorbent can be formed in which the particles are dispersed in a medium.
  • the thickness of the coating film is not particularly limited, but a thickness range of about 1 to 100 pm is preferred.
  • the printing and coating method is not particularly limited as far as the surface of the substrate can be evenly coated with the resin that includes the powder, and examples include screen printing, gravure printing, offset printing, bar coating, spray coating, dip coating, brush coating, and other methods.
  • the invention also provides a process for producing the laser-markable and laser-weldable polymers, characterized in that a polymer is mixed with the absorber and then shaped with exposure to heat.
  • the plastic is marked and welded with suitable laser radiation as follows.
  • the method of inscription by the laser is such that the specimen is placed in the path of a pulsed laser beam, preferably an Nd:YAG laser.
  • a pulsed laser beam preferably an Nd:YAG laser.
  • CO 2 laser e.g. by using a mask technique
  • the desired results can also be achieved by other conventional types of laser whose wavelength is within the region of high absorption of the pigment used.
  • the marking obtained is determined by the irradiation time (or number of pulses in the case of pulsed lasers) and by the power emitted by the laser, and also by the polymer system used.
  • the power of the laser used depends on the particular application and can readily be determined by the skilled worker in any particular case.
  • the laser used generally has a wavelength within the region from 157 nm to 10.6 pm, preferably within the region from 532 nm to 10.6 pm.
  • Examples which may be mentioned here are a CO 2 laser (10.6 ⁇ ) and an Nd:YAG laser (1064 or 532 nm), and a pulsed UV laser.
  • Excimer lasers have the following wavelengths: F 2 excimer laser: 157 nm, Arf excimer laser: 193 nm, KrCI excimer laser: 222 nm, KrF excimer laser: 248 nm, XeCI excimer laser: 308 nm, XeF excimer laser: 351 nm, and frequency-multiplied Nd:YAG laser: wavelength of 355 nm (frequency-tripled) or 265 nm (frequency-quadrupled). Particular preference is given to using Nd:YAG lasers (1064 or 532 nm) and C0 2 lasers.
  • the energy densities of the lasers used are generally within the range from 0.3 mJ/cm 2 to 50 J/cm 2 , preferably from 0.3 mJ/cm 2 to
  • the pulse frequency is generally within the range from 1 to 30 kHz.
  • Corresponding lasers which can be used in the process of the invention are commercially available.
  • the inscription with the laser is preferably carried out by introducing the article into the ray path of a pulsed laser, preferably of an Nd:YAG laser.
  • the laser welding is carried out by introducing the specimen into the ray path of a continuous wave laser, preferably an Nd:YAG or diode laser.
  • the wavelengths are preferably between 808 and 1100 nm. Since most polymers are more or less transparent at these wavelengths, the absorption property is achieved by the addition of additives. Weldings using other conventional types of laser are also possible if they operate at a wavelength at which the absorber used exhibits high absorption.
  • the welding is determined by the irradiation time and irradiation power of the laser and the plastic system used. The power of the lasers used depends on the respective application and can readily be determined by the person skilled in the art in the individual case.
  • the pigmented plastics of the invention can be used in any sector where conventional printing processes have hitherto been used to inscribe plastics.
  • mouldings made from the plastics of the invention may be used in the electrical industry, electronic industry or motor vehicle industry.
  • laser light With the aid of laser light, it is possible to produce identification markings or inscription markings even at locations to which it is difficult to gain access, for example, on cables, lines, decorative strips, or functional parts in the heating, ventilation or cooling sector, or on switches, plugs, levers or handles which consist of the plastics of the invention.
  • the polymer system of the invention it is also possible for the polymer system of the invention to be used for packaging in the food and drinks sector, or in the toy sector.
  • the markings on the packaging are wipe- and scratch-resistant, resistant to downstream sterilization processes, and can be applied by the marking process in a manner which is hygienically clean.
  • Complete label motifs can be applied durably to the packaging for a reusable system.
  • Another important application sector for laser inscription is that of the marking of plastics to produce individual identification marking for animals, known as cattle tags or ear tags. The information specifically associated with the animal is stored via a barcode system. It can be called up again when required with the aid of a scanner. The inscription must be highly durable since some tags remain on the animals for a number of years.
  • Laser welding with the polymers doped in accordance with the invention can be carried out in all areas where conventional joining methods have hitherto been employed and where it has hitherto not been possible to employ the welding process owing to the laser-transparent polymers and pale colours.
  • the laser-transmissive plastic welding process thus represents an alternative to conventional joining methods, for example high- frequency welding, vibration welding, ultrasound welding, hot-air welding or also the adhesive bonding of plastic parts.
  • Example 1 Process for the preparation of TPTO powder
  • the obtained TPTO precursor particles are then filtered, washed with deionized water and dried at 105 °C.
  • the dried powders are calcinated at 900 °C for 10 min. in an N2 gas atmosphere (less than 3 % of O 2 ).
  • Example 2 Process for the preparation of TPTO coated on TiO 2 powder
  • Example 1 250 g of TiO 2 pigments (mean particle diameter: 0.3 - 0.5 pm) is dispersed in 2 I of deionized water, and the suspension is heated at 75 °C under stirring. The following process is shown in Example 1.
  • Example 3 Process for the preparation of TPTO coated on SiO 2 powder
  • Plastic plates containing each an absorber according to Examples 1-3 are prepared. At first, 0.48 g of each absorber, 1.2 g of TiO 2 pigment and 0.42 g of zinc stearate are added to 300 g of granulate HDPE (High density poly ethylene, HI-ZEXTM2100J of Mitsui Chemicals) and dispersed therein. Then, white plastic plates (145 mm x 75mm x 2mm in thick) are prepared by injection molding process. The injection is carried out under heating at 230 - 250 °C and 100 rpm as a screw rotation speed. As a comparative example, natural plastic plates without absorber are prepared by the same injection molding condition.
  • HDPE High density poly ethylene
  • HI-ZEXTM2100J High density poly ethylene
  • Laser markings are conducted by Fiber laser marker (LP-V10 of Panasonic Electric Works SUNX, Wave length: 1064 nm) using laser with an output power of 12 W and pulse cycle of 40 ps. Black or dark brown markings are made on the plastic bodies by the action of laser irradiation using a scan speed of 500 mm/s. Also, the whiteness of prepared samples are evaluated by L* value in the L*a*b* color system as defined in JIS Z 8729. The L * value is measured by using CHROMA meter (CR-400 from Minolta Co., Ltd.).
  • Table 1 shows the results of the laser marking experiments. These results indicate that the TPTO powder, TPTO coated on TiO 2 powder and TPTO coated on S1O 2 powder are highly suitable for the use as laser marking additive. The color of the plastics does not change significantly by addition of the inventive absorbers.
  • Laminate films are prepared by the gravure printing process. At first, the absorbers according to Examples 1 and 2 are mixed with gravure printing inks and dispersed by mixers. Then, the layer structure of the films is prepared as follows:
  • Laser marking layer is printed on PET film with a thickness of 100 pm by the gravure printing press (180 Lines/inch, 25pm in cell depth).
  • Step 3 Opaque colorant is printed on the laser marking layer by the gravure printing press according to Step 1.
  • Sticker film (PET film with a thickness of 100 ⁇ ⁇ ⁇ ) is heat-sealed with above layers according to Steps 1 and 2.
  • NF 102 18.00 g (NF 102: Solvent for Fine Star R/ TOYO INK MFG. CO., LTD)
  • Multilac White 31.50 g (Multilac White: TiO2 dispersion/TOYO INK MFG. CO., LTD)
  • the laser absorbers according to Examples 1 and 2 are tested at different concentrations as a powder weight concentration.
  • Laser markings are conducted by using a standard YAG laser beam with varying pulse energies (ranging from about 1 to 7 W) and frequencies (ranging from about 1 to 45 kHz). The laser is radiated on the top of non-printed PET film. Then, a black or dark brown marking is made on the printed films by the action of laser marking. Scan speed is set at 500 mm/s. Also, the whiteness of prepared samples are evaluated by L * value in the L*a * b* color system as defined in JIS Z 8729. The L * value is measured by using CHROMA meter (CR-400 from Minolta Co., Ltd.).
  • Table 2 shows the results of the laser marking experiments. These results indicate that the TPTO powder and TPTO coated on TiO 2 powder are highly suitable for the use as laser marking additive. The color of the inks does not change by addition of the inventive absorbers. Table 2: Marking Results
  • the plastic plates containing each an absorber according to Examples 1-3 are prepared.
  • 2.4 g of Example samples 1.2 g of T1O 2 pigment and 0.7 g of zinc stearate are added to 300 g of granulate PP (polypropylene, NOVATEC MA-3 of Japan Polypropylene Co., Ltd.) and dispersed therein.
  • white plastic plates 145 mm x 75mm x 2mm in thick
  • the injection is carried out under heating at 230 - 250 °C and 100 rpm as a screw rotation speed.
  • Both plates are pinched each other by using a compression tools.
  • laser-transparent part are pinched each other by using a compression tools.
  • a laser beam is irradiated over 4 cm along the width direction from laser-transparent part side as shown in Fig. 1.
  • Laser welding is conducted by Fiber laser marker (LP-V10 of Panasonic Electric Works SUNX, Wave length: 1064 nm) using laser with an output power of 15 W and pulse cycle of 50 ps.
  • the laser welding between the laser-transparent part and the laser-absorbent part could be achieved by 5 times of laser irradiation using a scan speed of 2 mm/s.
  • Table 3 shows the results of the laser welding experiments. These results indicate that the TPTO powder, TPTO coated on T1O 2 powder and TPTO coated on Si0 2 powder are highly suitable as laser welding additive. The color of the plastics does not change significantly by addition of the inventive absorbers. Table 3: Welding Results
  • the gravure inks each mixed with the absorbers according to Example 1 and Example 2 are coated on PET film with 100 pm in thick by gravure press (Screen ruling: 180 Lines/inch, Cell depth: 30 pm).
  • Fine Star R 41.00 g ( * Fine Star R: Urethane system gravure
  • NF 102 18.00 g (NF 102: Solvent for Fine Star R/ TOYO INK MFG. CO., LTD)
  • Another PET film with 100 pm in thick is piled up to the printing surface of Laser-absorbent part by using glass plates.
  • laser-transparent parts are piled up to each other by using glass plates.
  • a laser beam is irradiated over 4 cm along the width direction from laser-transparent part side.
  • Laser welding is conducted by Fiber laser marker (LP-V10 of Panasonic Electric Works SUNX, Wave length: 1064 nm) using laser with an output power of 15 W and pulse cycle of 50 ps.
  • Fiber laser marker LP-V10 of Panasonic Electric Works SUNX, Wave length: 1064 nm
  • Table 4 shows the results of the laser welding experiments. These results indicate that the TPTO powder and TPTO coated on TiO 2 powder have highly aptitude for laser welding additive.
  • the color of the plastics does not change significantly by addition of the inventive absorbers.

Abstract

La présente invention porte sur des polymères aptes au marquage par laser et au soudage par laser qui comprennent, comme absorbeur, un oxyde d'étain dopé par du tungstène et/ou du phosphore ou un substrat revêtu d'un oxyde d'étain dopé par du tungstène et/ou du phosphore.
PCT/EP2012/000066 2011-02-03 2012-01-09 Polymères aptes au marquage par laser et au soudage par laser WO2012104006A1 (fr)

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EP2955029A1 (fr) * 2014-06-13 2015-12-16 Agfa-Gevaert Matériaux pouvant être marqués au laser et documents
JP2017196896A (ja) * 2016-04-26 2017-11-02 大日本印刷株式会社 レーザ印字用多層積層フィルム並びにそれよりなる包装体及び印字体
WO2018095834A1 (fr) * 2016-11-22 2018-05-31 Merck Patent Gmbh Additif pour matériaux polymères pouvant être marqués au laser et pouvant être soudés au laser
CN108219412A (zh) * 2016-12-10 2018-06-29 衡水润通公铁路桥器材有限公司 一种smc复合型高速公路过桥管箱的制备方法
WO2019026622A1 (fr) * 2017-07-31 2019-02-07 日本ゼオン株式会社 Film stratifié
CN110494520A (zh) * 2017-06-16 2019-11-22 欧姆龙株式会社 粘接剂组合物的硬化方法以及粘接结构体的制造方法
CN112724497A (zh) * 2020-12-09 2021-04-30 金发科技股份有限公司 一种聚乙烯激光打标母粒及其制备方法和应用
WO2022173765A1 (fr) * 2021-02-09 2022-08-18 Altamira Material Solutions Matériau d'isolation de fil coloré pouvant être marqué au laser uv
WO2022200009A1 (fr) * 2021-03-25 2022-09-29 Auto-Kabel Management Gmbh Agencement d'étanchéité de câble et procédé d'établissement d'une connexion entre un câble principal et un câble de dérivation dans un agencement d'étanchéité de câble

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TWI502565B (zh) * 2014-04-28 2015-10-01 Lite On Opto Technology Changzhou Co Ltd 發光二極體顯示器殼體及其製造方法、發光二極體顯示器
EP2955029A1 (fr) * 2014-06-13 2015-12-16 Agfa-Gevaert Matériaux pouvant être marqués au laser et documents
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CN109963702B (zh) * 2016-11-22 2022-02-18 默克专利股份有限公司 用于激光可标记及激光可焊接的聚合物材料的添加剂
WO2018095834A1 (fr) * 2016-11-22 2018-05-31 Merck Patent Gmbh Additif pour matériaux polymères pouvant être marqués au laser et pouvant être soudés au laser
US11618221B2 (en) 2016-11-22 2023-04-04 Merck Patent Gmbh Additive for laser-markable and laser-weldable polymer materials
CN109963702A (zh) * 2016-11-22 2019-07-02 默克专利股份有限公司 用于激光可标记及激光可焊接的聚合物材料的添加剂
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JP2020500967A (ja) * 2016-11-22 2020-01-16 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ レーザーマーク可能なおよびレーザー溶接可能なポリマー材料のための添加物
CN108219412A (zh) * 2016-12-10 2018-06-29 衡水润通公铁路桥器材有限公司 一种smc复合型高速公路过桥管箱的制备方法
CN110494520B (zh) * 2017-06-16 2022-04-05 欧姆龙株式会社 粘接剂组合物的硬化方法以及粘接结构体的制造方法
CN110494520A (zh) * 2017-06-16 2019-11-22 欧姆龙株式会社 粘接剂组合物的硬化方法以及粘接结构体的制造方法
US11773296B2 (en) 2017-06-16 2023-10-03 Omron Corporation Method for curing adhesive composition and method for manufacturing bonded structure
WO2019026622A1 (fr) * 2017-07-31 2019-02-07 日本ゼオン株式会社 Film stratifié
CN112724497A (zh) * 2020-12-09 2021-04-30 金发科技股份有限公司 一种聚乙烯激光打标母粒及其制备方法和应用
CN112724497B (zh) * 2020-12-09 2022-08-19 金发科技股份有限公司 一种聚乙烯激光打标母粒及其制备方法和应用
WO2022173765A1 (fr) * 2021-02-09 2022-08-18 Altamira Material Solutions Matériau d'isolation de fil coloré pouvant être marqué au laser uv
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