CN1260752A - Plastic which can be laser-marked - Google Patents

Plastic which can be laser-marked Download PDF

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Publication number
CN1260752A
CN1260752A CN98806243A CN98806243A CN1260752A CN 1260752 A CN1260752 A CN 1260752A CN 98806243 A CN98806243 A CN 98806243A CN 98806243 A CN98806243 A CN 98806243A CN 1260752 A CN1260752 A CN 1260752A
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CN
China
Prior art keywords
plastics
laser
laser marking
polymer
pigment
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Granted
Application number
CN98806243A
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Chinese (zh)
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CN1169677C (en
Inventor
R·德尔普
J·索尔姆斯
G·艾德勒
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Merck Patent GmbH
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Merck Patent GmbH
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Publication of CN1169677C publication Critical patent/CN1169677C/en
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Classifications

    • 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
    • B41M5/36—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties
    • B41M5/366—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties using materials comprising a polymeric matrix containing a polymeric particulate material, e.g. hydrophobic heat coalescing particles
    • 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
    • B41M5/36—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties
    • 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

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

The invention relates to plastics which can be marked by laser, characterised in that an absorber material in the form of a plastic which is not receptive to laser treatment contains a polymer whose intrinsic properties are such that it can be marked by laser. Said polymer is present in the form of micro-ground particles with a particle size of between 0.1 and 100 mu m.

Description

The plastics of laser marking
The present invention relates to the plastics of laser marking, it is characterized in that a kind of being difficult to comprise one or more polymer as the intrinsic laser marking of absorber material with the plastics of Laser Processing, this polymer is the broken particle form of micro mist that granularity is the 0.1-100 micron.
In nearly all industrial department, on the production article, label and become more and more important.For example, the trade mark of dated date of manufacture of frequent needs, validity date, bar code, company, series number etc.At present, mainly adopt for example printing, embossing, punching press and labelled conventional method to make these marks.Yet particularly under the situation of plastics, the importance of the non-contact type of employing laser, high speed and flexible mark is growing.Even on nonplanar surface this technology also can make high speed mint-mark graphical symbol for example bar code become possibility.Because this symbol is in plastic article the inside, thereby it is lasting with anti abrasive.
Prove so far, many plastics, for example polyethylene (PE), polypropylene (PP), polyamide (PA), polymethyl methacrylate (PMMA), polyformaldehyde (POM), polyurethane (PUR), polyester are difficult to or even may adopt laser to mark.Emission wavelength is the CO of 10.6 microns infrared region light 2Laser instrument, even under very high output level, only on polyolefin, produce faint, mark easy to identify hardly, this be since under above-mentioned wavelength the absorption coefficient of plastics to be processed be not high enough to cause due to the color change of polymeric material.These plastics must reflect or transmission laser by halves, because, if so just can not interact.Yet, must not be strong absorbent also, because these plastics can evaporate and only stay engraving (engraving) in this case.Absorb laser beam, thereby cause chemical constitution and the used Wavelength of Laser that depends on these plastics with the interaction of material.In many cases, need to add suitable additive, absorbent for example is so that make plastics become that laser can carve.
The pearl light luster pigment of marking and using for laser is disclosed in the article " pearl light luster pigment-characteristic and function (Pearl LustrePigments-Characteristics and Functional Effects) " of the 2nd the 2nd phase of volume of " special-purpose chemicals (Speciality chemicals) " May nineteen eighty-two.Yet pearl light luster pigment has the shortcoming that the plastics color characteristics is changed, this normally a kind of undesirable influence.
DE-A 29 36 926 discloses by adding in plastics and a kind ofly has been exposed to the filler that can fade under the high-energy radiation for example carbon black or graphite can realize using the laser beam marking polymeric material.
But EP 0 190 997 A have prepared the molding compounds of the laser mint-mark that comprises PE or PS by add at least a inorganic pigment in the organic material of HMW.
In EP 0 330 869, in PBT and PET, add TiO 2And carbon black.Under light background, the mint-mark literal is dark-coloured.Learn from EP 0 485 181,, used carbon black and/or graphite as absorbent about the laser labelling of polyester.
Yet, become known for the filler that laser marks shortcoming is arranged, they or for good and all make the coloring plastic for the treatment of mint-mark, thereby making is the enough contrasts of laser beam marking shortage of dark-coloured writing usually under light background, it is definition, or under kaolinic situation for example, mark is very fuzzy, and only just becomes when using a large amount of additives and see clearly easily.
DE 195 36 047 has narrated the use Merlon, and this Merlon itself is difficult to use laser labelling, and this is because in the polymeric matrix of polyalkylene terephthalates due to its impalpable structure.By absorbing the energy of laser, can obtain dark-coloured character under the light background in the polymeric matrix of polyalkylene terephthalates.
Yet, except that above-mentioned plastics, also have some not add the polymer that additive just can have darkness and big contrast by laser labelling.The example of this base polymer comprise PET, butadiene-styrene (ABS), polystyrene, polyphenylene oxide (PPO), liquid crystal polymer (LCP), polyphenylene sulfide, polyarylate, polyarylene sulfide, polyarylsufone, PAEK, and composition thereof.
Therefore, the objective of the invention is to find out the plastics of some laser markings, these plastics can obtain laser marking with high contrast when being subjected to the laser irradiation.In this case, must have very shallow, neutral inherent colour and must have the characteristic of precolor plastics to be marked maybe must be to few influence of these characteristics or not influence for filler or fruitful absorbent.
Be surprised to find that, be difficult to in the plastics of Laser Processing, just this plastics of mark very effectively if for example one of polymer of above-mentioned intrinsic laser marking is added to the form of meticulous distribution.Like this, just the intrinsic mark of this polymer can be passed to the plastics that almost do not have this specific character.After the laser irradiation, plastics that mixed like this even under low laser intensity, also can demonstrate the mark of high-contrast and sharp outline.
Therefore, the invention provides the plastics of some laser markings, but it is characterized in that some are difficult to comprise the polymer that one or more granularities are the intrinsic mark of 0.1-100 micron with the plastics of Laser Processing.
By add content for the 0.1-10% (weight) of this plastics system, preferred 0.1-5% (weight), particularly 0.1-2% (weight) but micro mist polymer broken, intrinsic mark can obtain laser marking with high contrast as absorbent.Yet, but the content of the polymer of intrinsic mark depends on used plastics system and employed laser in these plastics.
Suitable polymer blend or mixture of polymers all are the plastics of knowing that are easy to Laser Processing, for example PET, ABS, polystyrene, PPO, polyphenylene sulfide, PPSU, poly-imino group sulfone and LCP.
Have＞300 ℃ the broken thermoplastic of high-melting-point micro mist is suitable especially.The lucid and lively property of this mark profile depends on the granularity of the broken polymer of micro mist especially.The granularity of preferred polymers is 0.1-50 micron, particularly 1-20 micron.
If but the polymer of intrinsic mark comprises for example filler of photochromic pigment, for example conducting pigment and/or special effect pigment are as other absorbent, and so resulting mark is certain to be affected.Add another kind of absorbent and can strengthen contrast as used plastics system function.The photochromic pigment amount of adding must be between 0.1-90%.
Shi Yi photochromic pigment is a filler especially, for example TiO 2And SiO 2And phyllosilicate.Suitable silicate platelets is the mica or the muscovite of light color particularly.Certainly, also can use other natural micas, for example phlogopite and biotite, synthetic mica, talcum thin slice and glass flake.Special effect pigment refers to well-known gloss, metal and pearl light luster pigment, Mearl for example, the pigment that Eckart-Werken and Merck KGaA company sell.The example of suitable conducting pigment is that Merck KGaA is with trade name Minatec The pigment of selling.These pigment are to comprise the sheet TiO of tin oxide/antimony oxide skin as conductive coating 2/ pigments, mica.Other suitable photochromic pigments are for example oxide, hydroxide, sulfide, sulfate and phosphate of copper, bismuth, tin, zinc, silver, calcium halophosphate activated by antimony andmanganese, iron, nickel and chromium of some metals.What should be mentioned in that especially is the situation that adopts algaroth, bismoclite and alkali formula phosphoric acid hydroxyl two bronze medals (II).In this case, particularly preferably be by with blue cupric phosphate (II) (Cu 3(PO 4) 23H 2O) be heated to the product of 100-200 ℃ of formation, this product has experimental chemistry formula: 4CuOP 2O 5H 2O or Cu 3(PO 4) 2Cu (OH) 2The phosphate of the copper that other are suitable is 6CuOP 2O 53H 2O, Cu 3(PO 4) 23Cu (OH) 2, 5CuOP 2O 53H 2O, Cu 3(PO 4) 22Cu (OH) 2H 2O, 4CuOP 2O 5, 4CuOP 2O 53H 2O, 4CuOP 2O 51.5H 2O, 4CuOP 2O 51.2H 2O.
But, laser marking is improved if except the polymer of intrinsic mark, one or more above-mentioned photochromic pigments are added in these plastics as another kind of component.In this case, all absorbents in these plastics and the weight ratio of the broken polymer of micro mist, total amount should not surpass 10% (weight) of this plastics system.These plastics preferably contain the photochromic pigment of 0-5% (weight), particularly 0-1% (weight).In this case, the ratio of photochromic pigment and the broken mixed with polymers of micro mist without limits.
Also can add color pigment in the plastics that are difficult to Laser Processing, this pigment can make color do any variation, can positively keep laser labelling simultaneously.
Preferably photochromic pigment and/or color pigment are added with polymer, also be fine in principle though add respectively.Also different photochromic pigment mixtures can be added in these plastics.
The preferred wavelength that adopts is generally 150nm-10, and the high-energy radiation of 600nm, particularly 150nm-1100nm carries out mark.What can mention here is, for example CO 2Laser instrument (10,600nm), Nd:YAG laser instrument (1064nm or 532nm) or pulse UV laser instrument (excimer laser).Particularly preferred Nd:YAG laser instrument (1064nm and 532nm) and the CO of being to use 2Laser instrument (10,600nm).The energy density of used laser instrument is generally 0.3mJ/cm 2-50J/cm 2, preferred 0.3mJ/cm 2-10J/cm 2
As Ullmann, the 15th volume is below the 457th page, described in Verlag VCH or the SaechtlingKunststoff Taschenbuch, the plastics that can only carry out laser labelling with very big difficulty that all are known just can be used for laser and mark by adding polymer of the present invention.The example of these class plastics is thermosetting plastics, polyethylene (PE-HD, PE-LD, PE-LLD), polypropylene (PP), polyester, polyacetals, polyamide (PA), polyurethane (PUR), polybutylene terephthalate, polymethyl methacrylate (PMMA), Pioloform, polyvinyl acetal, polystyrene, butadiene-styrene (ABS), acrylonitrile-styrene-acrylic ester (ASA) and copolymer and/or its mixture.Particularly, polyolefin, polyurethane, polyformaldehyde and polyamide are because low processing method of their mechanical performance, cost and relatively poor laser marking thereof all are suitable for of the present invention polymer-doped.
To can adopt the known method that is used for pigment and filler to carry out in the fine polymer adding plastics.Thereafter, painted plastics are out of shape under the effect of heat.When but the polymer of selecting intrinsic mark grinds, must remember after adding, will keep its grain structure; In other words, this particle should not be dissolved in melt, but also must not fusion.This can adapt by the fusion range that suitably makes this plastics system and the broken polymer of micro mist and realize.
When fine polymer is added plastic grain, if desired, can be added under the operating condition is the coupling agent of temperature stabilization, organic solvent, stabilizing agent, fluorescent whitening agent, color pigment, dyestuff, filler, reinforcing agent, fire-proof additive, antistatic additive and/or the surfactant of polymer-compatible.Except normally used auxiliary agent, other additive (not proposing herein) can be added in the plastics.Yet other additives are present in the existing plastics system and can exert an influence to the mark result.
Usually with in the blender that it is suitable that plastic grain is packed into, it is wetting with any additive, add fine polymer then, and they are mixed therein with preparation plastic grain/polymeric blends.Then, can be with the mixture directly processing in extruder or injection moulding machine that obtains like this.The moulding article that forms in process presents the distribution of unusual homogeneous polymer or polymeric blends.At last, preferably adopt the Nd:YAG laser instrument to carry out laser labelling.
By sample is introduced pulse laser, the beam path of preferred Nd:YAG laser instrument carries out laser beam marking.Also can adopt CO 2Laser instrument or excimer laser carry out mint-mark.Yet the laser instrument that to adopt its wave-length coverage can make intrinsic laser marking polymer high absorption be the other types of characteristic also can obtain required result.The resulting shade of color and the degree of depth are decided by laser parameters, for example radiated time and radiation power output.The power output of used laser instrument depends on specific purposes, and can be by skilled staff by the rules decision under individual other situation.
The plastics that mixed according to the present invention can be used for the department that all have used conventional printing process mint-mark plastics so far.For example, plastic molded product of the present invention can be used for electrical equipment, electronics and auto industry.For example, the function part in shell, pipeline, keycap, transcription product (transcripts) or heating, ventilation and the cooling department that constitutes by plastics of the present invention or the labelling and the mint-mark of switch, plug, bar and handle, even on unapproachable position, all can mark by laser.Because its content of beary metal is low, plastics system of the present invention can also be used for the packing of food department or toy department.On the packing these are marked at anti-wiping and scratch, in sterilization process thereafter stability and in labeling process with hygiene on pure mode mint-mark all be conspicuous.For reusable system, can be on the packaging with the mint-mark enduringly of complete label design.Another important applied field of laser beam marking is identity card and the plastic label that is used for animal individual identification: so-called domestic animal label or earmark.Therefore, plastic products or the moulding article that is made of plastics of the present invention can be used laser labelling.
The following example be used for illustrating of the present invention, still, unrestricted extremely to the present invention.1 part of 199 parts of polypropylene of EXAMPLE Example (Stamylan PPH 10 derives from DSM) are ground to granularity less than 25 microns polyphenylene sulfide
These components are physically mixed and by the injection moulding machine homogenizing be shaped to form thin slice.With the Nd:YAG laser instrument 532 and the 1064nm wavelength under mint-mark, in very wide setting range, demonstrate high-contrast density bullet with smooth surface.0.5 part of 299.5 parts of polypropylene of embodiment (Stamylan PPH 10) are ground to granularity less than 10 microns PPSU
These components are mixed and by the injection moulding machine homogenizing be shaped to form platelet.With the mint-mark of Nd:YAG laser instrument, in very wide setting range, demonstrate high-contrast density bullet with smooth surface.1 part of 399 parts of polyamide 6 of embodiment (Ultramid B3K derives from BASF) are ground to granularity less than 15 microns poly-imino group sulfone
These components are mixed and by the injection moulding machine homogenizing be shaped to form thin slice.With the mint-mark of Nd:YAG laser instrument, in very wide setting range, demonstrate high-contrast aterrimus mark with smooth surface.0.4 part of 499.6 parts of polyamide 6 of embodiment (Ultramid B3K) are ground to granularity less than 10 microns polyphenylene sulfide
These components are mixed and by the injection moulding machine homogenizing be shaped to form thin slice.With the mint-mark of Nd:YAG laser instrument, in very wide setting range, demonstrate high-contrast density bullet with smooth surface.1 part of 599 parts of polyformaldehyde of embodiment (Delrin derives from Du Pont) are ground to granularity less than 5 microns polyphenylene sulfide
These components are mixed and by the injection moulding machine homogenizing be shaped to form platelet.With the mint-mark of Nd:YAG laser instrument, in very wide setting range, demonstrate high-contrast density bullet with smooth surface.1 part of 699 parts of unsaturated polyester resin of embodiment (Palatal derives from BASF) are ground to granularity less than 10 microns polyphenylene sulfide
With polyphenylene sulfide by adding in the liquid polyester casting resin with stirring.After adding promoter (cobalt octoate) and curing agent (cyclohexanone peroxide), pour this mixture into mould.After solidifying, obtain a kind of moulding article:, can provide the high-contrast density bullet with the mint-mark of Nd:YAG laser instrument.Embodiment 7
With 99 parts of polysulfones (Ultrason derives from BASF) and 1 part of mica chemical combination in extruder.With the little granularity that is crushed to of this compound less than 10 microns.0.5% powder that obtains is like this added among the PMMA.This mixture is processed in extruder to produce thin slice: 532 and 1, mint-mark under the wavelength of 064nm can provide black and mark high-contrast with the Nd:YAG laser instrument.Embodiment 8
The method that adopts embodiment 7 is with 96 parts of polyphenylene sulfides and 4 parts of alkali formula cupric phosphate chemical combination.The micro mist comminuted powder of 0.4% this mixture is just added in the plastics of common non-laser marking, and these plastics are (b) (c) (e) (f) polyformaldehyde (POM) of polyurethane (PU) of polyamide (PA) (d) polymethyl methacrylate (PMMA) of polypropylene (PP) of (a) polyethylene (PE) for example
Adopt the mint-mark of Nd:YAG laser instrument, can provide the aterrimus with sharp outline, the mark of high-contrast.

Claims (12)

1. the plastics of laser marking is characterized in that a kind of plastics that are difficult to laser labelling comprise the polymer as the intrinsic laser marking of absorber material, and this polymer is the broken particle form of micro mist that granularity is the 0.1-100 micron.
2. according to the plastics of the laser marking of claim 1, it is characterized in that this absorber material is resistant to elevated temperatures plastics.
3. according to the plastics of the laser marking of claim 1 or 2, it is characterized in that this absorber material is polyphenylene sulfide, polysulfones, polyarylate, polyimides, liquid crystal polymer or its mixture.
4. according to the plastics of each laser marking among the claim 1-3, it is characterized in that the 0.1-10% (weight) of the ratio of this absorber material for this plastics system.
5. according to the plastics of each laser marking among the claim 1-4, but it is characterized in that the grain structure of the polymer of intrinsic mark is remained in these plastics.
6. according to the plastics of each laser marking among the claim 1-5, it is characterized in that this absorber material comprises that also one or more photochromic pigments are as other absorbent.
7. according to the plastics of the laser marking of claim 6, it is characterized in that this photochromic pigment is natural or synthetic mica, cupric phosphate, special effect pigment, conducting pigment, metal nitrate, metal sulfate, metal sulfide or metal oxide.
8. according to the plastics of each laser marking among the claim 1-7, it is characterized in that the 0-5% (weight) of the ratio of this photochromic pigment in plastics for this plastics system.
9. according to the plastics of each laser marking among the claim 1-8, it is characterized in that these plastics that are difficult to Laser Processing are polyethylene, polypropylene, polyamide, polyformaldehyde, polyester, polymethyl methacrylate, polyurethane or its copolymer.
10. according to the plastics of each laser marking among the claim 1-9, it is characterized in that they also comprise color pigment.
11. according to the plastics of the laser marking of claim 1 as the application of producing the moulding article material of marking by laser.
12. the moulding article that constitutes by the laser marking plastics of claim 1.
CNB988062437A 1997-06-19 1998-05-30 Plastic which can be laser-marked Expired - Fee Related CN1169677C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19726136A DE19726136A1 (en) 1997-06-19 1997-06-19 Laser-markable plastics
DE19726136.1 1997-06-19

Publications (2)

Publication Number Publication Date
CN1260752A true CN1260752A (en) 2000-07-19
CN1169677C CN1169677C (en) 2004-10-06

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EP (1) EP0991523B1 (en)
JP (1) JP2002504947A (en)
KR (1) KR20010013893A (en)
CN (1) CN1169677C (en)
AU (1) AU7917898A (en)
BR (1) BR9810065A (en)
CA (1) CA2294235A1 (en)
DE (3) DE19726136A1 (en)
ES (1) ES2183381T3 (en)
TW (1) TW589339B (en)
WO (1) WO1998058805A1 (en)

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AU7917898A (en) 1999-01-04
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CA2294235A1 (en) 1998-12-30
WO1998058805A1 (en) 1998-12-30

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