CN1938161A - Sealing of plastic inscriptions - Google Patents
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- CN1938161A CN1938161A CNA2005800101497A CN200580010149A CN1938161A CN 1938161 A CN1938161 A CN 1938161A CN A2005800101497 A CNA2005800101497 A CN A2005800101497A CN 200580010149 A CN200580010149 A CN 200580010149A CN 1938161 A CN1938161 A CN 1938161A
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- engraving
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- layer
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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
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Abstract
The present invention relates to the sealing of plastic inscriptions that have been, preferably indirectly, produced by means of a laser on the plastic surface.
Description
Technical field
The present invention relates to utilizing laser instrument on frosting the preferably sealing of the plastic inscriptions that produces indirectly.
Background technology
Utilize the laser beam of various wavelength, for good and all mark and engrave material and product.
Term ＂ engraves the process that tags that ＂ is intended to represent utilize any kind of laser hereinafter, promptly engraves mark, coding etc.
The ＂ color laser engraves ＂ and is used to represent to use all colours and achromatic pigment or dyestuff (all colors comprise black, white and all tones of gray) engraving plastics.
Mark and/or engrave by the effect of laser energy is undertaken
Material from (directly engrave) on one's body or
2. engraving on the medium, this medium is transferred on the material that will engrave from the outside and (engraves indirectly).
Therefore, in the method for engraving 1) in, metal, for example, irradiation reflects various temper colors to laser, and timber becomes dead color (carbonization) in irradiation area, and plastics, and for example, PVC has shallow or dark-coloured variable color (foaming, carbonization), and this depends on coloring plastic.
In plastics, these effects often are enhanced by adding laser-sensitive pigment or cause.Shortcoming generally is, only can realize that ＂ color ＂ is white and black or various grey and bleaching tone, and laser-sensitive pigment must be added into whole plastic material in masterbatch.
In the method for engraving 2) in, to engrave medium be to contact with the material that will engrave with this if hit with the laser beam of wavelength (for example IR laser) if having suitable energy, engraves medium so and be transferred on the material and be fixed on it.Material can use suitable colour and achromatic pigment or dye mixture, suspension, and paste or laser film or band engrave indirectly.Like this, the colour of high-contrast and black/white engrave becomes possibility.The amount that engraves actual required laser-sensitive pigment this significantly less than, for example, the situation (engraving method 1) that masterbatch adds, or in some occasion, do not need.
The medium that engraves that comprises frit or frit precursor and laser energy absorption agent is well known to a person skilled in the art, adds inorganic and organic pigment according to required color in described medium, metal oxide, organic metal material or metal dust.Such technology for example is described in WO 99/16625, and US 6,238,847, and US 6,313, and 436 and WO 99/25562.
Pigment and/or dye mixture are being applied directly to and will are for example passing through to spray, brush, disseminate, electrostatic charging etc. and on the medium that engraves, or be administered to support base material, as band, on film or the analog after, use essential laser energy (1-30W power output, cw pattern) or laser energy density (100W/cm
2-3GW/cm
2, pulse mode) shine and engrave.Like this, can engrave glass, pottery, metal, stone, plastics and composite.This method that engraves for example is disclosed in WO 03/035411, WO 03/080334 and WO 03/080335.
EP 1279517 A1 and DE 19942316 A1 have described the laser-sensitive mixture of the color laser mark that is particularly useful for plastics and the glass pigment that engraves and plastics granula.
The major defect that the indirect laser of the plastics that produce according to these technologies engraves is to engrave local pigment or dye strength very high in the zone, and this often causes unintelligible the engraving of bluring, and it is frosting afterwards (effloresce) or bleeding also.Under the situation of using organic pigment or dyestuff, situation is especially true.
Although 〉=0.5% (at organic pigment) and 〉=the maximum pigment concentration of 2% (at inorganic pigment) is used for the conventional painted of plastics, for example, according to WO 99/16625 in addition the pigment concentration in the plastic areas that engraves of laser far above 20%.
Decide according to plastics that engrave and later serviceability temperature, this painted excessively pigment or dye migration of causing is to frosting, so-called frosting.
If contact with other material and excessive pigment or dyestuff are transferred in this process in these materials if engrave, then use the term bleeding.
This crosses the painted feasible cleaning and the drying steps that need carry out in addition subsequently, and this is undesirable or unacceptable technically, especially for the online production technology that engraves with production as final processing step.
In addition, engrave in use, for example because ambient influnence etc. and bleeding or frosting or fade.
For some occasion, as food, drug packages, toy, the engraving of medical product etc., so bleeding or engraving at all of frosting can not be used.
Summary of the invention
Therefore purpose of the present invention is to realize having the high rim definition and the laser non-blooming, not bleeding of the plastics of the high patience of ambient influnence is engraved, and wherein laser engraves on frosting, preferably produces indirectly.
Astoundingly, have been found that using laser instrument to carry out the frosting of coloured plastics that engrave or bleeding engraves the zone by sealing in engraving operating process and be inhibited.Sealing use preferred glass transition temperature 〉=90 ℃, especially the hyaline layer of 100 to 120 ℃ polymer carries out.This polymeric layer can be used as individual course and uses or surround and therefore seal colouring agent.
The present invention relates to a kind of with plastics the permanent and coloured method that engraves in wearability ground, it is characterized in that colouring agent and/or absorbent (laser-sensitive pigment) bleeding or the frosting in the plastic inscriptions zone engraves the zone and prevent by engraving in technology self process or sealing this laser with transparent polymer immediately after this.
Compared with prior art, the salient point of the method according to this invention is following characteristics:
-pigment or dyestuff defile and/or later bleeding/frosting is prevented
-engrave in reality that undesirable cleaning is unnecessary after the technology
-the color fastness that engraves in the use afterwards is guaranteed.
The polymeric layer that is used to seal can be administered to and engrave, and engraves with laser in this first step in one-step method and carries out, or carry out in two-step method.Coating systems shown in Fig. 1-12 has been proved suitable especially.
Use the plastic inscriptions of laser instrument preferably to be undertaken, for example be described in WO99/16625 or unpub DE 10352857 by engraving indirectly.Plastics utilize laser energy to be engraved by coloured by engraving medium and introducing in the plastic basis material.Engraving medium peels off and joins to enduringly subsequently equally by on the frosting warm and therefore local softening from support membrane.
One-step method
Fig. 1-6 diagram has shown the one-step method in the method according to this invention.In Fig. 1, coating systems is by the patience supporting layer 1 that to laser is the transparency, laser-sensitive energy absorber layer 2, and separation layer 3, independent sealant 4 and engrave medium 5 compositions at last, the latter comprises pigment and/or dyestuff.The side medium that engraves of this coating systems closely contacts with the plastics that will engrave.
Alternatively, the available sealed polymer layer of colouring agent self applies or is embedded in (Fig. 2,4,6) in the polymeric matrix 6.
Energy absorber can be introduced supporting layer (layer 7 is at Fig. 3, in 4) equally.
In this one-step method, the plastic inscriptions of employing sealing uses suitable laser instrument and produces.Be used for the required energy of this purpose and be transferred to separation layer 3 by energy absorber layer 2,7, the latter softens and therefore sealant 4 is transferred on the plastics with engraving medium 5 or sealing colouring agent 6.Laser energy must this selection make plastics engrave in the zone softening equally and formation with sealant 4 or seal the bonding by force of colouring agent 6.
In some occasion, as in self-absorption agent plastics (for example dark coloured plastics, plastics are to the good affinity of sealed polymer), it is successful engraving, even without additional absorbent (Fig. 5,6).
Two-step method
In two-step method, engrave the sealing of operating with subsequently and separate.In first step, generation engraves.This can utilize the layer structure shown in Fig. 7 to 10 and carry out.
Energy absorber is administered to laser for (Fig. 7) on the stable support membrane 1 of the transparency or introduce in the support membrane 7 (Fig. 8) or be unnecessary (Fig. 9) under the situation of self-absorption agent plastics as individual course 2, engrave medium 5 as individual course (Fig. 7-9) or as forms by the mixture that engraves medium 5 and energy absorber 2 layers 8 and use (Figure 10).
Utilize suitable laser instrument, must energy be transferred to and engrave on the medium 5 and be transferred on the plastics or directly be transferred on the plastics by layer 8 by energy absorber layer 2,7.Engraving medium 5 is transferred on the softening plastics and obtains plastic inscriptions.
In second step, sealing utilizes layer structure (Figure 11,12) and produces, and this structure is by the patience supporting layer 1 that to laser is the transparency, laser-sensitive energy absorber layer (2 or be introduced into 7), and separation layer 3 and sealant 4 are formed.
Utilize suitable laser instrument, essential energy is transferred on the separation layer 3 by energy absorber layer 2,7, and the latter softens and therefore sealant 4 is transferred on the plastics.Laser energy must select to make plastics softening again and form bonding by force to sealant in engraving the zone.
The material that is applicable to supporting layer 1 is that the laser in the described wave-length coverage is the transparency and/or translucence and all material that is not compromised or destroys because of the interaction with laser in the ideal case.
Suitable material for example is, glass and plastics, and they are in the ideal case with film, and the form of band or sheet material is used and is preferably had layer thickness 5-250 μ m, especially 10-150 μ m and preferred especially especially 15-75 μ m.
Suitable plastic is preferably thermoplastic.Especially, plastics are by polyester, Merlon, polyimides, polyacetals, polyethylene, polypropylene, polyamide, polyester-ester, polyether ester, polyphenylene ether, polybutylene terephthalate (PBT), PETG, polymethyl methacrylate, Pioloform, polyvinyl acetal, polyvinyl chloride, polystyrene, acrylonitrile-butadiene-styrene (ABS) (ABS), acrylonitrile-styrene-acrylic ester (ASA), polyether sulfone and polyether-ketone and copolymer and/or its mixture are formed.
In described plastics, particularly preferably be polyester, PETG, polyethylene, polypropylene, Merlon and polyimides.
Especially for three-dimensional plastic parts or surperficial engraving and mark, by PETG, the amorphous plastics support membrane that do not stretch that polyester and polyamide are made is suitable.
Operable energy absorber is to absorb laser energy and it is changed into all materials of heat energy in described wave-length coverage on appropriate level.
The energy absorber that is applicable to mark is preferably based on carbon, carbon black, and anthracene, IR-absorbability colouring agent, for example, and perylene/rylenes, pentaerythrite, phosphate, for example, and hydroxide phosphoric acid copper, sulfide, for example, and molybdenum bisuphide, oxide, for example, antimony oxide (III), Fe
2O
3And TiO
2, bismoclite, sheet form, especially transparent or semitransparent base material comprises, for example, phyllosilicate, for example, synthetic or natural mica, talcum, kaolin, glass flake, SiO
2Thin slice or synthetic no support slice.Also suitable is the metal oxide of sheet form, for example, and the iron oxide of sheet form, aluminium oxide, titanium dioxide, silica, LCP (liquid crystal polymer), holographic pigment, conducting pigment or coating graphite flake.
Operable sheet form pigment also has metal dust, and they can be uncoated or be covered by one or more layers metal oxide layer; For example preferred Al, Cu, Cr, Fe, Au, Ag and steel thin slice.If corrosion-prone sheet metal, for example, Al, Fe or steel thin slice use with uncoated form, and then they preferably scribble the protection polymeric layer.
Except the base material of sheet form, also can adopt spherical pigment, for example comprise Al, Cu, Cr, Fe, Au, Ag and/or Fe.
Especially preferred base material is the splitting that scribbles one or more metal oxides.Metal oxide is colourless high refractive index metal oxide as used herein, as, especially, titanium dioxide, antimony oxide (III), zinc oxide, tin oxide and/or zirconium dioxide, and nonferrous metal oxides, for example, chromium oxide, nickel oxide, cupric oxide, cobalt oxide and especially iron oxide (Fe
2O
3, Fe
3O
4).Used energy absorber is antimony oxide (III) especially preferably, and use combines separately or with tin oxide.
These base materials are known and in most of the cases can be for example with trade name Iridin
Lazerflair is available from Merck KGaA, and/or can make by standard method well known by persons skilled in the art.
Pigment based on transparent or semitransparent sheet form base material for example is described in Deutsche Bundespatent and patent application 1467468,1959998,2009566,2214454,2215191,2244298,2313331,2522572,3137808,3137809,3151343,3151354,3151355,3211602,3235017,3842330 and 4441223.
Apply SiO
2Thin slice for example is disclosed in WO 93/08237 (wet chemistry coating) and DE-A 19,614 637 (CVD technology).
Multi-layer pigments based on phyllosilicate for example is disclosed in DE-A 196 18 569, DE-A 19,638 708, DE-A 197 07 806 and DE-A 198 03 550.Especially suitable is the multi-layer pigments with following structure:
Mica+TiO
2+ SiO
2+ TiO
2
Mica+TiO
2+ SiO
2+ TiO
2/ Fe
2O
3
Mica+TiO
2+ SiO
2+ (Sn, Sb) O
2
SiO
2Thin slice+TiO
2+ SiO
2+ TiO
2
Especially preferred laser absorption material is an anthracene, perylene/rylenes, three and four rylene tetracarboxylic imidodicarbonic diamide for example, pentaerythrite, hydroxide phosphoric acid copper, molybdenum bisuphide, antimony oxide (III), bismoclite, carbon, carbon black, antimony, Sn (Sb) O
2, TiO
2, silicate, SiO
2Thin slice, the mica of metal oxide-coated and/or SiO
2Thin slice, conducting pigment, sulfide, phosphate, BiOCl, or its mixture.
Energy absorber also can be the mixture of two or more components.According to the present invention, it is administered on the supporter 1 as layer 2 (Fig. 1,2,5,8) or is introduced into supporting layer (Fig. 3,4,6,9), and ratio is 2-50 weight %.
If these energy absorbers have been used as additive or have been used for coloring plastic, in engraving band, there be not engraving of energy absorber to carry out under 6 and 9 the corresponding condition according to Fig. 5.
Organic and inorganic colourant all is applicable to and engraves.Suitable colouring agent be well known by persons skilled in the art in laser irradiation process Undec all colouring agents.Colouring agent also can be the mixture of two or more materials.The ratio of colouring agent in engraving medium is preferably 0.1-30 weight %, and especially 0.2-20 weight % and especially preferably 0.5-10 weight % are based on the gross weight that engraves medium (colouring agent+binding agent+solvent+optional polymer component).
Suitable colouring agent is all organic and inorganic dyestuff and a pigment well known by persons skilled in the art.Especially suitable is AZOpigments and dyestuff, for example, and monoazo and diazo pigment and dyestuff, many ring pigment and dyestuff, for example, Naphtocyclinon (perinones) perylene, anthraquinone, flavanthrone, isoindolinone, pyranthrone, anthrapyrimidine, quinacridone, thioindigo, two piperazines, indanthrone (indanthronones), diketopyrrolopyrrolecocrystals, quinoline promise phthalein ketone, pigment and dyestuff that metal cooperates, for example, phthalocyanine, azo, azomethine, dioxime and isoindolinone complex, metallic pigments, oxide and oxide hydroxide pigment, oxide mixed dyes of Fe, slaine pigment, for example, chromate and chromate-molybdate mixed dyes of Fe, carbonate pigment, sulfide and sulfide-selenium pigment, complex-pigment salt and water glass color.
In described colouring agent, particularly preferably be copper phthalocyanine, two piperazines, anthraquinone, monoazo and diazo pigment, diketopyrrolopyrrolecocrystals encircles pigment more, anthrapyrimidine, quinacridone, quinoline promise phthalein ketone, Naphtocyclinon ， perylene, acridine, azo dyes, phthalocyanine, xanthene, azophenlyene, colored oxide and oxide hydroxide pigment, oxide mixed dyes of Fe, sulfide and sulfide-selenium pigment, carbonate pigment, chromate and chromate-molybdate mixed dyes of Fe, complex-pigment salt and water glass color.
The colouring agent of two-step method (Figure 10)/absorbent ratio is preferably 10: 1-1: 10, especially 5: 1-1: 5, especially preferred 4: 1-1: 4.
In order to improve adhesiveness, the polymers compositions adding can be engraved in the medium.It is preferably by low melting point polymer, for example, and polyester, Merlon, polyolefin, polystyrene, polyvinyl chloride, polyimides, polyamide, the copolymer of polyacetals and described polymer, and vinyl chloride, the terpolymer of dicarboxylic ester and vinyl acetate or hydroxyl or methyl acrylate, or its mixture is formed.Polymers compositions may be dissolved in and engraves in the medium or exist with dissolved form not as fine powder.Particle size is preferably 10nm-100 μ m, especially 100nm-50 μ m and especially preferred 500nm-5 μ m.Also can adopt the not mixture of polymer beads of the same race, wherein particle size can be different with chemical group Chengdu.
Engrave medium and preferably comprise 10-50 weight %, especially 15-40 weight % and the especially preferably polymer of 20-35 weight % are based on the gross weight of the colorant paste that comprises colouring agent+binding agent+solvent+polymers compositions.
Polymers compositions/colouring agent ratio is preferably 200: 1-1: 1, especially 100: 1-2: 1, especially preferred 70: 1-3: 1.
As other component, engrave medium and comprise binding agent.Binding agent makes that engraving layer evenly is administered to ideally on the glass of film, band or sheet-form or plastics and so on the material.
All binding agents well known by persons skilled in the art are suitable, cellulose especially, cellulose derivative, for example, celluloid, cellulose acetate, hydrolysis/polyvinyl alcohol of acetalization, PVP, polyolefin, for example polypropylene and its derivative, polyacrylate, and the copolymer of ethylene/vinyl acrylate, polyvinyl butyral resin, epoxy resin, polyester, polyisobutene and polyamide.
Any additives that added promote to engrave tight in the process of engraving of medium 5 and plastics contacts and between engraving medium 5 and sealing 4 generation bonding by force.Additive is preferably by polyvinyl acetate, the polymer of methyl methacrylate, ethyl ester and butyl ester and copolymer, and unsaturated polyester resin, or its mixture is formed.
The layer thickness of multilayer system is preferably:
Supporting layer 1,7:5-250 μ m, preferred 15-75 μ m
Energy absorber layer 2:0.5-150 μ m, preferred 1.0-120 μ m
Separation layer 3:0.1-1 μ m, preferred 0.2-0.9 μ m
Sealant 4:1-10 μ m, preferred 4-9 μ m
Comprise the layer 8:10-150 μ m that engraves medium and energy absorber, preferred 15-100 μ m
The layer thickness of multilayer system should not surpass gross thickness 10-350 μ m, and preferred 10-250 μ m and especially 12-100 μ m are because can not guarantee sharp-edged mark of mark and sealing completely under the blocked up situation of coating systems.
Described multilayer system is placed on the plastics and utilizes the necessary pressure that contacts, for example mechanically, utilize vacuum or closely contact by the heat-activatable additive that optionally adds with the zone that will engrave.Engrave and use suitable laser instrument to be undertaken by beam deflection method or mask method.
According to the type of plastics, all laser instruments well known by persons skilled in the art all can be used for engraving.Laser parameter depends on specific occasions and can be determined by those skilled in the art easily.
Use engraving of laser by sample being introduced laser instrument, preferred Nd:YAG or Nd:YVO
4The ray path of laser instrument and carrying out.In addition, can for example use excimer laser to engrave by mask method.But required result also can use the laser of other common type with the wavelength in the high absorbing area territory of used laser absorption material and realize.Irradiation power and the used plastics system of gained mark by irradiation time (or umber of pulse, under the situation of pulse laser) and laser instrument is definite.The power of used laser instrument depends on specific occasions and can easily be determined by those skilled in the art under every kind of single situation.
Used laser instrument generally has wavelength 157nm to 10.6 μ m, preferred 532nm to 10.6 μ m.Can for example mention CO at this
2Laser instrument (10.6 μ m) and Nd:YAG laser instrument (be respectively 1064 and 532nm) or pulse UV laser instrument.Excimer laser has following wavelength: F
2Excimer laser (157nm), ArF excimer laser (193nm), KrCl excimer laser (222nm), KrF excimer laser (248nm), XeCl excimer laser (308nm), XeF excimer laser (351nm) has the frequency polyploidization Nd:YAG laser instrument of wavelength 355nm (frequency tripling) or 265nm (four times of changes of frequency).The particularly preferred Nd:YAG of being to use laser instrument (be respectively 1064 and 532nm) and CO
2Laser instrument.The energy density of used laser instrument generally is 0.3mJ/cm
2To 50J/cm
2, preferred 0.3mJ/cm
2To 10J/cm
2
Engrave preferred use in various optical maser wavelengths, 1064nm, the Nd:YAG laser instrument under 532nm or the 808-980nm, Nd:VO
4Laser instrument or CO
2Laser instrument carries out.The process of tagging can be carried out according to cw (continuous wave) pattern with according to pulse mode.The suitable power spectrum that engraves laser instrument is that 2 to 100 watts and pulse frequency are preferably 1 to 100Hz.
The corresponding laser instrument that can be used in the method according to this invention is commercially available.
Plastic inscriptions according to the present invention can be used for wherein, and plastics pass through printing so far, the all situations that embossing or artistic carving engrave, or wherein can not obtain so far color strong with permanent engraving/mark or can not get engraving/all situations of mark or engraved when only in plastics self, using laser-sensitive pigment/mark at all.This relates to linear plastic or according to crosslinked those of heat-labile mode, polyolefin for example, and polyvinyl, polyamide, polyester, polyacetals, Merlon also relates to polyurethane and ionomer in some cases.
The advantage that engraves type according to the present invention is a color fastness, persistence and pliability/individual character, and promptly the process of tagging can need not mask, stereotype or stamping technique condition and carry out.
But mark and/or engrave any kind and the plastics of shape, for example
In packaging industry (lot number uses the date, creation data, note)
In security fields (anti-fake code and label)
In motor vehicle and airplane industry (cable, plug, switch, container, functional part, flexible pipe, lid, handle, lever etc.)
In medical skill (equipment, instrument, implant)
In agricultural (animal ear tag note)
In electrician/electronics (cable, plug, switch, functional part, pattern plate, parameter plate)
In the decoration field (logo is used for the model indication of all kinds equipment, container, toy, instrument, individual mark).
The invention still further relates to by the method according to this invention have color marker or engrave and the sealed plastics of its mark.
The specific embodiment
Following examples are used to explain that the present invention is not intended to limit.Given percentage data is a percetage by weight.
Embodiment
Each coating systems depends on layer thickness and uses scraper or engraved roll to be administered on polyester support membrane or the layer formerly by intaglio printing or by serigraphy, and drying.
Embodiment 1: the making of energy absorber layer 2
18.5g ethyl acetate
1.5g NC Nitroncellulose
2.0g Sn (Sb) O
2(d
50Value＜1.1 μ m) (Du Pont)
NC Nitroncellulose be dissolved in the solvent ethyl acetate of initial introducing and fully and stir (Ultraturrax, 2000rpm).Stir subsequently and add the SnO that energy absorber Sb mixes
2, make homogeneous phase and stick with paste.The amount of energy absorber depends on the energy absorption of colouring agent and depends on the tagged plastics of wanting, and should set in view of the above.
Embodiment 2: the making of energy absorber layer 2
18.5g ethyl acetate
1.5g NC Nitroncellulose
2.0g channel black (special type deceives 6, available from Degussa) (d
50Value＜17nm)
Being similar to embodiment 1 processes.Used absorbent is a channel black.
Embodiment 3: the making of energy absorber layer 7
For the support membrane 7 that has wherein added energy absorber, will comprise effective energy absorption agent content, for example content of carbon black is the preferably polyethylene of 1-10%, polypropylene, the flat film of PET or its composite is extruded or blowing.
Embodiment 4: the making of separation layer 3
19.9g toluene
0.1g ester type waxes
PE wax is dissolved in the toluene and fully and stirs.
Embodiment 5: the making of sealant 4
8.0g methyl ethyl ketone
4.6g toluene
2.0g cyclohexanone
3.9g?PMMA(Tg：122℃)(Degussa)
1.5g PE wax
PE wax and PMMA are dissolved in the solvent mixture and use the dissolvers homogenizing.
Embodiment 6: the making of sealant 4
8.0g dimethylbenzene
4.0g polystyrene
2.0g PE wax
PE wax and polystyrene are dissolved in the dimethylbenzene and use the dissolvers homogenizing.
Embodiment 7: the making of sealant 4
40.0g n-butyl acetate
10.0g polystyrene
0.5g ethyl cellulose
0.5g UV stabilizing agent
Ethyl cellulose, polystyrene and UV stabilizing agent are dissolved in the n-butyl acetate and use the dissolvers homogenizing.
Embodiment 8: contain the preparation that engraves medium 5 of polymer
20.0g ethyl acetate
2.0g NC Nitroncellulose
6.0g polypropylene powder (d
50＜50mm) (for example Coathylene PB 0580, Du Pont)
2.0g Cu phthalocyanine
1.0g UV stabilizing agent (benzotriazole derivatives)
NC Nitroncellulose is dissolved in the solvent ethyl acetate of initial introducing and fully and stirs.Stir the adding polypropylene powder subsequently, colouring agent copper phthalocyanine and UV stabilizing agent are made homogeneous phase and are stuck with paste.If desired, use three-roll grinder to improve the uniformity of sticking with paste.
To stick with paste and for example use scraper to be coated on the polyester film and dry.
Embodiment 9: contain the preparation that engraves medium 5 of polymer
25.0g methyl ethyl ketone
34.0g toluene
12.0g PVC-PVAc copolymer
16.0g polyurethane
0.5g titanium oxide
Being similar to embodiment 8 processes.Used colouring agent is a titanium dioxide.
Embodiment 10: contain the preparation that engraves medium 5 of polymer
35.0g n-butyl acetate
6.0g polystyrene
2.0g NC Nitroncellulose
2.0g Cu phthalocyanine
Being similar to embodiment 8 processes.Used colouring agent is the Cu phthalocyanine.
Embodiment 11: by engraving medium 5 and energy absorber 2 producing zones 8
20.0g ethyl acetate
2.0g NC Nitroncellulose
6.0g Irgazin is red
1.2g?Sn(Sb)O
2
Being similar to embodiment 7 processes.Used colouring agent is that the red and used absorbent of Irgazin is Sn (Sb) O
2
Embodiment 12: labelling experiment and result
Nd-YVO
4, 20W power output Nd-YVO
4, the 10W power output
1064nm, 100kHz pulse frequency 1064nm, 50kHz pulse frequency
Nd-YVO
4, 6W power output Nd:YAG, 10W power output
532nm, 50-60kHz pulse frequency 1064nm, 50-60kHz pulse frequency
Embodiment 13: what have and do not have to seal is marked at the comparison in the influence of bleeding/frosting
The film that has contacted with mark that is marked at that does not have sealing
Bleeding on after bleeding
Merck?KGaA
The mark that has sealing does not have tangible bleeding
Claims (12)
1. permanent and wearability ground is coloured with plastics engraves and/or the method for mark, it is characterized in that the bleeding of colouring agent in the plastics and/or absorbent or frosting are by in engraving technical process or seal with transparent polymer immediately after this and prevent through the zone that laser engraves.
According to the permanent and wearability with plastics of claim 1 coloured engraving and/or the method for mark, it is characterized in that glass transition temperature 〉=90 ℃ of polymer.
According to the permanent and wearability with plastics of claim 1 or 2 coloured engraving and/or the method for mark, it is characterized in that sealant is made up of polymer, the polyvinyl fluoride of the acrylate of styrene, vinyl chloride, methyl methacrylate or hydroxyl-functional.
According in the claim 1 to 3 each the permanent and wearability with plastics coloured engraving and/or the method for mark, it is characterized in that it is 1-10 μ m that polymeric layer has thickness.
According in the claim 1 to 4 each the permanent and wearability with plastics coloured engraving and/or the method for mark, it is characterized in that mark is undertaken by engraving technology indirectly.
6. engrave and/or the method for mark according to each the permanent and wearability ground with plastics in the claim 1 to 5 is coloured, it is characterized in that engraving the use laser instrument and carry out and be sealed in the step carrying out.
According in the claim 1 to 5 each the permanent and wearability with plastics coloured engraving and/or the method for mark, it is characterized in that, in two-step method, at first use laser instrument to engrave, immediately in second step, seal engraving the zone.
According in the claim 1 to 6 each the permanent and wearability with plastics coloured engraving and/or the method for mark, it is characterized in that using the coating systems of forming by the layer of overlapping setting about in the of at least three, wherein ground floor is to the support membrane of laser for the transparency, on it, be applied with laser-sensitive energy absorber layer or energy absorber arranged to wherein introducing, follow by separation layer and sealant, with as last layer, the medium that engraves that comprises colouring agent and optional polymer component, or comprised the medium that engraves of sealed polymer, wherein engrave medium engraving/under laser action, be introduced into frosting in the labeling process.
According to the permanent and wearability with plastics of claim 7 coloured engraving and/or the method for mark, it is characterized in that engraving and use coating systems to carry out, described coating systems is by being the support membrane and the energy absorber layer of the transparency to laser and engraving medium and form as individual course, or this coating systems is formed by support membrane with by the layer that the mixture that engraves medium and energy absorber is formed, or this coating systems is by the support membrane of wherein having introduced energy absorber, with engrave medium and form, and described coating systems uses the laser instrument mark, engraving medium in this process is transferred on the softening plastics, and in second step, use coating systems to seal, described coating systems is by the supporting layer that to laser is the transparency, laser-sensitive absorber layer or wherein introduce the support membrane that energy absorber is arranged, separation layer and sealant are formed, and the use laser illumination, in this process, essential energy being transferred to separation layer by the energy absorber layer, therefore the latter is softening also is transferred to sealant on the plastics.
According in the claim 1 to 6 each the permanent and wearability with plastics coloured engraving and/or the method for mark, it is characterized in that using the coating systems of forming by the layer of overlapping setting about in the of at least three, wherein ground floor is to the self-absorption support membrane of laser for the transparency, on it, be applied with separation layer and sealant, with as last layer, comprise engraving medium or having comprised the medium that engraves of sealed polymer of colouring agent and optional polymer component with after-applied, wherein said engrave medium engraving/under laser action, be introduced into frosting in the labeling process.
11. according to the permanent and wearability with plastics of claim 7 coloured engraving and/or the method for mark, it is characterized in that for engraving, use coating systems, described coating systems is by to laser being the self-absorption support membrane of the transparency and by layer forming that the mixture that engraves medium and energy absorber is formed, or described coating systems is by the support membrane of wherein having introduced energy absorber, with engrave medium and form, and described coating systems uses the laser instrument mark, engraving medium in this process is transferred on the softening plastics, and in second step, use coating systems to seal, described coating systems is by the supporting layer that to laser is the transparency, laser-sensitive absorber layer or wherein introduce the support membrane that energy absorber is arranged, separation layer and sealant are formed, and the use laser illumination, in this process, essential energy being transferred to separation layer by the energy absorber layer, the latter is softening and therefore sealant is transferred to plastics.
12. by mark that obtains according to each method in the claim 1 to 11 and/or the plastics that engrave with sealing.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102004016037.6 | 2004-03-30 | ||
| DE200410016037 DE102004016037A1 (en) | 2004-03-30 | 2004-03-30 | Method for the permanent abrasion-resistant colored inscription and/or marking of plastics comprises preventing bleeding and/or blooming of the dye and/or absorber in the plastic during sealing of inscribed sites with a transparent polymer |
| DE102004026335.3 | 2004-05-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1938161A true CN1938161A (en) | 2007-03-28 |
| CN100496993C CN100496993C (en) | 2009-06-10 |
Family
ID=35456088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005800101497A Expired - Fee Related CN100496993C (en) | 2004-03-30 | 2005-03-11 | Method for the permanent abrasion-resistant colored inscription and/or marking of plastics and plastic obtained therefrom |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN100496993C (en) |
| DE (1) | DE102004016037A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103433622A (en) * | 2013-08-22 | 2013-12-11 | 广西容县风采印业有限公司 | Method for using laser for marking plastic film |
| CN107009559A (en) * | 2017-03-17 | 2017-08-04 | 天津工业大学 | A kind of preparation method of three-dimension code diaphragm |
| CN111853380A (en) * | 2014-07-02 | 2020-10-30 | 库博标准汽车配件有限公司 | Hose, abrasion resistant composition and hose manufacturing process |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102016219858A1 (en) * | 2016-10-12 | 2018-04-12 | Weilburger Coatings Gmbh | A method of making a coating having markings on a surface or part of a surface of an article |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3517275A1 (en) * | 1985-05-14 | 1986-11-20 | Bayer Ag, 5090 Leverkusen | METHOD FOR LABELING PLASTICS |
| CH677756A5 (en) * | 1989-01-26 | 1991-06-28 | Ciba Geigy Ag | |
| EP0605803A1 (en) * | 1992-12-12 | 1994-07-13 | Hoechst Aktiengesellschaft | Colour-marking of plastic surfaces by laser radiation |
| DE19942316A1 (en) * | 1999-09-04 | 2001-03-08 | Poesl Rudolf | Laser printing of a plastic substrate by heating a compound of plastic powder and glass pigments on the substrate with a laser beam |
| DE10136479A1 (en) * | 2001-07-27 | 2003-02-06 | Merck Patent Gmbh | Colored labeling and marking of plastics and paints |
-
2004
- 2004-03-30 DE DE200410016037 patent/DE102004016037A1/en not_active Withdrawn
-
2005
- 2005-03-11 CN CNB2005800101497A patent/CN100496993C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103433622A (en) * | 2013-08-22 | 2013-12-11 | 广西容县风采印业有限公司 | Method for using laser for marking plastic film |
| CN111853380A (en) * | 2014-07-02 | 2020-10-30 | 库博标准汽车配件有限公司 | Hose, abrasion resistant composition and hose manufacturing process |
| CN107009559A (en) * | 2017-03-17 | 2017-08-04 | 天津工业大学 | A kind of preparation method of three-dimension code diaphragm |
Also Published As
| Publication number | Publication date |
|---|---|
| DE102004016037A1 (en) | 2005-11-03 |
| CN100496993C (en) | 2009-06-10 |
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