CN101142089A - Two-color molded product for laser marking and laser marking method - Google Patents
Two-color molded product for laser marking and laser marking method Download PDFInfo
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- CN101142089A CN101142089A CNA2006800085836A CN200680008583A CN101142089A CN 101142089 A CN101142089 A CN 101142089A CN A2006800085836 A CNA2006800085836 A CN A2006800085836A CN 200680008583 A CN200680008583 A CN 200680008583A CN 101142089 A CN101142089 A CN 101142089A
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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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- 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
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0013—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor using fillers dispersed in the moulding material, e.g. metal particles
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- 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
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/16—Making multilayered or multicoloured articles
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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
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/46—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography characterised by the light-to-heat converting means; characterised by the heat or radiation filtering or absorbing means or layers
- B41M5/465—Infra-red radiation-absorbing materials, e.g. dyes, metals, silicates, C black
Abstract
This invention provides a two-color molded product for laser marking, which, even when a support is black, can realize marking of characters, symbols, designs and the like with good contrast and, at the same time, has semi-permanent abrasion resistance, and a method for laser marking for the two-color molded products. The two-color molded product comprises at least a support and a cover covering the support. The support comprises a resin composition comprising (A) 100 parts by mass of a thermoplastic resin, (B) 0.0001 to 5 parts by mass of at least one specific energy absorbent selected from the group consisting of carbon black, titanium black, triiron tetraoxide, mica, carbonate, and metal silicates, and (C) 0 to 10 parts by mass of a coloring matter other than the component (B). The cover is formed of (D) a trasparent thermoplastic resin.
Description
Technical field
The present invention relates to a kind of two-color molded product for laser marking and with respect to the laser marking method of this two-color molded product, described two-color molded product for laser marking passes through laser light irradiation, surface element at two-color molded product is printed, obtain the high literal clearly of the contrast of former background color and printing portion, symbol, pattern etc., and mar proof is good.
Background technology
At present, the printing of two-color molded product is undertaken by following method: after the back side of transparent nappe or painted supporting body surface are implemented printings such as serigraphy, liner printing, drop stamping printing to literal, symbol, pattern, the thermoplastic resin that constitutes supporter or nappe is embedded moulding.
But, in said method, there is following variety of issue:
(1) owing to use the printing ink that contains organic solvent, therefore on environmental sanitation, has problems.
(2) producing spreading and sinking in of printing ink when printing oozes.
(3) need drying printing ink before the embedding of subsequent handling forms, productivity is poor.
(4) when the thermoplastic resin that will constitute nappe or supporter embeds moulding, because the briquetting pressure of each resin, the literal that prints in last operation, symbol, pattern deform.
(5) because setting, the forming temperature in the molding procedure causes the literal, symbol, the pattern generation variable color that print.
(6) can not print complex-shaped two-color molded product.
(7) production process complexity, productivity is poor.
In addition, at present, as the printing process of not using printing ink, motion has irradiating laser light and in the laser-marking method (for example: with reference to patent documentation 1, patent documentation 2, patent documentation 3 and patent documentation 4) of plastic molded article surface printing.
This existing laser-marking method prints on the plastic molded article surface, it is to the additive of blended absorbent laser beam in thermoplastic resin and the plastic molded article irradiating laser light of moulding, the plastic molded article surface that acts on by additive produces thermal change such as foaming, decomposition, fusing, carbonization, gasification, manifests white text, white symbol and white pattern or black literal, black symbols and black pattern etc.
But, in this existing laser-marking method, there is such shortcoming, in order to produce sufficient contrast, it is uneven to identify literal sometimes, becomes literal, symbol, pattern of the state that burns of pitchy or bronzing class etc. sometimes, owing to can not obtain contrast fully and the effect of surface smoothing, therefore, the mar proof of sign literal portion is poor, has problems on the practicality.
Therefore, motion has contrast good and surface smoothing laser-marking good, that can carry out laser-marking resin combination and formed body (with reference to patent documentation 5 and 6) thereof.And then, in these documents, also record and use composition as internal layer usefulness, make the multi-layer sheet that is laminated with the top layer that constitutes by transparent thermoplastic resin.But, when on this formed body, carrying out laser-marking, though contrast is good when supporter is white, contrast and insufficient when supporter is black.In addition, the problem of existence is, when making contrast good when the output that improves laser beam, produces be full of cracks at the transparent surface layer that is made of thermoplastic resin.
Patent documentation 1: special public clear 61-11771 communique
Patent documentation 2: special public clear 61-41320 communique
Patent documentation 3: special public clear 62-59663 communique
Patent documentation 4: the spy opens flat 1-254743 communique
Patent documentation 5: the spy opens the 2002-273832 communique
Patent documentation 6: the spy opens the 2002-309104 communique
Summary of the invention
Therefore, the present invention finishes in view of the problem that exists in the above-mentioned existing laser-marking method, its purpose is, provide a kind of two-color molded product for laser marking and with respect to the laser marking method of this two-color molded product, described two-color molded product for laser marking also can contrast identify literal, symbol, case figure etc. well when supporter is black, and has semipermanent mar proof.
According to the present invention, a kind of two-color molded product for laser marking is provided, described two-color molded product for laser marking is made of the nappe of supporter and this supporter of covering at least, wherein, above-mentioned supporter is made of the resin combination that contains following compositions: with respect to (A) thermoplastic resin 100 mass parts, (B) be selected from that carbon black, titanium are black, at least a kind particular energy absorbent 0.0001～5 mass parts in tri-iron tetroxide, mica, carbonate and the metal silicate, and (C) colouring agent 0～10 mass parts except that above-mentioned (B) composition.Above-mentioned nappe is made of (D) transparent thermoplastic resin.
Above-mentioned two-color molded product preferably forms above-mentioned supporter and above-mentioned nappe by the common moulding of injection moulding.
In addition, in two-color molded product of the present invention, sometimes pass through laser light irradiation, the part that is irradiated to of above-mentioned (A) thermoplastic resin is peeled off foaming, any the above form that manifests white text, white symbol and white pattern, (A) thermoplastic resin of this moment are preferably selected from MABS resin, methyl methacrylate/styrene copolymerized resin, polymethyl methacrylate resin, rubber-reinforced polymethyl methacrylate resin, nylon resin, polyacetal resin, polylactic acid based resin, reach at least a kind in the vistanex.
And, in two-color molded product of the present invention, sometimes pass through laser light irradiation, the part generation carbonization that is irradiated to of above-mentioned (A) thermoplastic resin, manifest the black literal, the above form of any of black symbols and black pattern, (A) thermoplastic resin of this moment is preferably selected from ABS resin, the ASA resin, rubber-reinforced polystyrene resin, polycarbonate resin, pet resin, the polybutylene terephthalate (PBT) resin, polyphenylene oxide resin, polyphenylene sulfide, acrylic resin, polyvinyl resin, ABS/ polycarbonate alloy resin, reach at least a kind in the ABS/ polybutylene terephthalate (PBT) alloy resin.
In two-color molded product of the present invention, above-mentioned nappe and above-mentioned supporter are preferably the thickness constituent ratio of nappe/supporter=1/9～9/1.
In addition, according to the present invention, a kind of laser marking method is provided, promptly, to above-mentioned two-color molded product, with laser oscillation wavelength is that 532～1064nm, laser medium are that the laser-marking device irradiation of neodymium modified yttrium-aluminium-garnet or neodymium modification yttrium-four vanadium oxide prints, and the contrast of printing color development portion and basal part is more than 3.
According to the present invention, obtain following excellent results: can provide a kind of two-color molded product for laser marking and with respect to the laser marking method of this two-color molded product, described two-color molded product for laser marking also can contrast identify literal, symbol, pattern etc. well when supporter is black, and has semipermanent mar proof.
The specific embodiment
Below, embodiments of the present invention are elaborated, but the present invention is not limited to these embodiments.
Two-color molded product of the present invention is made of the nappe of supporter and this supporter of covering at least, wherein, above-mentioned supporter is made of the resin combination that contains following 3 kinds of compositions: (A) thermoplastic resin, (B) particular energy absorbent, and (C) colouring agent except that above-mentioned (B) composition.Above-mentioned nappe is made of (D) transparent thermoplastic resin.
Below each composition is described.
(A) thermoplastic resin:
There are following two kinds of situations in resin combination of the present invention: because laser light irradiation, the part that is irradiated to of this thermoplastic resin is peeled off foaming, manifests any above form of white text, white symbol and white pattern; Perhaps because laser light irradiation, the part generation carbonization that is irradiated to of above-mentioned thermoplastic resin manifests any above form of black literal, black symbols and black pattern.
In above-mentioned, passing through laser light irradiation, the part that is irradiated to of this thermoplastic resin is peeled off foaming, the situation that manifests any above form of white text, white symbol and white pattern, the thermoplastic resin of this moment is preferably selected from least a kind in MABS resin, methyl methacrylate/styrene copolymerized resin, polymethyl methacrylate resin (PMMA resin), rubber-reinforced polymethyl methacrylate resin (rubber-reinforced PMMA resin), nylon resin, polyacetal resin, polylactic acid based resin and the vistanex.Wherein, be preferably MABS resin, methyl methacrylate/styrene copolymerized resin, polymethyl methacrylate resin (PMMA resin), rubber-reinforced polymethyl methacrylate resin (rubber-reinforced PMMA resin) especially.It has been generally acknowledged that, pass through laser light irradiation, the side chain such as methyl, methylene, amino of these thermoplastic resins is peeled off, thus, illuminated portion is peeled off foaming, reach (C) interaction of colouring agent by (B) particular energy absorbent, clearly manifest white text, white symbol and white pattern with other.These thermoplastic resins can be used alone or two or more kinds may be used.That is, thermoplastic resin can be the polymer alloy that is made of the resin more than 2 kinds.
On the other hand, passing through laser light irradiation, thermoplastic resin be irradiated to partially carbonized, manifest the black literal, the situation of the above form of any of black symbols and black pattern, the thermoplastic resin of this moment is preferably selected from ABS resin, the ASA resin, rubber-reinforced polystyrene resin, polycarbonate resin, pet resin, the polybutylene terephthalate (PBT) resin, polyphenylene oxide resin, polyphenylene sulfide, acrylic resin, polyvinyl resin, in ABS/ polycarbonate alloy resin and the ABS/ polybutylene terephthalate (PBT) alloy resin at least a kind.Wherein, be preferably ABS resin, ASA resin, rubber-reinforced polystyrene resin, polycarbonate resin, pet resin, polybutylene terephthalate (PBT) resin especially.These thermoplastic resins can use a kind separately, and also two or more kinds may be used in addition.That is, thermoplastic resin can be the polymer alloy that is made of the resin more than 2 kinds.
(B) particular energy absorbent:
Secondly, the particular energy absorbent of energy that is used for the absorption laser beam of the present composition be selected from that carbon black, titanium are black, tri-iron tetroxide (iron oxide black), mica, carbonate and metal silicate at least a kind.
Wherein, passing through laser light irradiation, the part that is irradiated to of thermoplastic resin is peeled off foaming, manifest white text, the situation of any above form of white symbol and white pattern, being used for so-called basal part is the particular energy absorbent of the situation of black system, for example have: carbon black, titanium is black, mica, tri-iron tetroxide etc., passing through through laser light irradiation, thermoplastic resin be irradiated to partially carbonized, manifest the black literal, the situation of the above form of any of black symbols and black pattern, used particular energy absorbent for example has: carbon black, mica, carbonate such as calcium carbonate; Metal silicates such as the silicic acid aluminium oxide (mica) of silicic acid aluminium oxide, iron content, moisture silicic acid aluminium oxide (kaolin), magnesium silicate (talcum), calcium silicates.
Above particular energy absorbent can be used alone or two or more kinds may be used.
The addition that is used for particular energy absorbent of the present invention with respect to above-mentioned (A) thermoplastic resin 100 mass parts, is 0.0001～5 mass parts.
Promptly, passing through laser light irradiation, the part that is irradiated to of thermoplastic resin is peeled off foaming, the situation that manifests any above form of white text, white symbol and white pattern, the addition of particular energy absorbent with respect to (A) thermoplastic resin 100 mass parts, is 0.005～5 mass parts, preferred 0.01～3 mass parts, more preferably 0.02～1 mass parts.If be lower than 0.005 mass parts, then can not get sufficient contrast, on the other hand, when it surpassed 5 mass parts, the energy absorption function was excessive, and contrast descends equally.
On the other hand, passing through laser light irradiation, the part generation carbonization that is irradiated to of thermoplastic resin, the situation that manifests any above form of black literal, black symbols and black pattern, the addition of particular energy absorbent with respect to (A) thermoplastic resin 100 mass parts, is 0.0001～5 mass parts, preferred 0.00015～3 mass parts, more preferably 0.0002～1 mass parts.If be lower than 0.0001 mass parts, then can not get sufficient contrast, on the other hand, when it surpassed 5 mass parts, the energy absorption function was excessive, and contrast descends equally.
Should (C) colouring agent be the particular energy absorbent colouring agent in addition of above-mentioned (B) composition.(C) colouring agent for example has: inorganic pigment, organic pigment, dyestuff etc.Wherein, inorganic pigment for example has: as titanium oxide, barium sulfate, zinc sulphide, the zinc oxide of Chinese white; As the iron oxide of yellow uitramarine, titan yellow; Iron oxide as red pigment; As the cobalt blue of blue pigment, ultramarine etc.In addition, organic pigment for example has: as monoazo, condensation azo, anthraquinone, two diazonium, the heterocycle of yellow uitramarine; Quinoline a word used for translation ketone, anthraquinone, perylene, monoazo as red pigment; Phthalocyanine as blue pigment; As phthalocyanine of viridine green etc.And dyestuff for example has: as monoazo, anthraquinone, two diazonium, the heterocycle of weld; Anthraquinone, perylene ketone, thioindigo, two diazonium as orchil; As anthraquinone of blue dyes etc.
(C) use amount of colouring agent with respect to (A) thermoplastic resin 100 mass parts, is 0～10 mass parts, is preferably 0.7～8 mass parts.When (C) colouring agent surpasses 10 mass parts, may cause that the rerum natura as two-color molded product reduces, not preferred.
In the present invention; in order to prepare 2 kinds of compositions or 3 kinds of supporters that composition constitutes by (A)～(C); for example by will the mixing of (A)～(C) composition, dissolve mixing with common extruder etc. again and obtain, but be not limited thereto to make it ways such as granulating with Henschel mixer etc.In addition, the thickness of supporter is preferably 0.5～5mm, more preferably 0.7～4mm.
(D) transparent thermoplastic resin:
The transparent thermoplastic resin that forms nappe for example has: polymethylacrylic acid styrene resin (MS resin), AS resin, polymethyl methacrylate resin (PMMA resin), soft polymethyl methacrylate resin (soft PMMA resin), polycarbonate resin, pet resin, poly-cyclohexane 1,4-dimethyl benzene dioctyl phthalate resin, polystyrene resin, transparent ABS resin, Corvic, acrylic resin, polyvinyl resin etc.In these transparent thermoplastic resins, particularly from the case hardness characteristic, preferable methyl methyl acrylate resin, soft polymethyl methacrylate resin, polycarbonate resin, pet resin.More preferably polymethyl methacrylate resin, soft polymethyl methacrylate resin.In addition, the preferred 0.5～5mm of the thickness of nappe, more preferably 0.7～4mm.
Two-color molded product of the present invention is preferably by forming above-mentioned supporter and nappe with the common moulding of injection moulding.
Utilize the method for injection moulding coforming for example to have such double-colored (two kinds) resin is penetrated successively from separately injection barrel respectively such as core bag forming method, mould sliding method, rotary process to be filled into mould inside, make the method for forming of the moulding product of different materials or different colours material.
In this two-color molded product, above-mentioned nappe and supporter are preferably the thickness constituent ratio of nappe/supporter=1/9～9/1, the thickness constituent ratio of further preferred nappe/supporter=3/7～7/3.When it is this thickness constituent ratio, according to circumstances and different, when producing contrast, sometimes to implement laser-marking 2 times, even but like this, nappe can not chap yet, breakage, being the sheet thickness formation with laser-marking condition broadness, is preferred thickness constituent ratio.
In addition, the integral thickness of two-color molded product is generally 1.0～10mm, is preferably 1.5～8mm.
Need to prove, in the supporter and nappe of above-mentioned formation two-color molded product, as required, in the scope that does not influence its characteristic, can add other additive, for example: releasing agent, stabilizing agent, antioxidant, ultra-violet absorber, hardening agent etc.
When using two-color molded product of the present invention to carry out laser-marking, the following laser marking method of preferred employing, for example to these formed bodys, with laser oscillation wavelength is that 532～1064mm, laser medium are that the laser-marking device irradiation of neodymium modified yttrium-aluminium-garnet or neodymium modification yttrium-four vanadium oxide prints, and the contrast of printing color development portion and basal part is more than 3.
Need to prove that as the laser-marking device, laser beam can be monotype or multi-mode, in addition, beam diameter is controlled to be 20～40 μ m, in addition, the broad light beam of beam diameter as 80～100 μ m also can use.But in monotype, more than 3, and obtain the good print quality aspect of contrast and consider that the preferred light beam diameter is 20～40 μ m from the contrast that can obtain to print color development portion and basal part.
The laser-marking of two-color molded product for laser marking of the present invention is good, can describe literal, symbol, pattern etc. easily and clearly with laser on the surface of nappe and supporter.Therefore, two-color molded product for laser marking of the present invention can be used for the outer container of electrical accessorie, electronic components, auto parts machinery, various recording mediums, the printing of various display boards etc. effectively.
Embodiment
Below, be described more specifically the present invention by embodiment, but the present invention is not subjected to any qualification of these embodiment.Need to prove that " part " in the following examples and the comparative example reaches " % ", unless otherwise specified, be meant mass parts and quality %.In addition, the various evaluations among the embodiment, mensuration are implemented by following method.
Laser irradiation condition 1:
Laser device: the ROFIN BASEL RSM30D of company (Nd:YAG)
Aperture: 2.0mm φ
Sweep speed: 400mm/s
Wavelength: 1064nm
Frequency: 6000Hz
Current value: 34A
Laser irradiation condition 2:
Laser device: the ROFIN BASEL RSM30D of company (Nd:YAG)
Aperture: 2.0mm φ
Sweep speed: 400mm/s
Wavelength: 1064nm
Frequency: 6000Hz
Current value: 28A
Color emissivity is estimated:
(Gretag Macbeth corporate system 7000A), is measured WI: whiteness, YI: yellow chromaticity to use colour meter.
Contrast is estimated:
Use the luminance meter (LS100) of Konicaminolta corporate system to measure.Numerical value is big more, and contrast is high more, and visuality is high more.In the present invention, be 3 when above in contrast, be qualified (zero), contrast be 2～3 o'clock be △, be 2 to be defective (*) when following in contrast.
Have or not be full of cracks:
Use the zoom microscope (VH5900) of Keyence corporate system, observe nappe and have or not be full of cracks.
(embodiment 1)
To mix as the ACRYPET VRL40 (trade name) of the beautiful positive corporate system of Mitsubishi of the rubber-reinforced polymethyl methacrylate resin (rubber-reinforced PMMA resin) of thermoplastic resin with as the ACRYPET MF (trade name) of the beautiful positive corporate system of Mitsubishi of polymethyl methacrylate resin usually, be that 15 quality % prepare with rubber mass.The common extruder of preparation employing is granulated and is carried out.With respect to the rubber-reinforced polymethyl methacrylate resin of making (rubber-reinforced PMMA resin) 100 mass parts; add carbon black (Mitsubishi Chemical Ind's system, #20) 0.1 mass parts, as titanium oxide 0.02 mass parts of colouring agent, as ultramarine (first changes into corporate system, AP201) 0.1 mass parts of colouring agent; (eastern beautiful DOW CORNING organosilicon company makes, commercial grade: 125M) 2.0 mass parts to add dimethyl polysiloxane/silica mixture again; evenly mix with homogenizer; granulate the compound that the preparation supporter is used with extruder, granulator.
At first, making thickness with injection (mo(u)lding) machine is the flat board of 3.0mm, has estimated the color emissivity that uses the position that the Nd:YAG laser-marking crosses, and it be the results are shown in table 1.
Secondly, the PMMA resin that preparation is used as nappe (the beautiful positive corporate system of Mitsubishi, ACRYPET MF), soft PMMA resin (Kuraray corporate system trade name:, trade name: compound Parapet NW05), with supporter with and double-colored (two kinds) resin complexes of using of nappe penetrate successively from separately injection barrel respectively and be filled into mould inside, carry out coforming thus, the thickness of making separately is the two-color molded product of 2.0mm (whole thickness is 4.0mm).And, measured color emissivity and the contrast of in this two-color molded product, using the position of Nd:YAG laser-marking, it be the results are shown in table 1.
(embodiment 2)
Do not use ultramarine and dimethyl polysiloxane/silica mixture, in addition, estimate the dull and stereotyped color emissivity and the color emissivity and the contrast of two-color molded product similarly to Example 1.It is the results are shown in table 1.
(embodiment 3)
Do not use dimethyl polysiloxane/silica mixture, in addition, estimated the color emissivity and the contrast of dull and stereotyped color emissivity and two-color molded product similarly to Example 1, it be the results are shown in table 1.
(embodiment 4)
With respect to rubber-reinforced PMMA resin 100 mass parts, use carbon black 0.1 mass parts, do not use titanium oxide, ultramarine and dimethyl polysiloxane/silica mixture, in addition, estimated the color emissivity and the contrast of dull and stereotyped color emissivity and two-color molded product similarly to Example 1, it the results are shown in table 1.
(embodiment 5)
Use nylon resin (the emerging product corporate system of space portion, trade name: the nylon 1015GU6 of space portion) replace rubber-reinforced PMMA resin, in addition, estimated the color emissivity and the contrast of dull and stereotyped color emissivity and two-color molded product similarly to Example 1.It is the results are shown in table 1.
(comparative example 1)
Use transparent ABS resin (NABS resin) (eastern beautiful corporate system, trade name: Toyolac 920) to replace rubber-reinforced PMMA resin, in addition, estimated the color emissivity and the contrast of dull and stereotyped color emissivity and two-color molded product similarly to Example 1, it the results are shown in table 1.
(embodiment 6)
Use polycarbonate resin (the emerging product corporate system of bright dipping, trade name: TARFLON A 1700) replace rubber-reinforced PMMA resin, simultaneously, use carbon black 0.001 mass parts, titanium oxide 0.2 mass parts and zinc sulphide (サ Network ト Le ベ Application corporate system, trade name: 0.2 mass parts SACHTORITH HD), do not use as colouring agent ultramarine and dimethyl polysiloxane/silica mixture, in addition, the color emissivity and the contrast of two-color molded product have been estimated similarly to Example 1.It is the results are shown in table 2.
(embodiment 7)
Use ABS resin (Techno Polymer corporate system, trade name: Techno ABS110) replace polycarbonate resin, in addition, estimated the color emissivity and the contrast of two-color molded product similarly to Example 6, it be the results are shown in table 2.
[table 1]
| Laser-marking color development literal look | The white color development | ||||||
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | ||
| The chromonic layer pigmentary resin is formed | Rubber-reinforced PMMA resin nylon resin NABS resin polycarbonate resin/ABS resin carbon black titanium oxide ultramarine zinc sulphide dimethyl polysiloxane silica mixture | 100 - - - - 0.1 0.02 0.1 - 2.0 | 100 - - - - 0.1 0.02 - - - | 100 - - - - 0.1 0.02 0.1 - - | 100 - - - - 0.1 - - - - | - 100 - - - 0.1 0.02 0.1 - 2.0 | - 100 - - 0.1 0.02 0.1 - 2.0 |
| The color emissivity evaluation of pigmentary resin (white color development) | Lasing condition 1:WI value (%) YI value (%) | 41 6 | 23 22 | 30 13 | 22 22 | 40 8 | 11 21 |
| Lasing condition 2:WI value (%) YI value (%) | 27 0.2 | 18 2 | 22 2 | 14 5 | 25 0.4 | 11 7 | |
| The color emissivity evaluation of two-color molded product (2 layers of layer/chromonic layer) (white color development) | Lasing condition 1: top layer PMMA resin contrast has or not be full of cracks | ○ △～○ | ○ △～○ | ○ △～○ | ○ △～○ | ○ △～○ | × × |
| Lasing condition 2: have or not be full of cracks than degree during the PMMA resin of top layer | ○ ○ | ○ ○ | ○ ○ | △～○ ○ | ○ ○ | × ○ | |
| Lasing condition 1: have or not be full of cracks than degree during the soft PMMA resin in top layer | ○ ○ | ○ ○ | ○ ○ | ○ ○ | ○ ○ | × ○ | |
[table 2]
| Laser-marking color development literal look | The black color development | ||
| Embodiment 6 | Embodiment 7 | ||
| The chromonic layer pigmentary resin is formed | Rubber-reinforced PMMA resin nylon resin NABS resin polycarbonate resin/ABS resin carbon black titanium oxide ultramarine zinc sulphide dimethyl polysiloxane silica mixture | - - - 100 - 0.001 0.2 - 0.2 - | - - - - 100 0.001 0.2 - 0.2 - |
| The color emissivity evaluation (hyaline layer/chromonic layer is double-colored) (black color development) of two-color molded product | Lasing condition 1: top layer PMMA resin contrast has or not be full of cracks | ○ ○ | ○～△ ○ |
| Lasing condition 2: top layer PMMA resin contrast has or not be full of cracks | ○ ○ | △ ○ | |
| Lasing condition 1: top layer soft PMMA resin contrast has or not be full of cracks | ○ ○ | ○ ○ | |
Result by table 1 learns, as embodiment 1～5, when using rubber-reinforced PMMA resin, nylon resin as supporter, by laser light irradiation, illuminated portion is peeled off foaming and is clearly manifested white text etc., on the other hand, as comparative example 1, also by laser light irradiation, its illuminated portion is peeled off foaming to the transparent ABS resin, but the amount of the hydroxyl radical gas of peeling off is few, and the color emissivity of white text etc. is extremely low.In addition, learn by table 2, when using polycarbonate resin, ABS resin as supporter, by laser light irradiation, illuminated portion generation carbonization and clearly manifest black literal etc.
Industrial applicibility
Two-color molded product for laser marking of the present invention, when being black, supporter also can contrast identify well literal, symbol, pattern etc., and has a semipermanent mar proof, therefore, can effectively be used for the printing of the outer container of electrical accessorie, electronic components, auto parts machinery, various recording mediums, various display boards etc. And the gained Thickness Ratio is larger, so can be preferably applied to the keyboard switch of notebook computer etc.
Claims (9)
1. two-color molded product for laser marking, it is at least by supporter with cover the two-color molded product that the nappe of this supporter constitutes,
Wherein, above-mentioned supporter is made of the resin combination that contains following compositions: with respect to (A) thermoplastic resin 100 mass parts, (B) be selected from that carbon black, titanium are black, at least a kind particular energy absorbent 0.0001～5 mass parts in tri-iron tetroxide, mica, carbonate and the metal silicate, and (C) colouring agent 0～10 mass parts except that above-mentioned (B) composition;
Above-mentioned nappe is made of (D) transparent thermoplastic resin.
2. two-color molded product for laser marking as claimed in claim 1, wherein, above-mentioned supporter and above-mentioned nappe form by the common moulding of injection moulding.
3. two-color molded product for laser marking as claimed in claim 1 or 2, it is by laser light irradiation, and the part that is irradiated to of above-mentioned (A) thermoplastic resin is peeled off foaming, manifests more than any of white text, white symbol and white pattern.
4. two-color molded product for laser marking as claimed in claim 3, wherein, above-mentioned (A) thermoplastic resin is selected from MABS resin, methyl methacrylate/styrene copolymerized resin, polymethyl methacrylate resin, rubber-reinforced polymethyl methacrylate resin, nylon resin, polyacetal resin, polylactic acid based resin and the vistanex at least a kind.
5. two-color molded product for laser marking as claimed in claim 4, wherein, above-mentioned (A) thermoplastic resin is rubber-reinforced polymethyl methacrylate resin.
6. two-color molded product for laser marking as claimed in claim 1 or 2, it is by laser light irradiation, and the part generation carbonization that is irradiated to of above-mentioned (A) thermoplastic resin manifests more than any of black literal, black symbols and black pattern.
7. two-color molded product for laser marking as claimed in claim 6, wherein, above-mentioned (A) thermoplastic resin is selected from ABS resin, ASA resin, rubber-reinforced polystyrene resin, polycarbonate resin, pet resin, polybutylene terephthalate (PBT) resin, polyphenylene oxide resin, polyphenylene sulfide, acrylic resin, polyvinyl resin, ABS/ polycarbonate alloy resin and the ABS/ polybutylene terephthalate (PBT) alloy resin at least a kind.
8. as each described two-color molded product for laser marking in the claim 1～7, wherein, the thickness constituent ratio of above-mentioned nappe and above-mentioned supporter is nappe/supporter=1/9～9/1.
9. laser marking method, it is to each described two-color molded product for laser marking in the claim 1～8, with laser oscillation wavelength is that 532～1064nm, laser medium are that the laser-marking device irradiation of neodymium modified yttrium-aluminium-garnet or neodymium modification yttrium-four vanadium oxide prints, and the contrast of printing color development portion and basal part is more than 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005084995 | 2005-03-23 | ||
| JP084995/2005 | 2005-03-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101142089A true CN101142089A (en) | 2008-03-12 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800085836A Pending CN101142089A (en) | 2005-03-23 | 2006-03-20 | Two-color molded product for laser marking and laser marking method |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPWO2006101063A1 (en) |
| CN (1) | CN101142089A (en) |
| TW (1) | TW200702207A (en) |
| WO (1) | WO2006101063A1 (en) |
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- 2006-03-20 JP JP2007509253A patent/JPWO2006101063A1/en active Pending
- 2006-03-20 WO PCT/JP2006/305509 patent/WO2006101063A1/en active Application Filing
- 2006-03-20 CN CNA2006800085836A patent/CN101142089A/en active Pending
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2006101063A1 (en) | 2006-09-28 |
| JPWO2006101063A1 (en) | 2008-09-04 |
| TW200702207A (en) | 2007-01-16 |
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