CN101418110B - Laser marked resin composite and preparation method thereof - Google Patents
Laser marked resin composite and preparation method thereof Download PDFInfo
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- CN101418110B CN101418110B CN2007101764046A CN200710176404A CN101418110B CN 101418110 B CN101418110 B CN 101418110B CN 2007101764046 A CN2007101764046 A CN 2007101764046A CN 200710176404 A CN200710176404 A CN 200710176404A CN 101418110 B CN101418110 B CN 101418110B
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Abstract
The present invention relates to a resin composition which can be labeled by laser. The laser composition comprises acrylonitrile-butadiene-styrene copolymer, polycarbonate and acrylate powdered rubber, wherein the weight ratio of the acrylonitrile-butadiene-styrene copolymer to the polycarbonate is between 90 to 10 and 10 to 90, and the content of the acrylate powdered rubber is between 0.5 and 8percent of the total weight of the acrylonitrile-butadiene-styrene copolymer and the polycarbonate. The present invention also relates to a method for preparing plastic which can be labeled by the laser. The resin composition which can be labeled by the laser can obtain a laser label of a higher contrast under the action of the laser. The preparation method has simple and reliable process.
Description
Technical field
But the present invention relates to resin combination of a kind of mark and preparation method thereof, but be specifically related to a kind of laser labelling by resin combination of acrylonitrile-butadiene-styrene copolymer and polycarbonate blending and preparation method thereof.
Background technology
In nearly all industrial sector, on the production article, label and become more and more important.For example, often need on article, indicate the trade mark, series number etc. of date manufactured, expiration date, barcode, company.
At present, the technological method that stamps mark on object is a lot, all is well-known printing technology as silk screen printing and trans-printing, embossing, impression, printing ink seal etc.These printing processes belong to surface printing, this just means is difficult to identification because physical abuse, rubbing effect, chemical action and similar effect make resulting identification marking become, and this printing process is difficult to be applied to curved surface or net grain surface, and required special processing charges has increased the overall cost of product.
It also is well-known adopting laser system to come the benefit of marking objects: contactless property, high speed and flexible mark.Laser labeling method is such process: use laser, by with laser radiation target compound surface, literal, figure and symbol, barcode or image placed from the teeth outwards or the surface down.Laser labelling allow mark to be on the body surface or the surface down, mark is positioned at and helps mark under the body surface and remove the difficulty and false proof that becomes.In addition, the laser labelling technology can also be recorded in logotype such as barcode on nonplanar surface fast, makes the handiness of mark increase.Because it is the sign of laser labelling is to be recorded in the article itself, therefore wear-resisting lastingly.Laser seal target precision is big, this satisfied in addition littler plastics or metallic article on print the development need of mass data.
ABS (acrylonitrile-butadiene-styrene copolymer) resin has shock resistance, high rigidity, oil-proofness, performance such as low temperature resistant, is easy to processing, and the finish size good stability is widely used in fields such as automobile, electronic apparatus, instrument; PC (polycarbonate) high comprehensive performance, heat-resisting, cold-resistant, high-impact.The two blend has improved resistance toheat and the mechanical property of ABS; Reduced on the other hand PC tooling cost and melt viscosity, improved flowability, can improve its processibility.Therefore, the ABS/PC alloy is the alloy material that is widely used in electrical equipment, auto-parts at present.Owing to need to carry out mark on a lot of ABS/PC products, the laser labelling of raising ABS/PC highly significant.
But USPA20010021731 has described a kind of laser seal target plastics composite, comprises polymkeric substance, hotchpotch, comprises the graphite with which floor coating in the hotchpotch, and wherein applicator is CaCO
3, CaSO
4, Turnbull ' indigo plant, carbon black, TiO
2, (Sn, Sb) O
2(tin-antimony mixed oxide), or these substance mixture.1～4 layer of coating arranged on the graphite, and the middle layer is (Sn, Sb) O
2, TiO
2Or its mixture.Wherein hotchpotch is as the laser promotor of plastics.The mark effect is better, but the hotchpotch preparation is complicated, the cost height.
But US 6482879 has described laser seal target composition, comprising thermoplastic polyester, light pigment, laser auxiliary agent such as FUMARIC ACID TECH GRADE ketone, toxilic acid ketone make vibrin decompose under lasing to form black seal mark, addition is 0.5～5%, is preferably between 1～3%.The mark contrast gradient is higher, but the lines of mark are fine and smooth inadequately.
Summary of the invention
The present invention finds acrylate powder rubber is added in the ABS/PC resin combination as the laser auxiliary agent, and this resin combination has good laser labelling performance.
The purpose of this invention is to provide the very excellent ABS/PC resin combination of a kind of laser labelling performance, and can not change this resin combination institute inherent thermal characteristics and mechanical property.
But the present invention further provides the preparation method of the resin combination of above-mentioned laser labelling.
But the resin combination of laser labelling of the present invention, it comprises acrylonitrile-butadiene-styrene copolymer (ABS), polycarbonate (PC) and acrylate powder rubber, wherein the weight ratio of acrylonitrile-butadiene-styrene copolymer and polycarbonate is 90: 10～10: 90, be preferably 80: 20～and the content of 20: 80 acrylate powder rubber is 0.5～8% weight based on acrylonitrile-butadiene-styrene copolymer and polycarbonate gross weight.
In the present invention, the median size of described acrylate powder rubber is 50～200nm, is preferably 100～150nm.Its gel content is 60 weight % or higher, is preferably 75% weight or higher.
The thermoplastic engineering plastic that to invent selected resin PC be a kind of high comprehensive performance, with the ABS resin blend, the alloy material that obtains has good shock strength, flexibility, rigidity and thermotolerance, has good processing properties simultaneously again.PC is a kind of transparent resin, laser labelling better performances, but because transparent its mark effect that also influences.
The laser labelling performance of ABS/PC alloy (blend composition of ABS and PC) is better than the laser labelling performance of pure ABS, but still needs bigger laser output power during mark, and the vestige of mark font is fuzzy, unintelligible, fineless and smooth simultaneously.
The present invention has found that acrylate powder rubber joins the effect that can play laser absorbent in the ABS/PC alloy, acrylate powder rubber not only can improve the laser labelling of composition, contrast gradient is greatly improved, and the lines of mark font or figure obviously become clear, fine and smooth.
Acrylate powder rubber adds too many and all can influence the contrast gradient size very little, and acrylate powder rubber is very few not to have effect, too much can make the mark lines fine and smooth inadequately, and line color is yellow partially.So the add-on of acrylate powder rubber is selected from 0.5～8% weight based on ABS/PC weight in the present composition, preferred 2～6% weight, more preferably 2～4% weight.
Acrylate powder rubber of the present invention can be chosen the applicant, and (with Chinese patent application 99125530.5 is right of priority in the Chinese patent ZL00816450.9 of application on September 18th, 2000, priority date on December 3rd, 1999) prepared median size is 50～200nm, be preferably 100～150nm, gel content and be 60% weight or higher, be preferably 75% weight or higher acrylate powder rubber, also can grind chemical industry New Tech S. R. L. by Beijing's northization provides, commodity wherein are called Narpow, series of acrylate (VP301).
But the invention still further relates to a kind of method of resin combination of the present invention's of preparation laser labelling, but it is characterized in that the component that will comprise described acrylonitrile-butadiene-styrene copolymer, polycarbonate and acrylate powder rubber makes the resin combination of laser labelling by melt blending.What it was concrete may further comprise the steps:
(1) mixes: ABS and PC are mixed in high speed agitator; Acrylate powder rubber is joined in the ABS/PC alloy, and stirring at low speed is even then, discharging;
(2) extrude the back granulation with carrying out melt blending in the material adding melt blending equipment that mixes, but prepare the resin combination of laser labelling, wherein the temperature of melt blending equipment is the conventional melt processing temperature of ABS and PC, generally can be 230～255 ℃.
Injection moulding prepares sample behind cooling and dicing, the dry packing, and injection temperature is the conventional injecting forming temperature of ABS and PC, can be 230～250 ℃, then laser marking.
The blending equipment of mixing of materials can adopt various mixing equipments used in the prior art in preparation method of the present invention, as stirrer, kneading machine etc.
Employed melt blending equipment is the general blending equipment in the rubber and plastic processing industry in preparation method of the present invention, can be twin screw extruder, single screw extrusion machine, mill or Banbury mixer etc.
The optical maser wavelength that is used for plastics mark of the present invention can be at 200～10640nm, and particularly the high-energy radiation at 200～1064nm carries out mark.Can be with producing excimer laser that wavelength is a 200nm laser, can produce Nd:YAG laser apparatus that wavelength is 1064nm and 532nm laser, can producing the CO that wavelength is a 10640nm laser
2Laser apparatus.Be the laser labelling that the Nd:YAG laser apparatus of 1064nm laser carries out polymkeric substance preferably with producing wavelength.Wherein optional lamp pump laser of Nd:YAG laser apparatus (comprising semiconductor pump laser) and diode laser, preferred diode laser.
But resin by laser labelling of the present invention and preparation method thereof can be prepared the good ABS/PC alloy of labeling properties, and this resin combination can form dark mark under laser radiation, form mark and background has higher contrast ratio.Preparation method's simple and reliable process of the present invention.Plastics of the present invention need in the industrial sector can be applied to carry out on the article of plastics preparation of mark.
Embodiment
Further describe the present invention below in conjunction with embodiment.Scope of the present invention is not subjected to the restriction of these embodiment, and scope of the present invention proposes in the appended claims.
The testing method of the laser labelling of material and performance thereof is as follows in embodiment and the Comparative Examples:
Laser labelling: the present invention adopts that laser engineering branch office of China DaHeng (group) company limited produces, and to produce wavelength be that the DH-MFD03 N-type semiconductorN pumping Nd:YAG laser marking machine of 1064nm laser carries out the laser marking test to sample.Output rating during laser marking is 13.0W.
The test of laser labelling: the present invention adopts contrast gradient to characterize the laser labelling of plastics, promptly utilize spectrophotometric D65 rayed laser labelling zone and background area, adopt spectrophotometer respectively testing laser marked region (darker regions) and background area (light areas) to visible reflectance (reflection sources is a benchmark with spectrophotometer D65 light source) Y value, by following formula calculating contrast gradient:
Contrast gradient I=light areas is to the reflectivity Y1/ darker regions of the visible light reflectivity Y2 to visible light
The visible reflectance Y value of gained test result can be reacted practical situation, generally is that zone shallow more, bright then Y value is big more.The ratio of the Y1 value of light areas and the Y2 value of darker regions is contrast gradient of the present invention.The value of contrast gradient is big more, writing is clear more, shows that then the mark effect is good more.The value of contrast gradient has reflected an aspect of mark situation; Be on the other hand, can also whether smooth and clear by the lines of marked region after the visual assessment mark, so in the mark process also requirement the lines flow smoothly, attractive in appearance.
Spectrophotometer adopts U.S. Datacolor company to produce SF300 type spectrophotometer in the embodiment of the invention and the Comparative Examples.
Embodiment 1～11:
With PC (U.S. GE company) and ABS (strange beautiful production the in Taiwan), ultra-fine full propylene sulfide acid esters powdered rubber (trade mark VP301, the China Petrochemical Industry Beijing Chemical Research Institute, particle diameter 120nm, gel content 85wt%) place homogenizer to stir after, compound is added twin screw extruder (German WP company, model ZSK-25) carry out melt blending in and extrude the back granulation, each section extrusion temperature is 230-240-245-250-255-250 ℃, screw speed 350RPM.Pellet 80 ℃ of baking 6Hr in baking oven with extruding are injected into the standard batten then under 230-240-250-250 ℃ temperature condition, carry out laser labelling test and correlated performance test.Concrete prescription sees Table 1, and wherein each component concentration is all in weight part.Results of property is as shown in table 1.
Comparative Examples 1～6:
Except that not adding the ultra-fine full propylene sulfide acid esters powdered rubber and the difference of specifically filling a prescription, all the other conditions are all identical with previous embodiment.Concrete prescription sees Table 1, and wherein each component concentration is all in weight part.Results of property is as shown in table 1.
Table 1
| Sample | ABS (weight part) | PC (weight part) | VP301 (weight part) | Contrast gradient I | The mark effect |
| Embodiment 1 | 90 | 10 | 4 | 5.2 | Mark is more obvious, and lines are fine and smooth |
| Embodiment 2 | 80 | 20 | 0.5 | 5.1 | Mark is more obvious, and lines are fine and smooth |
| Embodiment 3 | 80 | 20 | 1 | 5.1 | Mark is more obvious, the lines exquisiteness |
| Embodiment 4 | 80 | 20 | 2 | 5.4 | Mark clearly, the lines exquisiteness |
| Embodiment 5 | 80 | 20 | 4 | 5.71 | Mark clearly, the lines exquisiteness |
| Embodiment 6 | 80 | 20 | 8 | 5.0 | Mark is more obvious, the lines exquisiteness |
| Embodiment 7 | 50 | 50 | 2 | 5.2 | Mark is more obvious, the lines exquisiteness |
| Embodiment 8 | 50 | 50 | 4 | 5.4 | Mark clearly, the lines exquisiteness |
| Embodiment 9 | 40 | 60 | 2 | 5.0 | Mark is more obvious, the lines exquisiteness |
| Sample | ABS (weight part) | PC (weight part) | VP301 (weight part) | Contrast gradient I | The mark effect |
| Embodiment 10 | 40 | 60 | 4 | 5.3 | Mark clearly, the lines exquisiteness |
| Embodiment 11 | 10 | 90 | 4 | 5.3 | Mark clearly, the lines exquisiteness |
| Comparative Examples 1 | 100 | -- | -- | 4.2 | Mark is more obvious, but the writing lines are fuzzy, fineless and smooth |
| Comparative Examples 2 | 90 | 10 | -- | 4.2 | Mark is more obvious, but the writing lines are fuzzy, fineless and smooth |
| Comparative Examples 3 | 80 | 20 | -- | 4.5 | Mark is more obvious, but the writing lines are fuzzy, fineless and smooth |
| Comparative Examples 4 | 50 | 50 | -- | 4.4 | Mark is more obvious, but the writing lines are fuzzy, fineless and smooth |
| Comparative Examples 5 | 40 | 60 | -- | 4.6 | Mark is more obvious, but the writing lines are fuzzy, fineless and smooth |
| Comparative Examples 6 | 10 | 90 | -- | 4.3 | Mark is more obvious, but the writing lines are fuzzy, fineless and smooth |
The test performance result is as shown in table 1.From above data as can be known, behind the adding powdered rubber, the contrast gradient of mark is improved, and mark is more clear.
Claims (6)
1. but the resin combination of a laser labelling, it comprises acrylonitrile-butadiene-styrene copolymer, polycarbonate and acrylate powder rubber, wherein the weight ratio of acrylonitrile-butadiene-styrene copolymer and polycarbonate is 90: 10～10: 90, and the content of acrylate powder rubber is 0.5～8% weight based on acrylonitrile-butadiene-styrene copolymer and polycarbonate gross weight; The median size of described acrylate powder rubber is 50～200nm, and its gel content is 60 weight % or higher.
2. but the resin combination of laser labelling according to claim 1, the weight ratio that it is characterized in that described acrylonitrile-butadiene-styrene copolymer and polycarbonate is 80: 20～20: 80.
3. but the resin combination of laser labelling according to claim 1, the median size that it is characterized in that described acrylate powder rubber is 100～150nm.
4. but the resin combination of laser labelling according to claim 1, the gel content that it is characterized in that described acrylate powder rubber is 75 weight % or higher.
5. but the resin combination of laser labelling according to claim 1 is characterized in that the content of described acrylate powder rubber is 2～6% weight based on acrylonitrile-butadiene-styrene copolymer and polycarbonate gross weight.
6. but the method for the resin combination of the laser labelling of one of preparation claim 1-5, but it is characterized in that the component that will comprise described acrylonitrile-butadiene-styrene copolymer, polycarbonate and acrylate powder rubber makes the resin combination of laser labelling by melt blending.
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|---|---|---|---|
| CN2007101764046A CN101418110B (en) | 2007-10-26 | 2007-10-26 | Laser marked resin composite and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101764046A CN101418110B (en) | 2007-10-26 | 2007-10-26 | Laser marked resin composite and preparation method thereof |
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| CN101418110B true CN101418110B (en) | 2010-04-21 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101927626B (en) * | 2009-06-18 | 2013-08-07 | 河南天海电器有限公司 | Master batch with function of plastic laser marking |
| CN103059557A (en) * | 2011-10-20 | 2013-04-24 | 合肥杰事杰新材料股份有限公司 | PA/ABS alloy with laser identification function, and preparation method thereof |
| CN108003550A (en) * | 2017-11-21 | 2018-05-08 | 天津金发新材料有限公司 | A kind of low smoke, it is antistatic, can laser labelling ABS composite material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1171130A (en) * | 1994-12-27 | 1998-01-21 | 巴斯福股份公司 | Thermoplastic moulding composition based on graft copolymer and block copolymer |
| EP0910058B1 (en) * | 1997-10-14 | 2002-02-06 | Minnesota Mining And Manufacturing Company | Recyclable label |
| CN1400573A (en) * | 2001-08-04 | 2003-03-05 | 大连路明发光科技股份有限公司 | Luminous-reflecting mark band and its making method |
| CN1668454A (en) * | 2002-07-18 | 2005-09-14 | 艾利丹尼森公司 | Multilayer in-mold film |
| CN1769345A (en) * | 2004-10-27 | 2006-05-10 | 中国石油化工股份有限公司 | High-brilliance high-ductility polycarbonate composition and its preparation method |
-
2007
- 2007-10-26 CN CN2007101764046A patent/CN101418110B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1171130A (en) * | 1994-12-27 | 1998-01-21 | 巴斯福股份公司 | Thermoplastic moulding composition based on graft copolymer and block copolymer |
| EP0910058B1 (en) * | 1997-10-14 | 2002-02-06 | Minnesota Mining And Manufacturing Company | Recyclable label |
| CN1400573A (en) * | 2001-08-04 | 2003-03-05 | 大连路明发光科技股份有限公司 | Luminous-reflecting mark band and its making method |
| CN1668454A (en) * | 2002-07-18 | 2005-09-14 | 艾利丹尼森公司 | Multilayer in-mold film |
| CN1769345A (en) * | 2004-10-27 | 2006-05-10 | 中国石油化工股份有限公司 | High-brilliance high-ductility polycarbonate composition and its preparation method |
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