CN101683793A - Polystyrene composition capable of being marked by laser and preparation method thereof - Google Patents
Polystyrene composition capable of being marked by laser and preparation method thereof Download PDFInfo
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- CN101683793A CN101683793A CN200810223641A CN200810223641A CN101683793A CN 101683793 A CN101683793 A CN 101683793A CN 200810223641 A CN200810223641 A CN 200810223641A CN 200810223641 A CN200810223641 A CN 200810223641A CN 101683793 A CN101683793 A CN 101683793A
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Abstract
The invention relates to a polystyrene composition capable of being marked by laser and a preparation method thereof. The composition contains the following blended components: 100 weight parts of polystyrene, 0.1 to 8 weight parts of powdered styrene-butadiene rubber or/and carboxylic powdered styrene-butadiene rubber with the average grain diameter between 50 and 200nm and the gel content more than 60 weight percent, and 0.01 to 0.2 weight part of carbon black. The preparation method comprises the step of performing melt blending on the components including the polystyrene, the powdered rubber and the carbon block according to the mixture ratio of the components. The composition can solve the problems that the polystyrene is difficultly marked by the laser and the reduction of physical and mechanical properties of a material is caused due to excessive addition of the prior laser additive. The preparation method has a simple and reliable process.
Description
Technical field
But the present invention relates to polyphenylacetylene combination of a kind of laser labelling and preparation method thereof, but be specifically related to a kind of under dark-background laser labelling light color seal target polyphenylacetylene combination and preparation method thereof.
Background technology
Polystyrene (PS) is formed by styrene polymerization, polystyrene is because raw material sources are abundant, polymerization technique is simple, excellent material performance, as light weight, inexpensive, water absorption rate is low, easy coloring, dimensional stability and good electrical property, goods are transparent, be easy to processing, thereby obtained using widely, be mainly used in meter case, household electrical appliance, toy for children, stationery, packing, high-frequency insulation material etc., making marks on these plastic products almost is an indispensable step in whole production processes, and more and more is subject to people's attention.
Laser marking is a kind of newer identification method, it is the high-energy that utilizes laser, making the frosting charing or making some composition of surface decompose generation gas makes plastic foamed, thereby obtain mark with the big aberration of primary colours, laser marking can substitute the present method that is useful on the plastics mark, and compare with the method for existing plastics mark and to have numerous advantages, at first laser marking device be labeled goods and do not contact, the medium that does not have mark to use, the material that environment is contacted with goods is without any pollution, the characteristic that also has fast and flexible, can the upper surface of goods and lower surface mark as: product brand, name of product, the date of production, useful life, bar code, literal such as series number, the mark of figure and symbol, utilize in addition laser marking method can also be on nonplanar surface mark, because laser labelling is to be recorded in goods inside, therefore wear-resisting lastingly, chemical stability is good, keeps permanent definition.Laser seal target precision is big, can satisfy the development need of printing mass data on the littler frosting of size.This is that conventional ink printer is difficult to realize.
Laser marking additives mostly is mica-based and applies multiple metal oxide, pigment, hydrated metal salt, metal oxide and composition thereof at present, as United States Patent (USP) 5,866,644 (open 1999 days, GE company) mentions, adding mineral black in polyester makes its background become black, add a certain amount of mica as laser absorbent, add a certain amount of hypophosphite monohydrate slaine (containing the crystallization water), under the laser irradiation, phosphate decomposes the release water outlet, and water evaporates causes plastic foamed, can obtain the seal mark of white like this under black background.Chinese patent 00809614.7 (open day 2002, DSM N.V.) but relate to a kind of laser labelling polymer composition, do laser marking additives with antimony trioxide and pearlescent pigment, can on light background, obtain dark mark, the particle size of antimony oxide is greater than 0.5 micron, most preferably be 2～5 microns, consumption is most preferably between 1～5%.Chinese patent 02809475.1 (open day 2004, Engelhard Corp) has been invented a kind of additive of the YAG of being specifically designed to laser labelling, and the YAG laser labelling agent of this invention is co-precipitation, the tin-oxide that mixes and the calcined powder of sb oxide.Adding 0.5～10wt% pearlescent pigment in the Chinese patent application 01116390.9 (open day calendar year 2001, Merck ﹠ Co., Inc.) can make the laser labelling of thermoplastic have quite high contrast.
Chinese patent 95192924.0 (open day 1997, Merck ﹠ Co., Inc.) mentions in, polyolefin and polystyrene are up to the present to be considered to be difficult to or may not use laser-marking, this patent uses the pigments, mica of doping stannic oxide coating as the plastics laser mark auxiliary agent, addition is 0.1～3%, adding to this pigment has metallic luster slightly in the transparent thermoplastics, but still transparent.
U.S. Pat 5,981,647 (1999 Japanese DCI) have described and formed white seal calibration method in the black resin matrixes.But in order to obtain the good laser seal mark resin of impact property, the resin combination of this invention is made up of styrene resin and acrylic resin.The mineral black of adding 0.01～3%, 0.01～10% Chinese white comprises CaCO
3, TiO
2(titanium white), ZnO, ZnS, lithopone, wherein the effect of titanium white is best, its dispersiveness.Shielding is good, can produce clear, tangible white seal mark.The size of Chinese white is at 0.01～1um, and consumption 0.1～3% is optimum.In above patent, all added the inorganic matter of high level as laser mark auxiliary agent, can obtain the good marking effect, but the physical and mechanical properties to material causes certain loss, also have the too high meeting of inorganic filler that conductivity of electrolyte materials is improved, material cost improves simultaneously, and these all can have influence on the application of material.U.S. Pat 5,981 adds the effect that inorganic Chinese white also can influence black background in 647.
Summary of the invention
But technical problem to be solved by this invention provides a kind of polyphenylacetylene combination of laser labelling, said composition can form light mark with Nd:YAG laser under dark-background, make seal mark and background have higher contrast ratio, and the physical and mechanical properties of base-material itself keep good.Said composition has overcome that polystyrene is difficult to carry out laser labelling and present laser additive dosage too much causes the problem that the physical and mechanical properties of material descends.
But the present invention further provides the preparation method of the polyphenylacetylene combination of described laser labelling.
But the polyphenylacetylene combination of laser labelling of the present invention includes the following component of blend: polystyrene, 100 parts by weight; Average grain diameter is that 50～200nm, gel content are the above butylbenzene powdered rubber of 60 weight % or/and carboxyl butylbenzene powdered rubber, the 0.1-8 parts by weight; Carbon black, the 0.01-0.2 parts by weight.
In the present invention, described polystyrene comprises the disclosed various types of polystyrene resins of prior art, comprises General Purpose Polystyrenre (GPPS) that mass polymerization and suspension polymerization make, the high impact polystyrene (HIPS) that makes with body-suspension method and grafting rubbers copolymerization and product that some have property etc.
In the present invention, described powdered rubber comprises the butylbenzene powdered rubber or/and carboxyl butylbenzene powdered rubber.Preferred average grain diameter is 50～200nm, is preferably 80～150nm; Gel content is 60 weight % or higher, is preferably 80 weight % or higher powdered rubber.This kind powdered rubber is preferably the rubber particles of equal phase structure.This kind powdered rubber is preferably the rubber particles of equal phase structure.This kind powdered rubber is selected from a kind of or its mixing in butylbenzene powdered rubber and the carboxyl butylbenzene powdered rubber.In polystyrene is 100 weight portions, and the powdered rubber consumption is 0.1～8 part, is preferably 0.3～3 part.Described powdered rubber consumption too much can reduce self physical and mechanical properties of polystyrene resin; Consumption crosses that I haven't seen you for ages and reduces the contrast of laser labelling, does not reach desirable mark effect.
Described powdered rubber can adopt according to the applicant in the prepared fully vulcanized powder rubber of the Chinese patent ZL00816450.9 of on September 18th, 2000 application (is priority with Chinese patent application 99125530.5, priority date on December 3rd, 1999).Be preferably form of finely divided powder, mehtod butadiene-styrene rubber or/and the form of finely divided powder, mehtod carboxylic styrene-butadiene rubber.This kind fully vulcanized powder rubber gel content reaches 60 weight % or higher, need not after the drying can flow freely with interleaving agent.Each particulate in this fully vulcanized powder rubber all is a homogeneous phase, and promptly single particulate all is a homogeneous on forming, and does not find layering in the particulate under the observation of existing microtechnic, divides the phenomenon that equates uneven phase.This fully vulcanized powder rubber gets by to the rubber latex cross-linking radiation rubber particles particle diameter being fixed.So the particle diameter of latex particle is consistent substantially in its average grain diameter and the rubber latex, the particle size scope of the latex particle that described rubber latex obtains when synthetic is the particle size range of gained fully vulcanized powder rubber particle, be generally 20～2000nm, preferred 30～1500nm, more preferably 50～500nm.
Above-described powdered rubber can also adopt the prepared cross-linked powdered rubber of Chinese patent ZL00130386.4 in application on November 3rd, 2000 according to the applicant.Be preferably cross-linked powdery butadiene-styrene rubber and/or cross-linked powdery carboxylic styrene-butadiene rubber.This kind cross-linked powdered rubber is a kind ofly (to have some rubber latexs between the rubber molecule certain cross can take place in synthetic process with cross-linking type synthetic rubber latex, thereby make resulting rubber latex have certain crosslinking degree, be referred to as crosslinking-type rubber latex) be raw material, the powdered rubber that drying obtains.The particle diameter of latex particle is consistent substantially in its average grain diameter and the crosslinking-type rubber latex, and the particle size scope of the latex particle that crosslinking-type rubber latex obtains when synthetic is the particle size range of gained cross-linked powdered rubber particle, is generally 50～300nm.This cross-linked powdered rubber need not add interleaving agent and can flow freely.Its gel content is consistent with gel content as the cross-linking type synthetic rubber latex of raw material, is 80% weight or higher, is preferably 85% weight or higher.Each particulate in this cross-linked powdered rubber all is a homogeneous phase, and promptly single particulate all is a homogeneous on forming, and does not find layering in the particulate under the observation of existing microtechnic, divides the phenomenon that equates uneven phase.
Described powdered rubber also can be the mixing of the above fully vulcanized powder rubber and cross-linked powdered rubber.
The inventor finds in the process of research laser marking plastics, in polystyrene, add dispensed in small quantity better elastic powdered rubber, can make the black polystyrene that is difficult for mark originally obtain the very high light mark of contrast, this is to form white seal mark because powdered rubber is easy to absorb laser and foaming and promotes, powdered rubber and polystyrene compatibility are fine simultaneously, be the good anti-impact modifier of polystyrene, the physical and mechanical properties of base-material do not had harmful effect so add powdered rubber.
In the present invention, described carbon black comprises disclosed all carbon blacks in the prior art, and preferable particle size is the carbon black of 10～90nm.Carbon black is given the effect of matrix resin black background and absorption laser in composition, is 100 weight portions in polystyrene, and the black pigment consumption is 0.01～0.2 part, is preferably 0.04～0.1 part.Described carbon black loading too much not only can influence the physical property of polystyrene, also can improve the cost of material; The very few composition that can not guarantee of consumption is a black background, reduces the contrast of laser labelling.
But the polyphenylacetylene combination of laser labelling of the present invention can also include white oil, and white oil can improve powdered rubber particle and the dispersiveness of pearlescent pigment particle in polystyrene resin, can also improve the processing characteristics of polyphenylacetylene combination.In polystyrene is 100 weight portions, and the consumption of described white oil is 0.1～0.5 weight portion.The white oil consumption too much can reduce the processing characteristics and the physical property of polyphenylacetylene combination, and consumption crosses that I haven't seen you for ages and reduce the dispersiveness of laser auxiliary agent.
In addition, but also can include polystyrene processing aid commonly used in the polyphenylacetylene combination of laser labelling of the present invention, as lubricant, antioxidant etc.Wherein lubricant such as calcium stearate, zinc stearate, stearic acid etc.; Antioxidant such as primary antioxidant 1076,1010, auxiliary antioxidant such as antioxidant 168, TPP etc.The consumption of the processing aid that these are commonly used is a conventional amount used, or suitably adjusts according to practical requirements.
But the present invention further provides the preparation method of the polyphenylacetylene combination of above-mentioned laser labelling.
But the preparation method of the polyphenylacetylene combination of laser labelling of the present invention comprises that the component that will include described polystyrene, powdered rubber, carbon black compares melt blending by described set of dispense.
In the preparation process of polyphenylacetylene combination of the present invention, material melt blending temperature is used blending temperature in the common polystyrene processing, can decide according to the polystyrene melt temperature, should select not only guaranteeing the complete fusion of polystyrene matrix plastics but also can not make in the scope of its decomposition.In addition, according to the processing needs, can add some auxiliary agents such as lubricant, antioxidant etc. commonly used in the polystyrene process in right amount in the blend material, its consumption is conventional amount used, or adjusts according to practical requirements.
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 mixer, 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 double screw extruder, single screw extrusion machine, mill or banbury etc.
But the preferred for preparation method of the polyphenylacetylene combination of laser labelling of the present invention comprises:
(1) the polystyrene base-material is even with a small amount of white oil high-speed mixing, p-poly-phenyl ethene carries out surface treatment, polystyrene and black pigment, nanometer grade powder rubber, the processing aid of handling well is mixed in high-speed mixer again;
(2) compound melt extrudes in the WPZSK25 double screw extruder, cooling and dicing.
(3) with the gained pellet 90 ℃ of dryings 4 hours, in 220 ℃ of injection mouldings, and preparation standard batten on request, the reflectivity of laser labelling and test badge is according to the cantilever beam notched Izod impact strength (outstanding lacking dashes) of the canonical measure composition of ASTM D 256.
The laser instrument that polyphenylacetylene combination of the present invention is carried out laser labelling can be CO
2Laser instrument (wavelength 10600nm), Nd:YAG laser instrument (wavelength 1064nm and 532nm), pulse UV laser instrument (excimer laser), especially semiconductor N d:YAG laser instrument (wavelength 1064nm).
Can whether smooth, clear to the sign of mark by visual font mark lines, whether the large tracts of land labeled surface is smooth determines, can also be with spectrophotometer degree of comparing quantitative test.
Preparation method's simple and reliable process of the present invention, in polystyrene, add dispensed in small quantity better elastic powdered rubber, can make the black polystyrene that is difficult for mark originally obtain the very high light mark of contrast, powdered rubber and polystyrene compatibility are fine simultaneously, be the good anti-impact modifier of polystyrene, the physical and mechanical properties of base-material do not had harmful effect so add powdered rubber.
The present invention can be applied to need in nearly all industrial department to carry out on the polystyrene article of mark.For example, often need on article, indicate the trade mark, series number etc. of date of manufacture, validity date, bar code, company.
The specific 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.
Adopt laser engineering branch company of China DaHeng (group) Co., Ltd to produce the semiconductor pumped YAG laser marking machine of DH-MFD03 type in following examples and the Comparative Examples sample is carried out the laser labelling test.
Measure the reflectivity of marked region and the reflectivity of background area with Datacolor SF300 (U.S.) spectrophotometer in following examples and the Comparative Examples, the test wave-length coverage is 400～700nm, and reflectivity is with D
65Light source is the basis, and test badge is the border circular areas of diameter 13mm.
Contrast=mark reflectivity/background reflectance rate
The contrast of mentioning in following examples and the Comparative Examples obtains by spectrophotometer, promptly utilize spectrophotometric D65 light source irradiating laser marked region and background area, the Y value of gained test result can be reacted actual conditions, generally is that zone shallow more, bright then Y value is big more.The ratio of the Y value of light areas and the Y value of darker regions is contrast I of the present invention.The value of contrast I is big more, writing is clear more, shows that then the mark effect is good more.
In addition, can also whether smooth and clear by the visual assessment marked region.
Embodiment 1～8
Place homogenizer to handle polystyrene resin (trade mark is 666D, Sinopec Yanshan Mountain branch company) and white oil (technical grade, commercially available); Polystyrene after will handling then, vulcanize nanometer grade powder butadiene-styrene rubber (trade mark VP 101 entirely, Beijing's northization is ground chemical industry New Tech S. R. L., particle diameter 80nm, gel content 90%), (U.S. Cabot company produces charcoal blacks, the trade mark is M470) stir after, compound added carries out melt blending in the double screw extruder (German WP company, model is ZSK-25) and extrude the back granulation, extrusion temperature is 180～210 ℃, screw speed 350rpm.The pellet of extruding is dried 4hr in 90 ℃ of baking ovens, under 220 ℃ condition, be injected into the standard batten then, carry out laser labelling test and Mechanics Performance Testing.Concrete prescription sees Table 1, and results of property is as shown in table 1.
Comparative example 1～2:
Except that do not add the butylbenzene 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 constituent content is all in weight portion.Results of property is as shown in table 1.
Table 1
| ??PS | ??VP101 | ??M470 | White oil | Contrast | Indicia appearance | Outstanding lacking, dash | |
| Unit | Weight portion | Weight portion | Weight portion | Weight portion | ??/ | ??/ | ??J/m |
| Comparative example 1 | ??100 | ??/ | ??/ | ??1 | ??/ | Some discontinuous stains | ??11.3 |
| Comparative example 2 | ??100 | ??/ | ??0.05 | ??1 | ??2.04 | Generally | ??10.9 |
| Embodiment 1 | ??100 | ??0.5 | ??0.05 | ??1 | ??3.36 | Good | ??12.9 |
| Embodiment 2 | ??100 | ??1 | ??0.05 | ??1 | ??3.50 | Good | ??13.6 |
| Embodiment 3 | ??100 | ??3 | ??0.05 | ??1 | ??3.78 | Good | ??14.1 |
| Embodiment 4 | ??100 | ??5 | ??0.05 | ??1 | ??3.99 | Good | ??14.9 |
| Embodiment 5 | ??100 | ??8 | ??0.05 | ??1 | ??4.30 | Fine | ??16.3 |
| Embodiment 6 | ??100 | ??3 | ??0.1 | ??1 | ??3.90 | Good | ??11.9 |
| Embodiment 7 | ??100 | ??0.3 | ??0.05 | ??1 | ??3.30 | Good | ??12.2 |
| Embodiment 8 | ??100 | ??3 | ??0.03 | ??1 | ??3.45 | Good | ??14.3 |
(the used power of laser marking is 14.5W)
The embodiment that lists from table 1 and the result of Comparative Examples are as can be seen, adding an amount of VP101 powdered rubber and carbon black in polystyrene can make the contrast of laser labelling be significantly improved, the mark effect obviously improves, simultaneously because the adding of powdered rubber also makes the impact strength of material obtain raising to a certain degree.
Claims (9)
1. but the polyphenylacetylene combination of a laser labelling includes the following component of blend: polystyrene, 100 parts by weight; Average grain diameter is that 50～200nm, gel content are the above butylbenzene powdered rubber of 60 weight % or/and carboxyl butylbenzene powdered rubber, the 0.1-8 parts by weight; Carbon black, the 0.01-0.2 parts by weight.
2. but the polyphenylacetylene combination of laser labelling as claimed in claim 1, it is characterized in that: the average grain diameter of described powdered rubber is 80～150nm.
3. but the polyphenylacetylene combination of laser labelling as claimed in claim 1, it is characterized in that: the gel content of described powdered rubber is 80 weight % or higher.
But 4. the polyphenylacetylene combination of laser labelling as claimed in claim 1, it is characterized in that: in polystyrene is 100 weight portions, described powdered rubber is 0.3～3 parts by weight.
5. but the polyphenylacetylene combination of laser labelling as claimed in claim 1, it is characterized in that: described powdered rubber is that fully vulcanized powder rubber is or/and cross-linked powdered rubber.
But 6. the polyphenylacetylene combination of laser labelling as claimed in claim 1, it is characterized in that: in polystyrene is 100 weight portions, described carbon black is 0.04～0.1 parts by weight.
But 7. the polyphenylacetylene combination of laser labelling as claimed in claim 1, it is characterized in that: described composition also includes white oil, is 100 weight portions in polystyrene, and the consumption of described white oil is 0.1～0.5 weight portion.
8. but as the preparation method of the polyphenylacetylene combination of each described laser labelling of claim 1～7, comprise that the component that will include described polystyrene, powdered rubber, carbon black compares melt blending by described set of dispense.
9. but the preparation method of the polyphenylacetylene combination of laser labelling as claimed in claim 8, it is characterized in that: carry out surface treatment with white oil p-poly-phenyl ethene, again polystyrene of handling well and the component that comprises powdered rubber, carbon black are compared melt blending by described set of dispense.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106696474A (en) * | 2016-12-19 | 2017-05-24 | 武汉华工激光工程有限责任公司 | Bottle cap, laser marking device and method |
| CN109130570A (en) * | 2018-07-26 | 2019-01-04 | 广州艾德旺斯珠宝科技有限公司 | A kind of laser marking method, electronic equipment and storage medium |
| CN110408165A (en) * | 2019-08-09 | 2019-11-05 | 四川大学 | A kind of discoloration auxiliary agent and preparation method thereof for manufacturing white or light-colored label |
| CN116178851A (en) * | 2021-11-26 | 2023-05-30 | 上海金发科技发展有限公司 | Styrene compound, product, preparation method and application thereof |
-
2008
- 2008-09-28 CN CN200810223641A patent/CN101683793A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106696474A (en) * | 2016-12-19 | 2017-05-24 | 武汉华工激光工程有限责任公司 | Bottle cap, laser marking device and method |
| CN109130570A (en) * | 2018-07-26 | 2019-01-04 | 广州艾德旺斯珠宝科技有限公司 | A kind of laser marking method, electronic equipment and storage medium |
| CN110408165A (en) * | 2019-08-09 | 2019-11-05 | 四川大学 | A kind of discoloration auxiliary agent and preparation method thereof for manufacturing white or light-colored label |
| CN110408165B (en) * | 2019-08-09 | 2022-04-05 | 四川大学 | Color change additive for manufacturing white or light-colored mark and preparation method thereof |
| CN116178851A (en) * | 2021-11-26 | 2023-05-30 | 上海金发科技发展有限公司 | Styrene compound, product, preparation method and application thereof |
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Open date: 20100331 |