CN101293985B - Polystyrene composition capable of marking with laser and preparation thereof - Google Patents
Polystyrene composition capable of marking with laser and preparation thereof Download PDFInfo
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- CN101293985B CN101293985B CN2007100988514A CN200710098851A CN101293985B CN 101293985 B CN101293985 B CN 101293985B CN 2007100988514 A CN2007100988514 A CN 2007100988514A CN 200710098851 A CN200710098851 A CN 200710098851A CN 101293985 B CN101293985 B CN 101293985B
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Abstract
The invention relates to a laser-marked polystyrene composition and a preparation method thereof. The composition comprises the blend of the following components: 100 weight parts of polystyrene and 0.1-10 weight parts of powdered rubber, wherein the powdered rubber is composed of powdered styrene-butadiene rubber and powdered carboxylated styrene-butadiene rubber. The preparation method comprises the steps of proportioning the components including polystyrene and powdered rubber, melting, and blending. The composition overcomes the problems that the polystyrene cannot conduct laser marking and an excessive amount of laser auxiliary in material can cause the decrease in physical and mechanical properties and light transmittance and the increase in price. The preparation method is simple and reliable.
Description
Technical field
But the present invention relates to polyphenylacetylene combination of a kind of laser labelling 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-intake 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 plastics almost is an indispensable step in the full scale production process, 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, time limit of service, barcode, 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 sharpness.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) 5866644 (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 metal-salt (containing crystal water), under laser radiation, phosphoric acid salt decomposes the release water outlet, 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 SB 203 99.8 PCT and pearly pigment, can on light background, obtain dark mark, the size of particles of antimonous 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% pearly pigment in the Chinese patent application 01116390.9 (open day calendar year 2001, Merck ﹠ Co., Inc.) can make the laser labelling of thermoplastics have quite high contrast gradient.In above patent documentation, all added the inorganics 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, can destroy the mechanical property of resin, especially impact property, also have the too high meeting of mineral filler that conductivity of electrolyte materials is improved, more meeting reduces the material transmittance greatly for the transparent material addition, and antimonous oxide and pearly pigment cost an arm and a leg, material cost improves, and these all can have influence on the application of material.
Chinese patent 95192924.0 (open day 1997, Merck ﹠ Co., Inc.) mentions in, polyolefine 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 metalluster slightly in the transparent thermoplastics, but still transparent.Chinese patent 01143302.7 (open day 2002, Merck ﹠ Co., Inc.) but relate to a kind of transparent or semitransparent plastics of laser labelling, this invention is chosen in the laser-sensitive pigment that adds pearly pigment and itself do not have any pearl effect in the plastics, can be observed the liquid level and the color of interior dress liquid with the bottle of this preparation of compositions.These two pieces of patents all relate to transparent and translucent plastic, but transparency is not had quantized sign, and used inorganic assistant agent amount certainly will cause greater loss to the transparency of material than higher.
Summary of the invention
But technical problem to be solved by this invention provides a kind of polyphenylacetylene combination of laser labelling, and said composition can overcome that polystyrene is difficult to carry out laser labelling and present laser additive dosage causes that too much the physical and mechanical properties of material descends, transmittance descends and expensive problem.
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; Powdered rubber, the 0.1-10 parts by weight; Pearly pigment, the 0-1 parts by weight; Wherein said powdered rubber comprises the butylbenzene powdered rubber or/and carboxyl butylbenzene powdered rubber is preferably the butylbenzene powdered rubber.
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 compares melt blending by described set of dispense.
In the present invention, described polystyrene comprises the disclosed various types of polystyrene resins of prior art, comprises mass polymerization polystyrene and suspension polymerization polystyrene etc.
In the present invention, described powdered rubber comprises the butylbenzene powdered rubber or/and carboxyl butylbenzene powdered rubber.Preferred median size 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.
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 right of priority with Chinese patent application 99125530.5, priority date on December 3rd, 1999).Be preferably form of finely divided powder, mehtod styrene-butadiene rubber(SBR) 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 to get final product unrestricted flow with separant.Each particulate in this fully vulcanized powder rubber all is a homogeneous, and promptly single particulate all is a homogeneous on forming, and does not find layering in the particulate under the observation of existing microtechnique, 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 median size and the rubber latex, the 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 styrene-butadiene rubber(SBR) 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 the 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 median size and the crosslinking-type rubber latex, and the 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 separant and get final product unrestricted flow.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, and promptly single particulate all is a homogeneous on forming, and does not find layering in the particulate under the observation of existing microtechnique, 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 transparent polystyrene, add paucidisperse good elasticity powdered rubber, can make the polystyrene that is difficult to mark originally obtain the very low density bullet of reflectivity, this is because powdered rubber helps laser absorption and becomes charcoal rapidly, can be so that laser marking significantly improves, form density bullet, simultaneously because the particle of powdered rubber is very tiny, particle diameter is significantly smaller than visible wavelength, join in the polystyrene less on a small quantity to its light transmission influence, also have powdered rubber and polystyrene consistency fine, be the good anti-impact modifier of polystyrene, the physical and mechanical properties of base-material do not had detrimentally affect so add powdered rubber.
In polystyrene is 100 weight parts, and described powdered rubber consumption is the 0.1-10 weight part, is preferably the 0.3-2.0 weight part, more preferably the 0.3-0.8 weight part.Described powdered rubber consumption too much can reduce its dispersiveness in polystyrene resin, thereby influences the light transmission of material; Consumption crosses that I haven't seen you for ages and reduces the color of laser labelling, does not reach ideal mark effect.
But the polyphenylacetylene combination of laser labelling of the present invention can also comprise pearly pigment, described pearly pigment generally is to be the sheet base with silicate such as light mica or white clouds master slices, the platy particle that covers which floor metal oxide again and obtain, metal oxide is selected from SnO
2, TiO
2, Fe
2O
3(Sn, Sb) O
2In at least a.Pearly pigment is as the auxiliary addition agent that applies dark laser labelling, be a kind of laser absorbent in essence, described pearly pigment has high refractive index, the compound laser sign property that can significantly improve polystyrene of pearly pigment and powdered rubber, making polyphenylacetylene combination of the present invention can be that the Laser Printing of 1064nm goes out mark clearly with wavelength.In polystyrene is 100 weight parts, and the pearly pigment consumption is the 0-1 weight part, is preferably the 0.05-0.3 weight part, more preferably the 0.05-0.1 weight part.Described pearly pigment consumption too much not only can influence the physicals of polystyrene, also can improve the cost of material; Consumption crosses that I haven't seen you for ages influences the absorption of material for laser light, reduces the sharpness 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 pearly pigment particle in polystyrene resin, can also improve the processing characteristics of polyphenylacetylene combination.In polystyrene is 100 weight parts, and the consumption of described white oil is 0.1～0.5 weight part.The white oil consumption too much can reduce the processing characteristics and the physicals 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, oxidation inhibitor etc.Wherein lubricant such as calcium stearate, Zinic stearas, stearic acid etc.; Oxidation inhibitor such as primary antioxidant 1076,1010, auxiliary antioxidant such as oxidation inhibitor 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 preferred preparation method of the polyphenylacetylene combination of laser labelling of the present invention comprises:
(1) polystyrene base-material, pearly pigment, nanoscale powder rubber and a small amount of white oil and oxidation inhibitor high-speed mixing is even;
(2) compound melt extrudes in the WPZSK25 twin screw extruder, cooling and dicing.Forcing machine heating zone temperature is respectively 205 ℃ of one section 189 ℃, two sections 202 ℃, three sections 210 ℃, four sections 210 ℃, five sections 210 ℃, head, and engine speed is 350 rev/mins;
(3) with the gained pellet 80 ℃ of dryings 5 hours, in 200 ℃ of injection moldings, and preparation standard batten on request, test mechanical property and optical property.
The laser apparatus that polyphenylacetylene combination of the present invention is carried out laser labelling can be CO
2Laser apparatus (wavelength 10600nm), Nd:YAG laser apparatus (wavelength 1064nm and 532nm), pulse UV laser apparatus (excimer laser), especially semiconductor N d:YAG laser apparatus (wavelength 1064nm).
According to the action principle of laser labelling, material must can absorb enough laser energies, just can be identified clearly, and most of laser sees through for transparent plastics, and incomplete absorption is difficult in product surface and forms mark clearly.But the polyphenylacetylene combination of laser labelling of the present invention has good laser marking, can use the Nd:YAG laser labelling, can obtain dark laser labelling under lasing, and makes the transparency of base-material itself and physical and mechanical properties keep good.
Preparation method's simple and reliable process of the present invention, the laser additive dosage is little, and the powdered rubber price is very low, and the composition total cost is reduced.The price of the Nano powder rubber per kilogram that uses among the present invention is about 20 yuan, add-on by 5 ‰ wt in polystyrene is calculated, this material cost per ton increases about 100 yuan, if and add the laser auxiliary agent product that the Engelhard company of the U.S. or the Merck company of Germany etc. release, because the price of its per kilogram is about 1000 yuans, even addition is 1 ‰ wt, increase cost per ton also can be about 1000 yuan.
The present invention can be applied to need in nearly all industrial sector to carry out on the polystyrene article of mark.For example, often need on article, indicate the trade mark, series number etc. of date manufactured, expiration date, barcode, company.
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.
Embodiment 1～8:
Place homogenizer to handle polystyrene resin (trade mark is 666D, Sinopec Yanshan Mountain branch office) and white oil (technical grade, commercially available); Polystyrene after will handling then, ultra-fine form of finely divided powder, mehtod styrene-butadiene rubber(SBR) (trade mark VP101, Beijing's northization is ground chemical industry New Tech S. R. L., particle diameter 80nm, gel content 90%), pearly pigment (trade mark LS825, Germany Merck), after antioxidant 1010 (ciba company) and oxidation inhibitor 168 (ciba company) stir, compound is added twin screw extruder (German WP company, model is ZSK-25) in carry out melt blending extrude the back granulation, extrusion temperature is 189～210 ℃, screw speed 350rpm.The pellet of extruding is dried 5hr in 80 ℃ of baking ovens, under 200 ℃ condition, be injected into the standard batten then, carry out laser labelling test and Mechanics Performance Testing.Concrete prescription sees Table 1, and wherein the white oil consumption is in all prescriptions: 0.5 part; Antioxidant 1010 is: 0.1 part; Oxidation inhibitor 168 is: 0.1 part, each component concentration is all in weight part.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 component concentration is all in weight part.Results of property is as shown in table 1.
Testing method to the laser labelling of the material for preparing in above embodiment and the comparative example and performance thereof is as follows:
The laser labelling instrument: the present invention adopts the product DH-MFD03 of laser engineering branch office of China DaHeng (group) company limited N-type semiconductorN LD pumped YAG laser marking machine that sample is carried out the laser labelling test.
The sign of laser labelling: can whether smooth, clear to the sign of mark by visual font mark lines, whether the big area labeled surface is smooth determines, can also be with spectrophotometer degree of comparing quantitative test.Because the background area of this experiment is a transparent plastics, the visible light major part sees through, so only the test badge zone is to the reflectivity of visible light, reflectivity is low more to show that the color of mark is dark more, this experiment represents with Y that with the reflectivity of DatacolorSF300 (U.S.) spectrophotometer mensuration marked region the test wavelength region is 400～700nm, reflectance value is based on the D65 light source, and test badge is the border circular areas of diameter 13mm.
Socle girder notched Izod impact strength according to the canonical measure polyphenylacetylene combination of ASTM D256.
Table 1
| PS | VP101 | LS825 | Mark Y value | Indicia appearance | The background transmittance | Outstanding lacking, dash | |
| Unit | Weight part | Weight part | Weight part | ％ | / | ％ | J/m |
| Comparative example 1 | 100 | / | / | Can't record | Some discontinuous stains | 88.5 | 11.3 |
| Comparative example 2 | 100 | / | 0.3 | 12.3 | Clear smooth | 63.0 | 10.9 |
| Embodiment 1 | 100 | 0.3 | / | 8.44 | Unfairness slightly | 84.0 | 11.9 |
| Embodiment 2 | 100 | 0.3 | 0.07 | 8.49 | Clear smooth | 81.7 | 11.6 |
| Embodiment 3 | 100 | 0.6 | 0.07 | 8.01 | Clear smooth | 78.0 | 13.1 |
| Embodiment 4 | 100 | 2.0 | 0.07 | 6.64 | Clear smooth | 74.2 | 15.2 |
| Embodiment 5 | 100 | 0.3 | 0.1 | 9.00 | Clear smooth | 80.0 | 11.3 |
| Embodiment 6 | 100 | 0.4 | 0.1 | 9.05 | Clear smooth | 80.1 | 11.9 |
| Embodiment 7 | 100 | 0.5 | 0.1 | 9.08 | Clear smooth | 77.2 | 12.2 |
| Embodiment 8 | 100 | 0.3 | 0.3 | 9.65 | Clear smooth | 74.1 | 11.1 |
(the used power of laser marking is 11.5W)
By in the table 1 as seen, the pure PS that comparative example 1 does not add powdered rubber and pearly pigment almost can't laser marking; 2 of comparative examples add a kind of LS825, though mark is clear smooth, color is more shallow, simultaneously because the LS825 intrinsic colour is gloomy, make the loss of composition transmittance bigger, and this composition cost height.Embodiment 1～8 is the sample that adds powdered rubber, and the mark effect is fine, and very little to the original performance impact of material.
Claims (9)
1. but the polyphenylacetylene combination of a laser labelling includes the following component of blend: polystyrene, 100 parts by weight; Median size is the powdered rubber of 50～200nm, the 0.3-0.8 weight part; Pearly pigment, the 0-1 parts by weight; Wherein, described powdered rubber is the rubber particles of equal phase structure, and its gel content is 60 weight % or higher, and described powdered rubber comprises the butylbenzene powdered rubber or/and carboxyl butylbenzene powdered rubber.
2. but the polyphenylacetylene combination of laser labelling as claimed in claim 1, it is characterized in that: the median size 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.
4. 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.
5. but the polyphenylacetylene combination of laser labelling as claimed in claim 1, it is characterized in that: described pearly pigment is the 0.05-0.3 weight part.
6. but the polyphenylacetylene combination of laser labelling as claimed in claim 5, it is characterized in that: described pearly pigment is the 0.05-0.1 weight part.
7. but the polyphenylacetylene combination of laser labelling as claimed in claim 1 is characterized in that: described pearly pigment is to be the sheet base with light mica or white clouds master slice, covers which floor metal oxide again and the platy particle that obtains, and described metal oxide is selected from SnO
2, TiO
2, Fe
2O
3(Sn, Sb) O
2In at least a.
But 8. 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 parts in polystyrene, and the consumption of described white oil is 0.1～0.5 weight part.
9. but, comprise that the component that will include described polystyrene, powdered rubber compares melt blending by described set of dispense as the preparation method of the polyphenylacetylene combination of each described laser labelling among the claim 1-8.
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| CN2007100988514A CN101293985B (en) | 2007-04-28 | 2007-04-28 | Polystyrene composition capable of marking with laser and preparation thereof |
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| CN101293985B true CN101293985B (en) | 2010-07-07 |
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| WO2014130814A1 (en) | 2013-02-22 | 2014-08-28 | Sun Chemical Corporation | Preparation of refined pigment from elastomer |
| WO2020073251A1 (en) * | 2018-10-10 | 2020-04-16 | 华为技术有限公司 | Housing structure and manufacturing method therefor, and mobile terminal |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318578A (en) * | 2000-04-14 | 2001-10-24 | 默克专利股份有限公司 | Laser marking plastic |
| CN1381526A (en) * | 2001-04-18 | 2002-11-27 | 中国石油化工股份有限公司 | Toughened polystyrene and its preparing process |
| CN1381527A (en) * | 2001-04-18 | 2002-11-27 | 中国石油化工股份有限公司 | Full-sulfurized thermoplastic polystyrene elastomer and its preparing process |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318578A (en) * | 2000-04-14 | 2001-10-24 | 默克专利股份有限公司 | Laser marking plastic |
| CN1381526A (en) * | 2001-04-18 | 2002-11-27 | 中国石油化工股份有限公司 | Toughened polystyrene and its preparing process |
| CN1381527A (en) * | 2001-04-18 | 2002-11-27 | 中国石油化工股份有限公司 | Full-sulfurized thermoplastic polystyrene elastomer and its preparing process |
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