CN101230164B - Laser markable polyethylene composition and preparation method thereof - Google Patents
Laser markable polyethylene composition and preparation method thereof Download PDFInfo
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- CN101230164B CN101230164B CN200710063074XA CN200710063074A CN101230164B CN 101230164 B CN101230164 B CN 101230164B CN 200710063074X A CN200710063074X A CN 200710063074XA CN 200710063074 A CN200710063074 A CN 200710063074A CN 101230164 B CN101230164 B CN 101230164B
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Abstract
The invention relates to polyethylene composition which can be marked with laser and the preparation method thereof. The composition includes the following blended components: 100 parts of polyethylene by weight, 0.1-15 parts of powdered rubber by weight, 0-2 parts of laser additive by weight, wherein, the powdered rubber comprises butylbenzene powdered rubber or / and carboxyl styrene butadiene powdered rubber. The preparation method comprises the step that the components including the polyethylene and the powdered rubber is melted and blended according to the compounding ratio of the components. The composition of the invention can overcome the problems that the polyethylene is difficult to be marked with laser, and the material physical performance is decreased and the cost is high caused by overabundant addition amount of the prior laser additive. In the preparation method of the invention, the process is simple and reliable. The polyethylene composition which can be marked with laser in the invention can be widely applied to the polyethylene products which are needed to be marked with laser.
Description
Technical field
But the present invention relates to a kind of polyethylene (PE) composition and method of making the same of laser labelling, but be specifically related to a kind of polyethylene composition and preparation method thereof of light color of laser labelling.
Background technology
Polyvinyl resin is the kind of output maximum in the general synthetic resin, and it comprises that mainly new LDPE (film grade) (LDPE), LLDPE (LLDPE), high density polyethylene(HDPE) (HDPE) and some have the product of property.Because its cost performance height is widely used in products such as film, sheet articles, injection-molded item, blow-molded article, tubing, electric wire.On polyethylene products, add sign and becoming more and more important, for example, often need be on goods the trade mark, series number etc. of labeling production date, expiration date, barcode, company.
At present, the technological method that adds sign on polyethylene products 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 these printing processes are difficult to be applied to curved surface or net grain surface, and required special processing charges has increased the overall cost of product.
Adopt laser system to come marking objects to have the advantage of contactless property, high speed and flexible mark.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.For example, 10 times of two-dimensional bars to conventional barcode of packing density are studied out, compare with former barcode, print two-dimensional bar and require more accurate, more clear.Laser seal mark can satisfy these requirements, and in 0.001 inch scope, the size of point and position can be repeated---and these performance impressions or ink printer are difficult to realize.From the angle of protection environment, laser seal mark occupies very big advantage.Laser labelling need not printing ink, does not also need the such high strength energy drying process of printing ink seal mark technology, and it provides long lasting application; And it is solvent-free, makes it have more environment friendly.
Along with being on the increase of plastics in the productive life, the flexible marker that adopt laser, forms with the high speed noncontact has become more and more important.For having very sufficient contrast gradient between laser labelling on the plastics and the base material, could guarantee to use laser scanner or CCD photographic camera reading automatically like this to sign.
Yet the laser labelling of polyethylene products is bad, and for the common polythene goods that non-modified is handled, when laser energy was low, the polyethylene products surface produced mark hardly; Under the moderate energy irradiation, only can produce distant mark; Behind further raising laser energy, though can produce mark, the mark that is produced is irregular, tangible calcination vestige is arranged, and can't obtain meticulousr structure.After having patent to be presented in the polyethylene to add the laser auxiliary agent, its laser marking performance can improve.
Polymkeric substance patent about laser labelling has CN 1359969A, CN 1361808A, CN1377314A, CN 1147227A, US 5981647A, US 5866644A, CN 1260752A etc. at present.
CN 1359969A has described plastic capable of laser labelling and preparation and purposes, the laser-sensitive pigment that it comprises pearly pigment and itself do not have any pearl effect by interpolation, the plastics that prepare by this mode have transparent or semitransparent property, adjuvant used is the product of its company, price is comparatively expensive, and the embodiment of this patent seldom, and just its laser photosensitizers of qualitative description has the effect that improves contrast gradient, and concrete effect quantitatively is not described in detail in detail.
But US 6482879B2 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%.
CN 1361808A has invented a kind of laser labelling polymer composition, and the average particulate size that its laser auxiliary agent comprises 0.1wt% at least is greater than 0.5 micron antimonous oxide, and pearly pigment.The antimonous oxide consumption is most preferably between 1～5%; Pearly pigment is as synergist, and content most preferably is 0.5～2wt%.When antimonous oxide content is higher than 2wt%,, the CTI improving agent can be added, in composition as barium sulfate for reducing specific conductivity.Because antimonous oxide is a kind of mineral filler, add mechanical property, the especially impact property that to destroy resin in the resin base to, and addition is more, causes to cost an arm and a leg, the cost height.
The known additive that is used for transparent or semitransparent polyethylene laser labelling now has certain shortcoming, and they make the dead color seal mark under the light background lack enough contrast gradients, i.e. sharpness; Or seal marking-up trace bar is fuzzy, not sharp-pointed; Perhaps additive dosage is too much, causes that the physicals of material descends, as the decline of the transparency or impact property etc.; And because the more meeting of addition makes that the cost raising is more, all there is laser auxiliary agent product to release as the Engelhard company of the U.S. and the Merck company of Germany etc., but the price of per kilogram is about 1000 yuans, add-on by 5 ‰ wt in polyethylene is calculated, and its material cost per ton of only this item will increase by 5000 yuan.
Summary of the invention
But technical problem to be solved by this invention provides a kind of polyethylene composition of laser labelling, and said composition can overcome that polyethylene is difficult to carry out laser labelling and present laser additive dosage causes that too much the physicals of material descends and expensive problem.
But the present invention further provides the preparation method of the polyethylene composition of described laser labelling.
But the polyethylene composition of laser labelling of the present invention includes the polyethylene and the powdered rubber of blend, and described powdered rubber comprises the butylbenzene powdered rubber or/and carboxyl butylbenzene powdered rubber is preferably the butylbenzene powdered rubber.Be 100 weight parts in polyethylene wherein, described powdered rubber is 0.1～15 weight part, is preferably 0.5～10 weight part.
But the preparation method of the polyethylene composition of laser labelling of the present invention comprises that the component that will include described polyethylene, powdered rubber compares melt blending by described set of dispense.
In polyethylene composition of the present invention, described polyethylene comprises the disclosed various types of polyvinyl resins of prior art, comprises that new LDPE (film grade) (LDPE), LLDPE (LLDPE), high density polyethylene(HDPE) (HDPE) and some have product of property etc.
In polyethylene composition of 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.
As laser labelling promotor, nano level butylbenzene powdered rubber or/and carboxyl butylbenzene powdered rubber join in the laser labelling PE composition, can promote the absorption of composition to laser, under lasing since carbonization decompose can be so that the laser marking of composition significantly improves, obtain the high dark color seal mark of contrast gradient, and nano level butylbenzene powdered rubber can not influence the toughness of PE or/and the consistency of carboxyl butylbenzene powdered rubber and PE is good.
In polyethylene is 100 weight parts, and described powdered rubber is 0.1～15 weight part, is preferably 0.5～10 weight part.If the powdered rubber consumption is too much, not only can improves the cost of material, and can destroy material inherent performance; If the powdered rubber consumption is very few, the raising of the laser labelling performance of material there is not tangible contribution.
But the polyethylene composition of laser labelling of the present invention can also comprise the laser auxiliary agent, and described laser auxiliary agent generally is to be the sheet base with silicate such as light mica or white clouds master slices, covers which floor metal oxide again to obtain, and metal oxide is selected from SnO
2, TiO
2, Fe
2O
3, ZnO and Sb
2O
3In one or more.The laser auxiliary agent can improve the laser labelling of polyethylene composition.In polyethylene is 100 weight parts, and described laser auxiliary agent is 0～2 weight part, is preferably 0.1～1.0 weight part.Consider that from cost and properties of materials the laser auxiliary dosage is unsuitable too many; From the laser absorption aspect is considered that the laser auxiliary dosage can not be very little.
But the polyethylene composition of laser labelling of the present invention also can include silicone oil, its effect be improve the processing characteristics of polyethylene composition and improve polyethylene and powdered rubber, laser auxiliary agent and other auxiliary agents between premixing effect.In polyethylene is 100 weight parts, and described silicone oil is 0.01～2 weight part, is preferably 0.1～1.5 weight part.Described silicon oil dosage too much can influence the processing characteristics and the physicals of polyethylene composition, consumption is crossed the pre-mixing deleterious that can make polyethylene particle and other auxiliary agent (mostly being Powdered) in the polyethylene composition at least, occurs particle and the isolating phenomenon of Powdered auxiliary agent in the actual course of processing.
In addition, but also can include polyethylene processing aid commonly used in the polyethylene composition 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 is the conventional oxidation inhibitor of polyethylene, as antioxidant 1076,1010, and auxiliary antioxidant such as DLTP, DSTP 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 concrete preparation method of the polyethylene composition of laser labelling of the present invention comprises: (1) places homogenizer with polyvinyl resin and silicone oil, polyethylene is carried out surface treatment, treatment time is between 0.5～3min, the general increase treatment time can be improved surface treatment effect, but can influence working (machining) efficiency simultaneously; (2) polyethylene after will handling, powdered rubber, laser auxiliary agent, oxidation inhibitor etc. stir; (3) compound is added carry out melt blending in the device of plastic processing and extrude the back granulation, but prepare the polyethylene composition of laser labelling.
The mixing of above step (1) can be carried out at normal temperatures, also can improve certain temperature and carry out.Temperature suitably improves, and can shorten the pretreated time, and general better suited temperature range is 20～50 ℃.
In the preparation process of polyethylene composition of the present invention, material melt blending temperature is blending temperature used in the common PE Processing, can decide according to the polyethylene melt temperature, should select not only guaranteeing the complete fusion of polyethylene 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, oxidation inhibitor etc. commonly used in the PE Processing 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 in preparation method of the present invention (comprising the mixing of polyethylene and silicone oil) can adopt various mixing equipments used in the prior art, 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 laser apparatus that polyethylene composition 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 Nd:YAG laser apparatus.
But by laser labelling polyethylene composition of the present invention and preparation method thereof, can prepare the good polyethylene composition of labeling properties, said composition 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 is compared present conventional formulation, and its material cost can reduce greatly, and laser labelling is good, just can obtain contrast gradient height, mark clearly when laser energy is low.Simultaneously because the adding of powdered rubber also makes the shock strength of material obtain raising to a certain degree.The price of the Nano powder rubber per kilogram that uses among the present invention is at 20 yuan, add-on by 5 ‰ wt in polyethylene is calculated, this its material cost per ton increases about 50 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, increase cost then per ton can be about 5000 yuan.
But laser labelling polyethylene composition of the present invention can be widely used in carrying out on the polyethylene products of laser labelling, as the polyethylene injection-molded item, polyvinyl piping materials, Polyethylene insulated cable sheath, sleeve pipe or the like, but the pattern of mark comprises date manufactured, expiration date, barcode, trade mark, series number, title of product or the like.
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 1～7:
Place homogenizer to handle polyvinyl resin (new LDPE (film grade), LDPE, trade mark 1F7B, Sinopec Yanshan Mountain branch office) and dimethyl silicone oil (trade mark 201, viscosity are 1000 centipoises, Beijing chemical industry two factories); Polyethylene 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%), laser auxiliary agent (trade mark LS825, Germany Merck), after antioxidant 1076 (Beijing Chemical Factory No. 3) and oxidation inhibitor DSTP (Beijing Chemical Factory No. 3) 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 130～190 ℃, screw speed 300rpm.The pellet of extruding is dried 6hr in 80 ℃ of baking ovens, under 150～210 ℃ condition, be injected into the standard batten then, 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 1～4
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 Examples and performance thereof is as follows:
Laser labelling: 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 test of laser labelling: the present invention adopts contrast gradient to characterize the laser labelling of polythene material.Concrete testing method is as follows: adopt U.S. Datacolor company produce SF300 type spectrophotometer respectively test badge zone (darker regions) and unmarked zone (light areas) to visible reflectance (reflection sources is a benchmark with the D65 light source), by following formula calculating contrast gradient:
Contrast gradient=light areas is to the reflectivity/darker regions of the visible light reflectivity to visible light
In addition, can also whether smooth and clear by the visual assessment marked region.
Socle girder notched Izod impact strength according to the canonical measure polyethylene composition of ASTM D 256.
Table 1
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 in polyethylene can make the contrast gradient of laser labelling be significantly improved, the mark effect obviously improves, simultaneously because the adding of powdered rubber also makes the shock strength of material obtain raising to a certain degree.
Claims (12)
1. but the polyethylene composition of a laser labelling includes the following component of blend: polyethylene, 100 parts by weight; Powdered rubber, 0.1～15 parts by weight; The laser auxiliary agent, 0～2 parts by weight; Wherein said powdered rubber is the butylbenzene powdered rubber or/and carboxyl butylbenzene powdered rubber, and median size is 50～200nm, and gel content is 60 weight % or higher; Described laser auxiliary agent is to be the sheet base with light mica or white clouds master slice, covers which floor metal oxide obtains again, and described metal oxide is selected from SnO
2, TiO
2, Fe
2O
3, ZnO and Sb
2O
3In one or more.
2. but the polyethylene composition of laser labelling as claimed in claim 1, it is characterized in that: described powdered rubber is 0.5～10 parts by weight.
3. but the polyethylene composition of laser labelling as claimed in claim 1, it is characterized in that: described laser auxiliary agent is 0.1～1.0 parts by weight.
4. but the polyethylene composition of laser labelling as claimed in claim 1, it is characterized in that: the median size of described powdered rubber is 80～150nm.
5. but the polyethylene composition 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.
6. but the polyethylene composition of laser labelling as claimed in claim 1, it is characterized in that: described powdered rubber is the rubber particles of equal phase structure.
7. but the polyethylene composition of laser labelling as claimed in claim 1, it is characterized in that: described powdered rubber is fully vulcanized powder rubber and/or cross-linked powdered rubber.
But 8. the polyethylene composition of laser labelling as claimed in claim 1, it is characterized in that: described polyethylene composition also includes silicone oil, is 100 weight parts in polyethylene, and described silicone oil is 0.01～2 weight part.
But 9. the polyethylene composition of laser labelling as claimed in claim 8, it is characterized in that: in polyethylene is 100 weight parts, described silicone oil is 0.1～1.5 weight part.
10. but, comprise that the component that will include described polyethylene, powdered rubber compares melt blending by described set of dispense as the preparation method of the polyethylene composition of each described laser labelling among the claim 1-9.
11. preparation method as claimed in claim 10, it is characterized in that: but the concrete preparation method of the polyethylene composition of described laser labelling comprises: and (1) places homogenizer with polyvinyl resin and silicone oil, polyethylene is carried out surface treatment, and the treatment time is between 0.5～3min; (2) polyethylene after will handling stirs with other component in the prescription; (3) compound is added carry out melt blending in the device of plastic processing and extrude the back granulation, but prepare the polyethylene composition of laser labelling.
12. preparation method as claimed in claim 11 is characterized in that: the blended temperature range of described step (1) is 20～50 ℃.
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Families Citing this family (8)
| 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 |
| CN102432935B (en) * | 2010-09-29 | 2014-01-08 | 中国石油化工股份有限公司 | Modified high-density polyethylene composition used in extrusion blow molding, and preparation method thereof |
| CN102417646B (en) * | 2011-10-24 | 2013-05-29 | 上海交通大学 | Laser-markable polyethylene composition |
| CN106674680B (en) * | 2015-11-06 | 2020-07-24 | 中国石油化工股份有限公司 | Polyethylene composition and high density polyethylene articles and methods of making the same |
| CN105741949A (en) * | 2016-04-07 | 2016-07-06 | 国网天津市电力公司 | Application of laser jet printing technology on electrical cable |
| CN106566068A (en) * | 2016-10-19 | 2017-04-19 | 玫瑰塑胶(昆山)有限公司 | Composition capable of laser color marking and preparation method thereof |
| CN111730209A (en) * | 2019-03-24 | 2020-10-02 | 张翔 | Method for making colored mark on object surface by using laser and application |
| CN110294883B (en) * | 2019-05-09 | 2021-06-01 | 江苏中天科技股份有限公司 | Efficient laser marking material and preparation method thereof |
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