CN116178851A - Styrene compound, product, preparation method and application thereof - Google Patents
Styrene compound, product, preparation method and application thereof Download PDFInfo
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- CN116178851A CN116178851A CN202111425849.XA CN202111425849A CN116178851A CN 116178851 A CN116178851 A CN 116178851A CN 202111425849 A CN202111425849 A CN 202111425849A CN 116178851 A CN116178851 A CN 116178851A
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- styrene
- butadiene
- black
- white
- laser
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 66
- -1 Styrene compound Chemical class 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000010330 laser marking Methods 0.000 claims abstract description 28
- 239000003550 marker Substances 0.000 claims abstract description 24
- 239000012745 toughening agent Substances 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims description 13
- 238000010147 laser engraving Methods 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 5
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 238000001746 injection moulding Methods 0.000 claims description 2
- 238000004445 quantitative analysis Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 21
- 239000002344 surface layer Substances 0.000 abstract description 4
- 238000010329 laser etching Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 8
- 239000000155 melt Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 5
- 239000004926 polymethyl methacrylate Substances 0.000 description 5
- 230000003678 scratch resistant effect Effects 0.000 description 5
- 229920000638 styrene acrylonitrile Polymers 0.000 description 5
- 238000009472 formulation Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000003440 styrenes Chemical class 0.000 description 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
Abstract
The invention relates to a styrene compound, a product, a preparation method and application thereof. The styrene compound comprises a styrene polymer, a butadiene toughening agent and a black-and-white laser marking agent. The invention takes the styrene polymer as the base material, and adds a specific amount of black-and-white laser marking agent, so that white marks can be laser-carved in the base material, and the surface layer of the base material has excellent scratch resistance.
Description
Technical Field
The invention belongs to the technical field of plastic laser carving, and particularly relates to a styrene compound, a product, a preparation method and application thereof.
Background
The laser carving processing technology is widely applied to the surface of plastic products for the texture modification of various patterns and marks due to the characteristics of economy, environmental protection, automation, flexible design and the like. The plastic laser carving can generally carry out black and white, white and black and other colors, wherein the laser carving black and white is popular in the black household appliances and OA industries because letters, LOGO and patterns can be laser carved on a black electric appliance shell. However, the plastic laser carving black whitening is characterized in that the surface is excited by laser to foam to present a white mark, the foamed white mark has very poor scratch resistance and is easy to scratch to form scratches, and the attractiveness is seriously affected.
At present, the existing patent provides a polypropylene composite material, wherein polypropylene is taken as a base material, barium sulfate, a toughening compatilizer and the like are utilized to improve scratch resistance, and a laser carving additive is added to realize laser carving, but the scratch resistance of the polypropylene composite material is improved, and the mark on the surface of the material after laser carving still has the defect of poor scratch resistance.
Therefore, developing a laser etching material capable of laser etching to obtain scratch-resistant white marks has important research significance and application value.
Disclosure of Invention
The invention aims to overcome the defect or defect that a white mark after laser engraving of a laser engraving material is not scratch-resistant in the prior art, and provides a styrene compound. The invention takes the styrene polymer as the base material, and adds a specific amount of black-and-white laser marking agent, so that white marks can be laser-carved in the base material, and the surface layer of the base material has excellent scratch resistance.
Another object of the present invention is to provide a method for producing the above styrene complex.
Another object of the present invention is to provide the use of the above-mentioned styrene compound in laser engraving.
Another object of the present invention is to provide an article laser engraved with a white marking.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a styrene compound comprises the following components in parts by weight:
100 parts of a styrene polymer, and,
0 to 3 parts of butadiene toughening agent,
0.01 to 0.05 portion of black and white laser marking agent.
According to the invention, the styrene polymer is used as a base material, and a specific amount of black and white laser marking agent is added, so that when the obtained styrene compound is subjected to laser marking, the black and white laser marking agent only generates bubbles in the base material after absorbing laser energy, so that a white mark can be obtained in the base material, the problem that the surface layer is foamed and is not scratch-resistant can be avoided, and the styrene compound has excellent scratch resistance and can be widely applied to products such as black household appliances and the like needing laser carving of the white mark.
The selection of the base material, the selection and the dosage of the black-and-white laser marking agent have great influence on the position of bubbles and the laser engraving effect. If other common laser carving materials are selected as the base material, such as polymethyl methacrylate or polycarbonate, which is easy to be heated to carbon under the excitation of laser, dark marks are formed after laser carving, and black and white cannot be realized. If the dosage of the black-and-white laser marking agent is too small, better laser etching cannot be performed; if the dosage of the black-and-white laser marking agent is too large, when laser carving is carried out, a large amount of bubbles can be formed in the compound and on the surface by the laser, and the surface of the white mark is not scratch-resistant. If other laser marking agents, such as pearlescent pigments, are selected, although the laser engraving marks have certain scratch resistance, the laser engraving marks are black and yellow in color, so that the white laser engraving marks are difficult to obtain and are generally used for dark laser marking.
Preferably, the styrene polymer is one or more of styrene-acrylonitrile copolymer or polystyrene.
The melt index of the styrene polymer has a large influence on the processability and a slight influence on the scratch resistance.
Preferably, the styrene polymer has a melt index of 1-10 g/10min at 200 ℃ and 5kg according to ISO 1133-2011; more preferably 2.5 to 8g/10min.
Preferably, the butadiene toughening agent is one or more of a styrene-butadiene-acrylonitrile copolymer or a styrene-butadiene copolymer.
Preferably, the butadiene toughening agent has a BD structure (butadiene structure) component content of 60wt.% to 80wt.% according to infrared quantitative analysis; further preferably 60wt.% to 75wt.%.
Preferably, the butadiene toughening agent is 0.01 to 3 parts by weight, and more preferably 0.01 to 1 part by weight.
The mechanical property of the styrene compound can be improved on the premise of not affecting the laser carving effect by adding a proper amount of butadiene toughening agent. If the addition amount of the butadiene toughening agent is too large, bubbles can not be generated only in the base material during laser etching, and the scratch resistance is affected.
Preferably, the black-and-white laser marking agent is carbon black.
The preparation method of the styrene compound comprises the following steps: and uniformly mixing the styrene polymer, the butadiene toughening agent and the black-and-white laser marking agent to obtain a mixture, and then carrying out melt extrusion and granulation on the mixture to obtain the styrene compound.
Preferably, the styrene polymer, the butadiene toughening agent and the black-and-white laser marking agent are uniformly mixed in a high-speed mixer to obtain a mixture, and then the mixture is added into a double-screw extruder to be melt extruded and granulated to obtain the styrene compound.
More preferably, the high speed mixer is used for stirring and mixing, the stirring rotating speed is 60-100 rpm, and the stirring time is 3-5 min.
Preferably, the melt extrusion and granulation are carried out by a double screw extruder; the extrusion temperature of the double screw extruder is 160-220 ℃, the length-diameter ratio is 40-65:1, and the screw rotating speed is 300-450 rpm.
The application of the styrene compound in laser carving is also within the protection scope of the invention.
And (3) carrying out laser etching treatment on the product with the white mark after injection molding of the styrene compound to obtain the white mark, thus obtaining the product.
Preferably, the article is a black appliance.
Compared with the prior art, the invention has the following beneficial effects:
the invention takes the styrene polymer as the base material, and adds a specific amount of black-and-white laser marking agent, so that white marks can be laser-carved in the base material, and the surface layer of the base material has excellent scratch resistance.
Detailed Description
The invention is further illustrated below with reference to examples. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. The experimental procedures in the examples below, without specific details, are generally performed under conditions conventional in the art or recommended by the manufacturer; the raw materials, reagents and the like used, unless otherwise specified, are those commercially available from conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art in light of the above teachings are intended to be within the scope of the invention as claimed.
The reagents selected for the examples and comparative examples of the present invention are described below:
A. polymer
Styrene-acrylonitrile copolymer # 1 (SAN 1 #): SAN-2437, medium oil is vitrified, and the melt index under the condition of 5kg at 200 ℃ is 2.5g/10min according to ISO 1133-2011;
styrene-acrylonitrile copolymer # 2 (SAN # 2): SAN 310NTR, korean brocade lake, according to ISO1133-2011, melt index under 5kg condition at 200deg.C is 3.0g/10min;
styrene-acrylonitrile copolymer 3# (SAN 3 #): SAN NX3400, ningbo-placating, according to ISO1133-2011, the melt index under the condition of 5kg at 200 ℃ is 1.0g/10min;
polystyren1# (gpps1#): GPPS123P, shanghai Seisaceae, has a melt index of 8.0g/10min at 200deg.C under 5kg conditions in accordance with ISO 1133-2011;
polystyrene # 2 (gpps2 #): GPPS861N, taida chemical, melt index at 200℃under 5kg is 6.6g/10min according to ISO 1133-2011;
PMMA (polymethyl methacrylate): PMMA CM-207, taiwan Qimei, has a melt index of 8.5ml/10min at 230℃and 3.8kg according to ISO 1133-2011;
B. butadiene toughening agent
Styrene-butadiene-acrylonitrile copolymer 1# (B1-1 #): ABS POW HR181, korean Jinhu, BD structure component content 60%;
styrene-butadiene-acrylonitrile copolymer # 2 (B1-2 #): ABS high-rubber powder 60P, taiwan Qiao, BD structure component content 68%;
styrene-butadiene copolymer # 1 (B2-1 #): TUFPRENE 125, xudi Cheng, BD component content 75%;
styrene-butadiene copolymer # 1 (B2-2 #): TUFPRENE 126, xudi, BD component content 74%;
C. laser marking agent:
carbon BLACK, BLACK-and-white laser marking agent, DENKA BLACK, japan electric chemical industry, inc;
pearlescent pigment, dark laser marking agent, IRIODIN 183, merck.
The composites of examples 1 to 13 and comparative examples 1 to 5 of the present invention were prepared by the following procedure:
weighing the raw materials, putting the raw materials into a mixer with the rotating speed of about 100 revolutions per minute, dry mixing for 3-5 minutes, and then melting, extruding and granulating the mixed raw materials in a double-screw extruder with the length-diameter ratio of 40:1 and the temperature interval of 160 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃ and the rotating speed of 450 revolutions per minute to obtain plastic particles, namely the composite.
The plastic particles are injection molded into a color plate (thickness is 2 mm) at the temperature of about 200 ℃, and then a large-family laser EP-12 type laser marking machine is adopted to carry out laser etching under the conditions that the current is 20A, the marking speed is 1000mm/s and the frequency is 17kHz, so as to obtain the laser etching mark.
Testing the color, pencil hardness and scratch resistance of the surface of the color plate before laser engraving, and testing the pencil hardness and scratch resistance of the surface of the color mark at the mark position of the color plate after laser marking; the testing position points before laser etching are consistent with the testing position points after laser etching.
(1) Color: under visible light, the color was observed visually.
(2) Pencil hardness: the measurement was carried out according to the GB/T6739-2006 standard.
(3) Scratch resistance: the scratch resistance of the plastic inner cavity member of the popular automobile hundred grid cross scratch PV3952-2019 is measured according to the scratch resistance standard, the load is 10N, and the scratch speed is 1000mm/min. L values and glossiness of the same positions are tested before and after the scratch resistance performance test, and the L values are measured by a color difference meter according to the GB/T11186-1989 standard; gloss is measured according to GB/T8807-1988 using a gloss meter (60 ℃). If the L value is increased more, or the gloss is reduced more, the scratch resistance is relatively poor in parallel.
Examples 1 to 13
This example provides a series of styrene compounds with the formulations shown in Table 1.
Table 1 formulations (parts) of examples 1 to 13
Comparative examples 1 to 5
This comparative example provides a series of compounds with the formulations shown in table 2.
Table 2 formulations (parts) of comparative examples 1 to 5
The styrene compounds (or compounds) provided in each example and comparative example were tested for their properties according to the performance test methods described above, and the results are shown in Table 3.
TABLE 3 results of Performance test of the compositions provided in examples 1-13 and comparative examples 1-5
From the above test results, the styrene compounds provided in examples 1 to 13 can be laser etched to obtain white marks by black-and-white laser. The pencil hardness test is carried out on the same position, and the pencil hardness before and after laser carving is basically consistent and has no change. By comparing the L and the change condition of the gloss before and after laser etching, the scratch resistance of the white mark and the scratch resistance before laser etching are hardly changed. It is clear that the styrene compound provided in examples 1 to 13 had hardness consistent with that of the non-laser etched region on the laser etched white marking surface, and had good scratch resistance, since the styrene compound was only foamed in the matrix during laser etching, and bubbles were present in the matrix and did not migrate to the surface. In comparative example 1, an excessive amount of butadiene toughening agent was added, and bubbles were generated on both the surface and the inside of the substrate during laser etching, resulting in poor scratch resistance of the white mark. The black-and-white laser marking agent added in comparative example 2 was too small to laser engraving. The black-and-white laser marking agent added in comparative example 3 is too much, and when laser carving, the laser forms a large number of bubbles in the compound and on the surface, so that the white mark surface obtained by laser carving is not scratch-resistant. PMMA selected in comparative example 4 is used as a base material, and when laser carving is performed, the compound is seriously carbonized, the surface is uneven, the mark is black and yellow, a white mark cannot be formed, and pencil hardness and scratch resistance tests cannot be performed. In comparative example 5, pearlescent pigment laser marking agent is selected, and when laser carving is carried out, the compound is carbonized seriously, the surface is uneven, the mark is black and yellow, a white mark cannot be formed, and pencil hardness and scratch resistance test cannot be carried out.
Those of ordinary skill in the art will recognize that the embodiments herein are intended to assist the reader in understanding the principles of the invention and should be understood that the scope of the invention is not limited to such specific statements and embodiments. Those of ordinary skill in the art can make various other specific modifications and combinations from the teachings of the present disclosure without departing from the spirit thereof, and such modifications and combinations remain within the scope of the present disclosure.
Claims (10)
1. The styrene compound is characterized by comprising the following components in parts by weight:
100 parts of a styrene polymer, and,
0 to 3 parts of butadiene toughening agent,
0.01 to 0.05 portion of black and white laser marking agent.
2. The styrene composite according to claim 1, wherein the styrene polymer is one or more of styrene-acrylonitrile copolymer or polystyrene.
3. The styrene composite according to claim 1, wherein the butadiene toughening agent is one or more of a styrene-butadiene-acrylonitrile copolymer or a styrene-butadiene copolymer.
4. The styrene compound according to claim 1, wherein the butadiene toughening agent has a BD structural component content of 60wt.% to 80wt.% according to infrared quantitative analysis.
5. The styrene composite according to claim 1, wherein the butadiene toughening agent is 0.01 to 1 part by weight.
6. The styrene composite of claim 1, wherein the black-and-white laser marking agent is carbon black.
7. The method for producing a styrene compound according to any one of claims 1 to 6, comprising the steps of: and uniformly mixing the styrene polymer, the butadiene toughening agent and the black-and-white laser marking agent to obtain a mixture, and then carrying out melt extrusion and granulation on the mixture to obtain the styrene compound.
8. The method of manufacturing according to claim 7, comprising the steps of: and (3) uniformly mixing the styrene polymer, the butadiene toughening agent and the black-and-white laser marking agent in a high-speed mixer to obtain a mixture, adding the mixture into a double-screw extruder for melt extrusion, and granulating to obtain the styrene compound.
9. Use of the styrene complex according to any one of claims 1 to 6 in laser engraving.
10. A product with white marks by laser engraving, which is characterized in that the product is obtained by carrying out laser engraving treatment on the styrene compound according to any one of claims 1 to 6 after injection molding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111425849.XA CN116178851A (en) | 2021-11-26 | 2021-11-26 | Styrene compound, product, preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111425849.XA CN116178851A (en) | 2021-11-26 | 2021-11-26 | Styrene compound, product, preparation method and application thereof |
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| CN116178851A true CN116178851A (en) | 2023-05-30 |
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| CN202111425849.XA Pending CN116178851A (en) | 2021-11-26 | 2021-11-26 | Styrene compound, product, preparation method and application thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5981647A (en) * | 1996-09-10 | 1999-11-09 | Daicel Chemical Industries, Ltd. | Resin composition for a white marking |
| JP2002206045A (en) * | 2001-01-11 | 2002-07-26 | Toray Ind Inc | Antistatic resin composition for laser marking |
| CN101319075A (en) * | 2008-06-13 | 2008-12-10 | 华中科技大学 | Copolymer based powdered material for selective laser sintering and preparation method thereof |
| CN101683793A (en) * | 2008-09-28 | 2010-03-31 | 中国石油化工股份有限公司 | Polystyrene composition capable of being marked by laser and preparation method thereof |
| JP2011032452A (en) * | 2009-08-04 | 2011-02-17 | Samsung Total Petrochemicals Co Ltd | Resin composition for white-laser-marking |
| KR20110085444A (en) * | 2010-01-20 | 2011-07-27 | 삼성토탈 주식회사 | Resin composition for laser marking |
-
2021
- 2021-11-26 CN CN202111425849.XA patent/CN116178851A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5981647A (en) * | 1996-09-10 | 1999-11-09 | Daicel Chemical Industries, Ltd. | Resin composition for a white marking |
| JP2002206045A (en) * | 2001-01-11 | 2002-07-26 | Toray Ind Inc | Antistatic resin composition for laser marking |
| CN101319075A (en) * | 2008-06-13 | 2008-12-10 | 华中科技大学 | Copolymer based powdered material for selective laser sintering and preparation method thereof |
| CN101683793A (en) * | 2008-09-28 | 2010-03-31 | 中国石油化工股份有限公司 | Polystyrene composition capable of being marked by laser and preparation method thereof |
| JP2011032452A (en) * | 2009-08-04 | 2011-02-17 | Samsung Total Petrochemicals Co Ltd | Resin composition for white-laser-marking |
| KR20110085444A (en) * | 2010-01-20 | 2011-07-27 | 삼성토탈 주식회사 | Resin composition for laser marking |
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