CN114456535B - Blue laser marked black ABS material and preparation method and application thereof - Google Patents
Blue laser marked black ABS material and preparation method and application thereof Download PDFInfo
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- CN114456535B CN114456535B CN202210096581.8A CN202210096581A CN114456535B CN 114456535 B CN114456535 B CN 114456535B CN 202210096581 A CN202210096581 A CN 202210096581A CN 114456535 B CN114456535 B CN 114456535B
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/10—Greenhouse gas [GHG] capture, material saving, heat recovery or other energy efficient measures, e.g. motor control, characterised by manufacturing processes, e.g. for rolling metal or metal working
Abstract
The invention discloses a black ABS material marked by blue laser, a preparation method and application thereof. The black ABS material with the blue laser marking comprises the following components: 920-998 parts of ABS resin, 0.6-1.4 parts of black pigment, 1-4 parts of toner mixture and 1-5 parts of processing aid. The black pigment is copper-chromium black. The toner mixture is selected from blue pigments and/or blue dyes. The black ABS material for blue laser marking expands the color diversity of the ABS laser marking fonts, overturns the traditional black marking and white, presents the blue marking effect, ensures clear marking without blurring, meets the market diversity requirement, does not need to add expensive laser marking agents, and reduces the production cost.
Description
Technical Field
The invention relates to the field of plastics, in particular to a black ABS material marked by blue laser, a preparation method and application thereof.
Background
The ABS plastic is a terpolymer of three monomers of acrylonitrile (A), butadiene (B) and styrene (S), and the relative content of the three monomers can be arbitrarily changed to prepare various resins; the ABS plastic has the common properties of three components, and the acrylonitrile (A) ensures that the ABS plastic is resistant to chemical corrosion and heat and has certain surface hardness; butadiene (B) imparts high elasticity and toughness; styrene (S) imparts thermoplastic processability and improves electrical properties. Therefore, the ABS plastic is a tough, hard and rigid material with easily obtained raw materials, good comprehensive performance, low price and wide application range. ABS plastic is widely applied in manufacturing industries such as machinery, electricity, textile, automobiles, airplanes, ships and the like and chemical industry, and particularly in the field of household appliances, the ABS plastic is widely applied and needs laser marking.
The laser marking has the advantages of permanence, anti-counterfeiting property, non-contact property, wide applicability, high engraving precision, high processing efficiency and the like, and the laser marking technology is increasingly widely applied to plastics. At present, laser marking in an ABS material cannot produce a color effect, a marked font can only be "white" in black, and the mark is single, so that the requirements of market diversification and specialization cannot be met; particularly, in the black ABS material, as the black ABS material absorbs the energy of the laser beam, all light energy is converted into heat energy, the marking effect is poor, and only a fuzzy mark which can not be identified almost can be marked, so that the black ABS material generally needs to be added with a laser marking agent, and proper technological parameters need to be set, so that the grey-white marking effect can be marked in the black ABS. But the laser marking agent is generally expensive, and the production cost is greatly increased. Therefore, there is a need for an ABS material that can be used to print color marks in laser marking while providing significant cost savings.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a black ABS material marked by blue laser, and a preparation method and application thereof. The black ABS material with the blue laser marking comprises the following components: ABS resin, black pigment, toner mixture and processing aid. The black pigment is copper-chromium black. The toner mixture is selected from blue pigments and/or blue dyes.
The invention provides a black ABS material marked by blue laser, which comprises the following components:
the toner mixture is selected from blue pigment and/or blue dye. The toner mixture can be a mixture of blue pigments, a mixture of blue dyes, or a mixture of blue pigments and blue dyes. Preferably a mixture of phthalocyanine blue and oil blue. The weight ratio of the oiling blue to the phthalocyanine blue is (1-3): 1. the preferred blue dye mixture can make the laser marked blue mark appear positive blue with good aesthetic effect. Pure phthalocyanine blue is greenish, and pure dye blue is reddish, so that pure marking blue can be obtained according to the proportion; principle of infrared laser marking: the laser generator generates high-energy continuous laser beams, the focused laser acts on the printing material to enable the surface material to be instantaneously melted and even gasified, membranous substances are formed on the surface of the material, the color of the membranous substances is the ground color of the material, the ground color of the scheme is blue, and the scheme is different from the reactions of thermal decomposition, oxidation and the like of the temperature-sensitive substances under the condition of heat.
Further, the melt index of the ABS resin is 2-6g/10min. The test standard is ISO1133-1:2011 (200 ℃,5 kg).
Further, the black pigment is copper chrome black. The infrared reflectivity of copper chrome black is 13-33%, which is higher than that of the common carbon black, and can reflect a part of laser energy, so that the marks marked by laser are clear and not blurred, and the carbon black can absorb more laser energy, so that the marks are blurred. The infrared reflectivity is measured by GB/T36540-2018, the test wave band is 760-1600nm, and the infrared reflectivity is measured by a spectrophotometer.
The key point of the invention is that the special black pigment copper-chromium black and the toner mixture are combined to present the blue laser marking effect, and no laser marking agent is required to be added, thereby reducing the cost. The infrared reflectivity of copper chrome black is high, and part of laser energy can be reflected, so that the marks marked by laser are clear and not blurred. The blue dye or the blue pigment mixture which is preferable in the invention can lead the blue mark marked by laser to be in positive blue, and has good aesthetic effect.
Further, the processing aid is a lubricant, and the lubricant is one or more of high molecular polyethylene wax, ethylene bis-stearamide and stearate.
The invention also provides a preparation method of the black ABS material marked by the blue laser, which comprises the following steps:
(1) Adding the components into a high-speed mixer or an internal mixer according to the proportion, and uniformly mixing to obtain a mixed material;
(2) Feeding the mixed material obtained in the step (1) into an extruder or an internal mixer through a precisely metered feeder, and carrying out mixing, extrusion, cooling and granulating.
Further, the extruder is a twin screw extruder.
Further, the length-diameter ratio of the double-screw extruder is (40-48): 1, the temperature is 190-220 ℃, the screw rotating speed is 350-550 r/min, and the feeding rotating speed is 30-80 r/min.
The invention also provides application of the black ABS material marked by the blue laser in preparation of black ABS plastic products marked by the blue laser.
In conclusion, compared with the prior art, the invention achieves the following technical effects:
(1) The black ABS material for blue laser marking expands the color diversity of the ABS laser marking fonts, overturns the traditional black marking and white, presents the blue marking effect, has high marking definition, does not blur, and meets the market diversification requirement.
(2) The black ABS material marked by blue laser does not need to be added with expensive laser marking agent, has an economical formula and greatly reduces the production cost.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution of the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, shall fall within the scope of the invention.
Examples
The raw materials used in the examples and comparative examples are commercially available, and are as follows:
ABS resin 1: the brand ABS DG-417 has a melt index of 2.3g/10min and is available from Tianjin Dazhu chemical Co., ltd;
ABS resin 2: the brand ABS 275, the melt index is 1g/10min, liaoning Hua Jin company;
copper chromium black: pigment black 28, infrared reflectance 28%, hunan Yingxu pigment Co., ltd;
coloring carbon black: brand M717, cabot corporation;
phthalocyanine blue: the brand of phthalocyanine blue is 15:3, and the Basf company;
oiling blue: anthraquinone blue brand 38, of the company Clariant;
ultramarine blue: the trade mark is ultramarine 08, neofeilai company;
processing aid: lubricant ethylene bis stearamide, trade name EBS, liaoning JiaKai Seiyun Co., ltd.
Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
The raw material formulations of the blue laser marked black ABS materials of examples and comparative examples are shown in tables 1 and 2, respectively:
table 1 raw material formulation (parts by weight) of examples
Table 2 raw material formulation (parts by weight) of comparative example
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
| ABS resin 1 | 996 | 996 | 996 | 996 | 994 | 996 |
| Copper chromium black | 2 | 0.2 | 1 | 1 | 1 | |
| Colored carbon black | 1 | |||||
| Phthalocyanine blue | 0.5 | 0.5 | 0.5 | 0.25 | 2 | |
| Oiling blue | 0.5 | 0.5 | 0.5 | 0.25 | 4 | |
| Ultramarine blue | 1 | |||||
| Processing aid | 2 | 2 | 2 | 2 | 2 | 2 |
The ABS material is prepared by the following steps:
(1) Adding the components into a high-speed mixer or an internal mixer according to the proportion, and uniformly mixing to obtain a mixed material;
(2) Feeding the mixed material obtained in the step (1) into a double-screw extruder (Keplong) through a precisely-metered feeder, and carrying out mixing, extrusion, cooling and granulating. The length-diameter ratio of the twin-screw extruder is (40-48): 1, the temperature is 190-220 ℃, the screw rotating speed is 350-550 r/min, and the feeding rotating speed is 30-80 r/min.
The performance test method comprises the following steps:
(1) And (3) injecting the prepared ABS material particles into a flat square plate (100 mm x 100 mm) by an injection molding machine, wherein the selected injection molding machine is a horizontal extruder (sea day), and the injection molding temperature is 200+/-5 ℃. And performing laser marking observation effect on the obtained square plate. The laser marking machine is special infrared laser marking equipment for plastics. "O" means that the definition is "poor", "OO" means that the definition is "medium", and "OOO" means that the definition is "excellent".
(2) Impact strength, test standard ISO180 2001, qualification standard 14KJ/m 2 。
(3) And testing the color of the marked font on the square board after the laser marking. The color meter is alice 7000A. A represents a red-green value, B represents Huang Lanzhi, L represents a white-black value, DL represents a difference in the shades of colors, and the larger DL is, the higher the contrast ratio is, and the better the definition is; db represents yellow blue, and smaller Db represents more pronounced blue phase.
Performing color test and marking effect test on the black ABS material marked by the blue laser prepared in each example and comparative example; the results of the examples are shown in Table 3, and the results of the comparative examples are shown in Table 4:
table 3 example test results
Table 4 comparative test results
As can be seen from the above examples, the ABS materials in examples 1 to 9 were black during laser marking, and blue fonts were printed, and were positive blue and high in sharpness. The ABS materials of test examples 1 to 9 all had impact strengths higher than 14KJ/m 2 The invention can achieve excellent blue laser marking effect on the premise of keeping the mechanical properties of the material unchanged basically.
Comparative examples 1 to 4 and 6 are all single variables as in example 2, and the color black is used for replacing copper chrome black in comparative example 1, the printed fonts are gray blue, and the definition is very poor, so that the effect of using copper chrome black on the improvement of the marking definition is more obvious than that of using the color black. The comparative example 2 was used in an amount exceeding the range of 0.6 to 1.4 parts by weight, only gray marks were marked and the definition was poor. Comparative example 3 copper chrome black was used in an amount less than 0.6 to 1.4 parts by weight, and the material was not black but gray blue in color, but was poor in definition although blue marks were made. In comparative example 4, the amount of the mixture of phthalocyanine blue and oil-made blue was less than 1 to 4 parts by weight, and a blue mark could not be made, and only a dark gray mark could be made. Comparative example 6 replacement of the toner mixture of the present invention with ultramarine blue did not produce a clear positive blue mark. Comparative example 5 in comparison with example 4, the amount of the toner mixture was outside the range of 1 to 4 parts by weight, and the color of the ABS material was not black, but was black and blue, and although blue marks were marked, the sharpness was poor. The above comparative examples were poor in marking clarity, and the ABS material was either not black or could not be marked blue.
In summary, the invention discloses a black ABS material marked by blue laser, a preparation method and application thereof. The black ABS material with the blue laser marking comprises the following components: 920-998 parts of ABS resin, 0.6-1.4 parts of black pigment, 1-4 parts of toner mixture and 1-5 parts of processing aid. The black pigment is copper-chromium black. The toner mixture is selected from blue pigments and/or blue dyes. The black ABS material for blue laser marking expands the color diversity of the ABS laser marking fonts, overturns the traditional black marking and white, presents the blue marking effect, ensures clear marking without blurring, meets the market diversity requirement, does not need to add expensive laser marking agents, and reduces the production cost.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (8)
1. The black ABS material with the blue laser marking is characterized by comprising the following components:
920-998 parts by weight of ABS resin;
0.6 to 1.4 parts by weight of a black pigment;
1-4 parts by weight of a toner mixture;
1-5 parts by weight of a processing aid;
the toner mixture is selected from blue pigment and/or blue dye;
the black pigment is copper-chromium black;
the toner mixture is a mixture of phthalocyanine blue and oiled blue.
2. The blue laser marked black ABS material according to claim 1 wherein the ABS resin has a melt index of 2-6g/10min.
3. The blue laser marked black ABS material according to claim 1, wherein the weight ratio of the oil blue to the phthalocyanine blue is (1-3): 1.
4. the black ABS material of claim 1 wherein the processing aid is a lubricant which is any one or more of a high molecular polyethylene wax, ethylene bis stearamide, and stearates.
5. The method for preparing the black ABS material marked by blue laser according to any one of claims 1 to 4, which is characterized by comprising the following steps:
(1) Adding the components into a high-speed mixer or an internal mixer according to the proportion, and uniformly mixing to obtain a mixed material;
(2) Feeding the mixed material obtained in the step (1) into an extruder or an internal mixer through a precisely metered feeder, and carrying out mixing, extrusion, cooling and granulating.
6. The method of claim 5, wherein the extruder is a twin screw extruder.
7. The method of claim 6, wherein the twin screw extruder has an aspect ratio of (40-48): 1, the temperature is 190-220 ℃, the screw rotating speed is 350-550 r/min, and the feeding rotating speed is 30-80 r/min.
8. The use of a blue laser marked black ABS material according to any one of claims 1 to 4 for the preparation of blue laser marked black ABS plastic articles.
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| CN202210096581.8A CN114456535B (en) | 2022-01-26 | 2022-01-26 | Blue laser marked black ABS material and preparation method and application thereof |
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| CN202210096581.8A CN114456535B (en) | 2022-01-26 | 2022-01-26 | Blue laser marked black ABS material and preparation method and application thereof |
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| CN114456535B true CN114456535B (en) | 2023-06-06 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1162175A1 (en) * | 2000-06-07 | 2001-12-12 | dmc2 Degussa Metals Catalysts Cerdec AG | Rare earth manganese oxide pigments |
| WO2018130886A1 (en) * | 2017-01-11 | 2018-07-19 | Sabic Global Technologies B.V. | Laser direct structure compositions with high heat stability and broader color space |
| CN109608770A (en) * | 2019-01-24 | 2019-04-12 | 江南大学 | A kind of black matrix blue laser labelling polymer composition and preparation method |
| CN112175290A (en) * | 2020-10-02 | 2021-01-05 | 东莞市烁康新材料科技有限公司 | Laser etching powder applied to laser marking and preparation process thereof |
| CN112375347A (en) * | 2020-11-12 | 2021-02-19 | 江苏金发科技新材料有限公司 | Black PBT composition capable of laser marking blue fonts and preparation thereof |
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- 2022-01-26 CN CN202210096581.8A patent/CN114456535B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1162175A1 (en) * | 2000-06-07 | 2001-12-12 | dmc2 Degussa Metals Catalysts Cerdec AG | Rare earth manganese oxide pigments |
| WO2018130886A1 (en) * | 2017-01-11 | 2018-07-19 | Sabic Global Technologies B.V. | Laser direct structure compositions with high heat stability and broader color space |
| CN109608770A (en) * | 2019-01-24 | 2019-04-12 | 江南大学 | A kind of black matrix blue laser labelling polymer composition and preparation method |
| CN112175290A (en) * | 2020-10-02 | 2021-01-05 | 东莞市烁康新材料科技有限公司 | Laser etching powder applied to laser marking and preparation process thereof |
| CN112375347A (en) * | 2020-11-12 | 2021-02-19 | 江苏金发科技新材料有限公司 | Black PBT composition capable of laser marking blue fonts and preparation thereof |
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| CN114456535A (en) | 2022-05-10 |
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