CN114456535A

CN114456535A - Black ABS material marked by blue laser and preparation method and application thereof

Info

Publication number: CN114456535A
Application number: CN202210096581.8A
Authority: CN
Inventors: 左泽强; 敬新柯; 何勇刚; 陶四平; 黄志�
Original assignee: Tianjin Kingfa Advanced Materials Co Ltd
Current assignee: Tianjin Kingfa Advanced Materials Co Ltd
Priority date: 2022-01-26
Filing date: 2022-01-26
Publication date: 2022-05-10
Anticipated expiration: 2042-01-26
Also published as: CN114456535B

Abstract

The invention discloses a black ABS material marked by blue laser and a preparation method and application thereof. The black ABS material marked by the blue laser comprises the following components: ABS resin 920-998 weight portions, black pigment 0.6-1.4 weight portions, toner mixture 1-4 weight portions, and processing assistant 1-5 weight portions. The black pigment is copper-chromium black. The toner mixture is selected from blue pigments and/or blue dyes. The black ABS material marked by the blue laser expands the color diversity of ABS laser marking fonts, subverts the traditional 'black and white marking', presents a blue marking effect, is clear and not fuzzy in marking, meets the market diversification requirement, does not need to add expensive laser marking agents, and reduces the production cost.

Description

Black ABS material marked by blue laser and preparation method and application thereof

Technical Field

The invention relates to the field of plastics, in particular to a black ABS material marked by blue laser and 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 contents of the three monomers can be changed at will to prepare various resins; the ABS plastic has the common performance of three components, and 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 the processing and molding characteristics of thermoplastics and improves electrical properties. Therefore, the ABS plastic is a tough, hard and rigid material which has easily obtained raw materials, good comprehensive performance, low price and wide application. ABS plastics are widely applied in the manufacturing industry and chemical industry of machinery, electricity, textile, automobiles, airplanes, ships and the like, and particularly, the ABS plastics are widely applied in the field of household appliances and need 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 more and more widely applied to plastics. At present, the laser marking in the ABS material can not achieve the color effect, the marked characters can only be 'white' in black, the mark is single, and the market diversification and specialization requirements can not be met; especially in the black ABS material, because the black ABS material absorbs the energy of the laser beam, all convert the light energy into heat energy, the marking effect is poor, generally only can beat the fuzzy, and almost unidentifiable mark, therefore generally need add laser marking agent in the black ABS, and need presume the appropriate technological parameter, can beat the grey-white marking effect in the black ABS. However, laser marking agents are generally expensive, which greatly increases the production cost. Therefore, there is a need for an ABS material that can be used for laser marking to produce a color mark and at the same time can be used for a great cost saving.

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 marked by the blue laser 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 pigments and/or blue dyes. The toner mixture may 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 oiled blue to the phthalocyanine blue is (1-3): 1. the preferred blue dye mixture can make the laser marked blue mark appear positive blue, and has good aesthetic effect. Pure phthalocyanine blue is green phase, pure dye blue is red phase, pure mark 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 beams act on a printing material to instantly melt and even gasify the surface material, and a film-shaped substance is formed on the surface of the material, the color of the substance is the ground color of the material, the ground color of the scheme is blue, and the scheme is different from the scheme that the temperature-sensitive substance generates thermal decomposition, oxidation and other reactions under the condition of heat.

Further, the melt index of the ABS resin is 2-6g/10 min. The test standard was ISO1133-1:2011(200 ℃, 5 kg).

Further, the black pigment is copper-chromium black. The infrared reflectivity of the copper-chromium black is 13-33%, the copper-chromium black is higher than that of common carbon black, and the energy of a part of laser can be reflected, so that the laser marked mark is clear and not blurred, and more laser energy can be absorbed by the carbon black to cause the mark to be blurred. The infrared reflectivity is measured by GB/T36540-.

The key point of the invention is that the special black pigment of copper-chromium black and toner mixture is used to show the effect of blue laser marking without adding a laser marking agent, thereby reducing the cost. The copper-chromium black has high infrared reflectivity and can reflect a part of laser energy, so that the laser marked mark is clear and not fuzzy. The preferred blue dye or blue pigment mixture of the present invention can make the laser marked blue mark appear positive blue, and has good aesthetic effect.

Further, the processing aid is a lubricant, and the lubricant is any one or more of high molecular polyethylene wax, ethylene bis stearamide and stearate.

The invention also provides a preparation method of the blue laser marked black ABS material, 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) and (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 granulation.

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 blue laser marked black ABS material in preparing blue laser marked black ABS plastic products.

In summary, compared with the prior art, the invention achieves the following technical effects:

(1) the black ABS material marked by the blue laser expands the color diversity of ABS laser marking fonts, subverts the traditional 'black and white marking', presents a blue marking effect, has high marking definition, is not fuzzy, and meets the market diversification requirements.

(2) The blue laser marked black ABS material does not need to add expensive laser marking agent, has economic formula and greatly reduces the production cost.

Detailed Description

In order to make the technical solutions of the present invention better understood by those skilled in the art, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, shall fall within the scope of protection of the present invention.

Examples

The raw materials used in the examples and comparative examples were commercially available as follows:

ABS resin 1: ABS DG-417, 2.3g/10min melt index, Tianjin Staphylea chemical Co., Ltd;

ABS resin 2: a designation ABS 275, melt index 1g/10min, Liaoning Huajin Co;

copper chromium black: pigment black 28, infrared reflectance 28%, Hunan Yingxu pigment, Inc.;

coloring carbon black: brand number M717, cabot corporation;

phthalocyanine blue: phthalocyanine blue 15:3, Basff;

oil blue: anthraquinone blue 38, by clariant corporation;

ultramarine blue: brand ultramarine 08, nyu ben ley corporation;

processing aid: ethylene bis stearamide, lubricating agent EBS, Kai Kogyo, Liaoning, Inc.

Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.

The raw material formulations of the blue laser marked black ABS materials of the examples and comparative examples are shown in table 1 and table 2, respectively:

table 1 raw material formulation (parts by weight) of examples

TABLE 2 raw material formulation of comparative example (parts by weight)

	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 from the raw materials according to the following method:

(2) and (2) feeding the mixed material obtained in the step (1) into a double-screw extruder (Kekuolong) through a precisely-metered feeder, and carrying out mixing, extrusion, cooling and grain cutting. 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 performance test method comprises the following steps:

(1) the prepared ABS material particles are injected into flat square plates (100mm x 100mm) by an injection molding machine, the selected injection molding machine is a horizontal extruder (Haitian), and the injection molding temperature is 200 +/-5 ℃. And carrying out laser marking observation on the obtained square plate. The laser marking machine is special infrared laser marking equipment for plastics. "O" indicates "poor" definition, "OO" indicates "medium" definition, and "OOO" indicates "excellent" definition.

(2) The impact strength is ISO 1802001, and the qualification standard is 14KJ/m²。

(3) And testing the color of the marking font of the obtained laser marked square plate. The color measuring instrument is Escierose 7000A. A represents a red-green value, B represents a yellow-blue value, L represents a white-black value, DL represents the difference of the shade of the color, and the larger the DL is, the higher the contrast is, the better the definition is; db represents yellow blue, and the smaller Db represents the more distinct blue phase.

Carrying out color test and marking effect test on the blue laser marked black ABS materials prepared in the embodiments and the comparative examples; 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 example test results

As can be seen from the above embodiments, the ABS materials in the embodiments 1-9 are all black when laser is applied, can be applied to the process of applying blue characters, and are blue, and have high definition. The ABS materials of the test examples 1-9 all have the impact strength higher than 14KJ/m²The invention can achieve excellent blue laser marking effect on the premise of keeping the mechanical property of the material basically unchanged.

Comparative examples 1-4 and 6 all have single variable with example 2, and comparative example 1 replaces copper chromium black with colored carbon black, and the typeface of beating out is grey blue, and the definition is very poor, shows that the effect on the promotion of marking definition is more obvious than colored carbon black to use copper chromium black. Comparative example 2 the amount of copper chrome black out of the range of 0.6 to 1.4 parts by weight resulted in only grey marks and poor clarity. Comparative example 3 copper chrome black was used in an amount less than 0.6 to 1.4 parts by weight, and the color of the material did not appear black but grayish blue, which can give a blue mark but was poor in clarity. In comparative example 4, the amount of the mixture of phthalocyanine blue and oil blue is less than 1 to 4 parts by weight, and a blue mark cannot be formed but a dark gray mark can be formed. Comparative example 6 replacing the toner mixture of the present invention with ultramarine blue did not produce a clear positive blue mark. Comparative example 5 compared to example 4, where the toner mixture was used in an amount exceeding the range of 1 to 4 parts by weight, the ABS material was not black in color, appeared dark blue, and could give a blue mark, but had poor clarity. The marking clarity of the above comparative examples was poor, and the ABS material was not black or could not be marked blue.

In conclusion, the invention discloses a black ABS material marked by blue laser and a preparation method and application thereof. The black ABS material marked by the blue laser comprises the following components: ABS resin 920-998 weight portions, black pigment 0.6-1.4 weight portions, toner mixture 1-4 weight portions, and processing assistant 1-5 weight portions. The black pigment is copper-chromium black. The toner mixture is selected from a blue pigment and/or a blue dye. The black ABS material marked by the blue laser expands the color diversity of ABS laser marking fonts, subverts the traditional 'black and white marking', presents a blue marking effect, is clear and not fuzzy in marking, meets the market diversification requirement, does not need to add expensive laser marking agents, and reduces the production cost.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims

1. The black ABS material marked by blue laser is characterized by comprising the following components:

the toner mixture is selected from blue pigments and/or blue dyes.

2. The blue laser marked black ABS material of claim 1, wherein the ABS resin has a melt index of 2-6g/10 min.

3. The blue laser marked black ABS material of claim 1, wherein the black pigment is copper chrome black.

4. The blue laser marked black ABS material of claim 1, wherein the toner mixture is a mixture of phthalocyanine blue and oil blue.

5. The blue laser marked black ABS material according to claim 4, wherein the weight ratio of the oiled blue to the phthalocyanine blue is (1-3): 1.

6. the blue laser marked black ABS material according to claim 1, wherein the processing aid is a lubricant, and the lubricant is one or more of polyethylene wax, ethylene bis stearamide, and stearate.

7. The method for preparing the blue laser marked black ABS material according to any of claims 1 to 6, characterized by comprising the following steps:

8. The method of claim 7, wherein the extruder is a twin-screw extruder.

9. The preparation method according to claim 8, wherein 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.

10. Use of the blue laser marked black ABS material of any of claims 1-6 in the preparation of blue laser marked black ABS plastic products.