Color marking laser marking material and its preparation method and application

Abstract

The present invention discloses a color-marking laser marking material, its preparation method, and its application. The color-marking laser marking material comprises, by weight, 90-100 parts of a transparent resin, 0.5-5 parts of tourmaline, 0.02-1 parts of a black colorant, 0.1-2 parts of a color colorant, 0.1-2 parts of a laser marking agent, and 0.5-6 parts of a scratch-resistant agent. The tourmaline used in the present invention effectively improves the rigidity of the material surface. When used in conjunction with the scratch-resistant agent in the system, it creates a synergistic effect, further enhancing the scratch resistance of the color marking. The color difference before and after the scratch resistance test can be controlled to within 2.

Description

Technical Field

[0001] The present invention belongs to the technical field of laser marking materials, and more specifically, relates to a color marking laser marking material and a preparation method and application thereof. Background Art

[0002] Laser marking is a new marking method that uses the high energy of laser to irradiate the plastic surface to cause carbonization, foaming, color change, etc., thereby obtaining a mark with a different color from the substrate. Currently, laser marking is mainly used for permanent marking, product anti-counterfeiting, and tracking of important parts. Compared with traditional printing marking technology, it has three advantages: (1) non-contact processing, small heat impact, ensuring the original accuracy of the workpiece, clear and durable marking; (2) fast marking speed, easy operation, high-speed automatic operation, low production cost; (3) low pollution, it is a clean and environmentally friendly processing technology. Lasers used for laser marking of plastics can be divided into near-infrared (e.g., wavelength 1064nm) and far-infrared (e.g., wavelength 10600nm) lasers, visible light lasers (e.g., wavelength 532nm) or ultraviolet lasers (e.g., wavelength 355nm) according to their working bands.

[0003] The Chinese patent "A polymer composition containing a temperature-sensitive substance capable of laser color marking and its preparation method" discloses a polymer composition containing a temperature-sensitive substance capable of laser color marking and its preparation method. This invention utilizes the heat generated during the laser marking process by adding a temperature-sensitive substance to cause the temperature-sensitive substance to undergo thermal decomposition and oxidation reactions at a certain temperature. These reactions destroy the original material structure or generate a new substance, simultaneously producing a new color. The Chinese patent "A color-marking laser marking material with a luminous effect and its application" discloses a color-marking laser marking material with a luminous effect and its application. This laser marking material, prepared using this formula, produces a highly vivid color mark after laser marking.

[0004] However, the color markings produced by existing laser printing have poor scratch resistance and are easily worn and discolored during use, resulting in a significant color difference before and after a period of use, making them difficult to apply in actual product design. Summary of the Invention

[0005] In response to the above-mentioned existing technical problems, the purpose of the present invention is to provide a color marking laser marking material, which uses tourmaline and a scratch-resistant agent to produce a synergistic effect, thereby further improving the scratch resistance of the color marking laser marking material. The color difference before and after the scratch resistance test can be controlled within 2.

[0006] The second object of the present invention is to provide a method for preparing a color-marked laser marking material.

[0007] The third object of the present invention is to provide an application of a color-marked laser marking material in consumer electronic products.

[0008] In order to achieve the above object, the present invention is implemented through the following technical solutions:

[0009] A color marking laser marking material comprises, by weight, 90-100 parts of transparent resin, 0.5-5 parts of tourmaline, 0.02-1 parts of black colorant, 0.1-2 parts of color colorant, 0.1-2 parts of laser marking agent and 0.5-6 parts of scratch-resistant agent.

[0010] Conventional tourmaline can be used as a natural adsorbent and can also be used to release negative ions to enhance or activate biological cells. The inventors have discovered that tourmaline can effectively increase the rigidity of material surfaces. When used in conjunction with the scratch-resistant agent in laser marking systems, it creates a synergistic effect, further improving the scratch resistance of color markings. The color difference before and after scratch resistance testing can be controlled to within 2.

[0011] Preferably, the color marking laser marking material includes, by weight, 90-100 parts of transparent resin, 0.5-5 parts of tourmaline, 0.05-0.5 parts of black colorant, 0.1-2 parts of color colorant, 0.1-1 parts of laser marking agent, and 0.5-4 parts of scratch-resistant agent.

[0012] Preferably, the scratch resistant agent is selected from one or more of silicone masterbatch, polysiloxane or erucamide. Within this preferred range, the color difference of the color mark before and after the scratch resistance test can be controlled within 1.5.

[0013] Preferably, the haze of the transparent resin at a thickness of 2 mm is 0-4%, and the light transmittance of the transparent resin at a thickness of 2 mm is ≥87%. Color laser marking materials within this transmittance range can exhibit superior scratch resistance, color saturation, total color difference before and after laser marking, and weather resistance.

[0014] More preferably, the light transmittance of the transparent resin at a thickness of 2 mm is 88 to 99.9%.

[0015] Preferably, the D of the tourmaline 50 The particle size is 100 to 2000 nm. 50The technical effects of the present invention can be achieved when the particle size is 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm, 1100nm, 1200nm, 1300nm, 1400nm, 1500nm, 1600nm, 1700nm, 1800nm, 1900nm, and 2000nm.

[0016] Preferably, the transparent resin is selected from one or more of MABS, PMMA, GPPS or PC.

[0017] Preferably, the laser marking agent is doped tin oxide with a tin content of 4.0-5.0%.

[0018] Further preferably, the laser marking agent is selected from one or more of indium tin oxide, fluoride tin oxide or antimony tin oxide.

[0019] Preferably, the black colorant is selected from one or more of aniline black, azo black, copper chromium black, iron chromium black, acetylene black, conductive carbon black, channel black, or furnace black. The above preferred black colorants can improve the absorption of laser energy by the laser marking material.

[0020] Preferably, the weight ratio of the tourmaline to the laser marking agent is (1-10): 1. The combination of tourmaline and the laser marking agent within a specific weight ratio range can achieve higher laser marking clarity, color saturation, and scratch resistance.

[0021] Preferably, the color colorant is selected from one or more of a purple phase, a blue phase, a red phase, an orange phase, and a yellow phase; wherein the purple phase is preferably selected from 1-hydroxy-4-p-toluaminoanthraquinone; the blue phase is preferably selected from one or two of 1,4-bis[(2,6-diethyl-4-methylphenyl)amino]-9,10-anthracene dione and 1,4-bis[(2,4,6-trimethylphenyl)amino]-9,10-anthracene dione; the red phase is preferably selected from one or two of 14H-phenyl[4,5]isoquinolino[2,1-A]perylene-14-one and 8,9,10,11-tetrachloro-12H-phthaloperin-12-one; the orange phase is preferably selected from 12H-Phthaloperin-12-one; and the yellow phase is preferably selected from 2-(3-hydroxy-2-quinolinyl)-1,3-indene dione. The preferred color colorant can greatly improve the color saturation of the color mark after laser marking. The combination of black colorant and color colorant further improves the laser marking clarity of the color mark.

[0022] Specifically, 1-hydroxy-4-p-toluaminoanthraquinone, also known as Solvent Violet 13, exhibits a purple color under visible light and is used to adjust the purple phase. 1,4-Bis[(2,6-diethyl-4-methylphenyl)amino]-9,10-anthracenedione, also known as Solvent Blue 97, exhibits a blue color under visible light and is used to adjust the blue phase. 1,4-Bis[(2,4,6-trimethylphenyl)amino]-9,10-anthracenedione, also known as Solvent Blue 104, exhibits a blue color under visible light and is used to adjust the blue phase. 14H-Benzo[4,5]isoquino[2,1-A]perylene-14-one, also known as Solvent Red 179, exhibits a red color under visible light and is used to adjust the red phase. 8,9,10,11-tetrachloro-12H-phthaloperin-12-one, also known as Solvent Red 135, exhibits a red color under visible light and is used to adjust the red phase. 12H-Phthaloperin-12-one, also known as Solvent Orange 60, exhibits an orange color under visible light and is used to adjust orange phases. 2-(3-Hydroxy-2-quinolinyl)-1,3-indanedione, also known as Solvent Yellow 114, exhibits a yellow color under visible light and is used to adjust yellow phases.

[0023] Further preferably, the colored colorant is selected from a combination of a blue shade and a yellow shade.

[0024] The conventionally used tourmaline particle size range is in the millimeter range, which can be used as a natural adsorbent, and can also be used to release negative ions to enhance or activate biological cells. Through long-term research, the inventors found that nano-scale tourmaline within a specific particle size range has better dispersion properties in this system, making the laser marking material absorb the laser energy more uniformly, and thus making the overall material heated more uniformly. The inventors found that by combining nano-scale tourmaline within a specific particle size range with a preferred laser marking agent, not only can the weather resistance of the color mark be effectively improved, but also the laser marking clarity of the color mark can be improved. The color mark obtained by laser marking of the present invention has been tested for weather resistance, and the color difference before and after marking can be maintained within 1.5; the total color difference before and after marking is greater than 20; and after long-term use, the saturation of the color mark is still greater than 10. The color mark prepared by the present invention not only has excellent weather resistance and high laser marking clarity, but also has good color saturation.

[0025] In addition, the present invention also provides a method for preparing a color marking laser marking material, comprising uniformly mixing a transparent resin, tourmaline, a scratch-resistant agent, a black colorant, a color colorant and a laser marking agent, melt-extruding and granulating the mixture to obtain the color marking laser marking material.

[0026] Furthermore, the temperature of the melt extrusion is 200-250°C.

[0027] Furthermore, a twin-screw extruder is used for melt extrusion, wherein the aspect ratio of the twin-screw extruder is 25 to 40:1 and the screw speed is 200 to 800 rpm.

[0028] Furthermore, the present invention also provides applications of the color-marked laser marking material in consumer electronic products, including but not limited to applications in housings of consumer electronic products such as smart speakers, mice, and keyboards.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] (1) The present invention provides a color marking laser marking material, which uses tourmaline and a scratch-resistant agent to produce a synergistic effect, which can further improve the scratch resistance of the color marking laser marking material. The color difference before and after the scratch resistance test can be controlled within 2.

[0031] (2) The present invention provides a color marking laser marking material. By selecting nano-scale tourmaline in a specific particle size range and combining it with a specific laser marking agent, and then combining it with a preferred black colorant and a color colorant, the prepared color marking has excellent weather resistance. After the weather resistance test, the color difference is maintained within 1.5; the laser marking clarity is high, and the total color difference before and after laser marking is greater than 20; and after long-term use, it also has good color saturation, and the saturation of the color marking is still greater than 10. DETAILED DESCRIPTION

[0032] The present invention is further described below with reference to specific examples, which, however, are not intended to limit the present invention in any way. Unless otherwise specified, the reagents, methods, and equipment used in the present invention are conventional reagents, methods, and equipment in the art.

[0033] Description of raw materials for embodiments and comparative examples:

[0034] Transparent resin 1, ABS, transmittance 88%, haze 2%, MABS TR558A, LG Chem.

[0035] Transparent resin 2, PMMA, transmittance 90%, haze 2%, PMMA LG2, Sumitomo Chemical.

[0036] Transparent resin 3, ABS, transmittance 20%, haze 95%, ABS 8391, North Huajin Chemical Industry Group Co., Ltd.

[0037] In the above transparent resin, the test method for light transmittance and haze is ASTM D1003-2013.

[0038] Tourmaline 1, D 50Particle size is 100-2000 nm, KNS-FIR68, Cairns Nanomaterials Co., Ltd.

[0039] Tourmaline 2, D 50 The particle size is 3.5-10μm, from Shijiazhuang Tourmaline Company.

[0040] Black colorant 1, acetylene carbon black, DENKA BLACK, Shanghai Huazhongrong Industry and Trade Co., Ltd.

[0041] Black colorant 2, CI pigment black 32, Black L 0086, BASF.

[0042] Black colorant 3, channel carbon black, M717, BASF.

[0043] Black Colorant 4, Conductive Carbon Black, 250g, Timcole Graphite & Carbon Co.

[0044] Laser marking agent 1, antimony tin oxide (ATO), Shanghai Huzheng Nanotechnology, tin content is 4.0% to 4.5%.

[0045] Laser marking agent 2, mica + Fe3O4, iriotec 8841, Merck, tin content 0%.

[0046] Laser marking agent 3, indium tin oxide (ITO), Shanghai Huzheng Nanotechnology, tin content is 4.2% to 4.8%.

[0047] Laser marking agent 4, mica + antimony tin oxide, Iriotec 8825, Merck, tin content of 1% to 2.3%.

[0048] Color Colorant 1, Solvent Blue 104, Elbaplast Blue R, HDC.

[0049] Color Colorant 2, Solvent Yellow 114, Macrolex Yellow G, BAY.

[0050] Color Colorant 3, Pigment Blue 29, Ultramarine blue 5008, HOLLIDAY PIGMENTS.

[0051] Color stain 4, Solvent Red 135, Oplas Red 330, ORIENT.

[0052] Color stain 5, solvent violet 59, Kenawax Violet 5RP, HAYS.

[0053] Color Tint 6, Solvent Green 3, Alizarine Green Base, BASF.

[0054] Color stain 7, solvent blue 97, Macrolex Blue RR, BAY.

[0055] Scratch resistant agent 1, polysiloxane, HG-600, Jiahua Specialty Chemical Co., Ltd.

[0056] Scratch resistant agent 2, wollastonite, mineral fiber grade wollastonite, Dalian Global Minerals Co., Ltd., China.

[0057] Examples 1 to 21

[0058] The weight parts of the raw materials used in the following examples are shown in Table 1.

[0059] The following examples adopt the same preparation method, and the specific steps include:

[0060] (1) adding a transparent resin, tourmaline, a scratch-resistant agent, a black colorant, a color colorant, and a laser marking agent into a mixer and mixing for 30 minutes to obtain a mixture;

[0061] (2) The mixture is added into a twin-screw extruder, and under the shearing, mixing and conveying of the screw, it is melted, extruded, granulated and dried to obtain a color marking laser marking material; wherein, the temperature of the twin-screw extruder from the feeding section to the die head is 200°C, 205°C, 210°C, 215°C, 220°C, 220°C, 225°C, 225°C, 220°C, 210°C respectively, the aspect ratio of the twin-screw extruder is 40:1, and the screw speed is 400rpm.

[0062] Comparative Examples 1 to 4

[0063] The weight parts of the raw materials used in the following comparative examples are shown in Table 2.

[0064] The specific preparation steps of each comparative example are the same as those of Example 1.

[0065] Table 1 is the formula components of each embodiment:

[0066] Table 1

[0067]

[0068]

[0069]

[0070] Table 2 shows the formula components of each comparative example:

[0071] Table 2

[0072] Components Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Transparent resin 1 100 100 100 100 Tourmaline 1 0 1 0 6 Black colorant 1 0.1 0.1 0.1 0.1 Color colorant 1 0.1 0.1 0.1 0.1 Color colorant 2 0.1 0.1 0.1 0.1 Laser marking agent 1 0.5 0.5 0.5 0.5 Scratch resistant agent 1 1 0 0 1

[0073] The color marking laser marking materials prepared in the above examples and comparative examples were subjected to the following laser marking, color measurement, scratch resistance test, and weather resistance test methods:

[0074] (1) Laser marking method: A TED semiconductor-pumped fiber laser marking machine (laser beam output power 20 W) with a laser wavelength of 1064 nm was used. The laser marking process was: power 50%, frequency 20 kHz, speed 1400 mm / s. A 40 mm × 40 mm square was marked on the flat plate for color measurement, scratch resistance test, and weather resistance test.

[0075] (2) Color measurement method: Using a spectrophotometer in reflection mode, the L* value, a* value, b* value, and C* value of the color of a 30mm×30mm square before and after laser marking are measured in the CIELab color space. The spectrophotometer is an X-Rite Color-Eye 7000A spectrophotometer. By measuring the spectral reflectance factor or spectral transmittance of the object, the tristimulus values ​​of the sample color are calculated and converted into CIELab. The CIELab color space is a color model announced by the International Commission on Illumination (English: International Commission on illumination, French: Commission Internationale del′Eclairage, abbreviated in French as CIE) in 1976. It is a color model determined by the CIE organization that theoretically includes all colors visible to the human eye. The L*, a*, and b* values ​​represent the lightness, red-green color, and yellow-blue color of a color, respectively.

[0076] L* represents lightness, ranging from 0 to 100, indicating that the color goes from dark (black) to light (white).

[0077] a* represents red and green, and the value changes from positive to negative, indicating that the color changes from red to green.

[0078] b* represents yellow-blue, and the value changes from positive to negative, indicating that the color changes from yellow to blue.

[0079] C* represents saturation, C*=(a*^2+b*^2)^0.5. The larger the C*, the higher the color saturation and the brighter the color. The smaller the C*, the lower the color saturation and the lighter the color.

[0080] DL* is the difference in lightness, with positive values ​​indicating lighter (white) and negative values ​​indicating darker (black).

[0081] Da* is the difference between red and green, with positive values ​​indicating more red and negative values ​​indicating more green.

[0082] Db* is the difference between yellow and blue, with positive values ​​indicating more yellow and negative values ​​indicating more blue.

[0083] DC* represents the difference in saturation, with positive values ​​indicating an increase in saturation and negative values ​​indicating a decrease in saturation.

[0084] DE represents the total color difference. The calculation formula is as follows:

[0085]

[0086] The larger the DC* value of the color change before and after laser marking, the more it can reflect the saturation of the material; the larger the DE value of the color change before and after laser marking, the more it can reflect the marking clarity of the material.

[0087] (3) Scratch resistance test: The scratch resistance test is conducted according to the scratch resistance standard PV3952 (2002) of Volkswagen AG for interior parts. The scratch resistance of the material is determined by measuring the color difference DE before and after scratching at the marked position. The lower the value, the better the scratch resistance, and vice versa.

[0088] (4) Weathering performance test: Xenon lamp aging is measured according to ISO 4892.2:2013 cycle 2. The color difference DE of the marked area is measured before and after 500 hours of weathering test. The lower the value, the better the weathering performance, and vice versa.

[0089] Table 3 and Table 4 are the performance test results of each embodiment and comparative example respectively.

[0090] Table 3

[0091]

[0092]

[0093]

[0094] Table 4

[0095]

[0096]

[0097] It can be seen from Examples 1 to 21 that the color marking laser marking material prepared by the present invention has excellent scratch resistance, and the color difference before and after the scratch resistance test can be controlled within 2; in addition, the color difference before and after the weather resistance test is within 3.6, the saturation (DC*) before and after laser marking is between 3.8 and 14.1, and the total color difference (DE) before and after laser marking is between 12 and 28.

[0098] Furthermore, from Example 2, it can be seen that Example 1 uses a transparent resin with a haze of 0-4% and a transmittance of ≥87%, which can significantly improve the scratch resistance, color saturation, total color difference before and after laser marking, and weather resistance of the color mark.

[0099] It can be seen from Examples 1 and 3 that using D 50 Tourmaline with a particle size of 100 to 2000 nm significantly improves the scratch resistance, weather resistance, and total color difference before and after laser marking of color markings, and slightly improves color saturation.

[0100] As can be seen from Examples 1, 4, and 5, the use of a specific laser marking agent and black colorant in Example 1 can effectively improve the weather resistance, total color difference before and after laser marking, and color saturation of the color mark. As can be seen from Examples 1 and 6, the use of a specific color colorant in Example 1 can greatly improve the color saturation, total color difference before and after laser marking, and scratch resistance of the color mark.

[0101] It can be seen from Examples 7 and 8, as well as Examples 14 and 15, that when the amount of the black colorant in Examples 14 and 15 is within the preferred range, the color marking has better scratch resistance, weather resistance, total color difference before and after laser marking, and color saturation.

[0102] Examples 1 and 9 demonstrate that specific scratch-resistant agents can significantly improve the scratch resistance of color markings. Examples 10 and 11 illustrate different types of black colorants employed in the present invention, while Examples 12 and 13 demonstrate different types of colorant employed in the present invention. The data demonstrate that these black and colorant types can achieve the same technical benefits. Example 17 demonstrates that the optimal ratio of tourmaline and laser marking agent employed in Example 1 significantly improves the scratch resistance of color markings and the overall color difference before and after laser marking.

[0103] It can be seen from Example 1, Example 18 and Example 19 that when the tin content in the doped tin oxide in Example 18 and Example 19 is within a specific range, the color marking has better weather resistance, total color difference and color saturation.

[0104] As shown in Examples 14 and 15, as well as Examples 20 and 21, Example 20 employs 6 parts of a scratch-resistant agent. Although the color mark prepared in Example 20 exhibits better scratch resistance, the total color difference and color saturation before and after laser marking are significantly reduced. Example 21 employs 2 parts of a laser marking agent. The total color difference, color saturation, and scratch resistance of the color mark prepared in Example 21 are significantly reduced before and after laser marking.

[0105] Comparative Example 1 shows that the addition of tourmaline significantly improves the scratch resistance, weather resistance, total color difference before and after laser marking, and color saturation of the color marking. Comparative Example 2 shows that the addition of a scratch-resistant agent significantly improves the scratch resistance of the color marking. Comparative Example 3 shows that the absence of tourmaline and a scratch-resistant agent significantly affects the scratch resistance, weather resistance, total color difference before and after laser marking, and color saturation. Comparative Example 4 shows that excessive tourmaline significantly affects the scratch resistance of the color marking.

[0106] The foregoing examples are merely illustrative, serving to illustrate some of the features of the method of the present invention. The appended claims are intended to claim the widest possible scope that can be envisioned, and the examples presented herein are demonstrated by the applicant's actual experimental results. Therefore, the applicant intends that the appended claims are not limited by the selection of examples illustrating the features of the present invention. Some numerical ranges used in the claims also include subranges therein, and variations within these ranges should also be interpreted as being covered by the appended claims where possible.

Claims

1. A color marking laser marking material, characterized in that: Calculated by weight, it includes 90-100 parts of transparent resin, 0.5-5 parts of tourmaline, 0.02-1 parts of black colorant, 0.1-2 parts of color colorant, 0.1-2 parts of laser marking agent, and 0.5-6 parts of scratch-resistant agent; The scratch-resistant agent is selected from one or more of silicone masterbatch, polysiloxane or erucamide; The light transmittance of the transparent resin at a thickness of 2 mm is ≥87%; The color colorant is selected from one or more of a purple phase, a blue phase, a red phase, an orange phase, and a yellow phase; wherein the purple phase is selected from 1-hydroxy-4-p-toluaminoanthraquinone; the blue phase is selected from one or two of 1,4-bis[(2,6-diethyl-4-methylphenyl)amino]-9,10-anthracene dione and 1,4-bis[(2,4,6-trimethylphenyl)amino]-9,10-anthracene dione; the red phase is selected from one or two of 14H-phenyl[4,5]isoquinolino[2,1-A]perylene-14-one and 8,9,10,11-tetrachloro-12H-phthaloperin-12-one; the orange phase is selected from 12H-Phthaloperin-12-one; and the yellow phase is selected from 2-(3-hydroxy-2-quinolinyl)-1,3-indene dione; The weight ratio of the tourmaline to the laser marking agent is (1-10):

1.

2. The color marking laser marking material according to claim 1, characterized in that: The transparent resin has a haze of 0-4% at a thickness of 2 mm.

3. The color marking laser marking material according to any one of claims 1 to 2, characterized in that: The tourmaline D 50 The particle size is 100~2000nm.

4. The color marking laser marking material according to claim 3, characterized in that: The laser marking agent is doped tin oxide with a tin content of 4.0-5.0%.

5. The color marking laser marking material according to claim 1, characterized in that: The black colorant is selected from one or more of aniline black, azo black, copper chromium black, iron chromium black, acetylene black, conductive carbon black, channel black or furnace black.

6. The method for preparing the color marking laser marking material according to any one of claims 1 to 5, characterized in that: The color marking laser marking material is obtained by uniformly mixing the transparent resin, tourmaline, scratch-resistant agent, black colorant, color colorant and laser marking agent, melting and extruding, and granulating.

7. Use of the color marking laser marking material according to any one of claims 1 to 5 in the preparation of consumer electronic products.

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