Laser marking material and preparation method and application thereof

Abstract

The invention discloses a laser marking material and a preparation method and application thereof, and relates to the technical field of laser marking materials. The laser marking material comprises the following components in parts by weight: 10-95 parts of MABS (Methyl Acrylonitrile Butadiene Styrene) resin; 5 to 30 parts of SAN resin; 10 to 70 parts of PMMA resin; 0-25 parts of an elastomer; 0.01 to 0.5 part of a black pigment; 0.01 to 0.8 part of a coloring agent; the black pigment is carbon black; and the coloring agent is solvent yellow 160 or coumarin 6. The fluorescent dye and the carbon black are jointly used for coloring MABS to obtain bright green resin, then laser marking is adopted for marking, the color of a marking area is changed under the action of laser and becomes bright yellow, and therefore the color marking effect of different hues is achieved.

Description

Technical Field

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

[0002] Laser marking is a marking method with low operating cost, high precision, good flexibility and environmental protection. It has been widely used in many industries. At present, the marking effects mainly include black on white, white on black, black on color, etc., among which color marking is particularly popular. Color marking usually involves coloring the resin with color colorant and carbon black. After marking, the color of the colorant is displayed. Therefore, due to the limitation of the marking principle, the color marking effect is usually black on color, and the marking color is a single hue, making it difficult to achieve color marking of different hues. Summary of the invention

[0003] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a laser marking material and a preparation method and application thereof. The present invention uses fluorescent dye and carbon black together to color MABS to obtain a bright green resin, and then uses laser marking to mark it. Under the action of the laser, the color of the marked area changes to bright yellow, thereby achieving a color marking effect of different hues.

[0004] To achieve the above object, the technical solution adopted by the present invention is:

[0005] In a first aspect, the present invention provides a laser marking material comprising the following components in parts by weight:

[0006] MABS resin 10-95 parts; SAN resin 5-30 parts; PMMA resin 10-70 parts; elastomer 0-25 parts; black pigment 0.01-0.5 parts; colorant 0.01-0.8 parts;

[0007] The black pigment is carbon black; the colorant is solvent yellow 160 or coumarin 6.

[0008] The present invention selects a suitable ratio, and uses a suitable colorant and carbon black together for coloring MABS to obtain a bright green resin. The colorant can weaken the masking effect of carbon black on the hue, so that the product appears colorful. Then, laser marking is used for marking. Under the action of the laser, the color of the marked area changes to a bright yellow, thereby achieving a color marking effect of different hues. In addition, the present invention is beneficial to improving the scratch resistance of the material by adding SAN resin and PMMA resin.

[0009] Preferably, the laser marking material comprises the following components in parts by weight:

[0010] 12-90 parts of MABS resin; 6-29 parts of SAN resin; 12-64 parts of PMMA resin; 5-20 parts of elastomer; 0.1-0.4 parts of black pigment; 0.1-0.5 parts of colorant.

[0011] Preferably, the light transmittance of the MABS resin is greater than 80%.

[0012] Preferably, the MABS resin has a melt mass flow rate of 5-30 g / 10 min, preferably 8-21 g / 10 min, measured at 220° C. and 10 kg load according to ASTM D1238.

[0013] More preferably, the melt mass flow rate of the MABS resin measured at 220° C. and 10 kg load is in the range of any one or both of 8 g / 10 min, 10 g / 10 min, 12 g / 10 min, 15 g / 10 min, 18 g / 10 min, 20 g / 10 min, and 21 g / 10 min.

[0014] If the melt mass flow rate of the MABS resin is too large or too small, the processing performance will be affected, and the dispersion of the toner in it may also be affected, such as the appearance of toner spots and uneven color. Therefore, the present invention is beneficial to improving the processing performance and appearance effect of the laser marking material by controlling the melt mass flow rate of the MABS resin within the above range.

[0015] Preferably, the SAN resin has a melt mass flow rate of 5-20 g / 10 min, preferably 5-10 g / 10 min, measured at 230° C. and 3.8 kg load according to ASTM D1238.

[0016] More preferably, the melt mass flow rate of the SAN resin measured at 230° C. and 3.8 kg load is in the range of any one or both of 5 g / 10 min, 6 g / 10 min, 7 g / 10 min, 8 g / 10 min, 9 g / 10 min, and 10 g / 10 min.

[0017] Preferably, the PMMA resin has a melt mass flow rate of 1-20 g / 10 min, preferably 1-10 g / 10 min, measured at 230° C. and 3.8 kg load according to ISO 1133 standard.

[0018] Preferably, the melt mass flow rate of the PMMA resin measured at 230° C. and 3.8 kg load is in the range of any one or both of 1 g / 10 min, 2 g / 10 min, 4 g / 10 min, 5 g / 10 min, 6 g / 10 min, 8 g / 10 min, and 10 g / 10 min.

[0019] Preferably, the transmittance of the PMMA resin is greater than 90%.

[0020] Preferably, the density of the PMMA resin is 1.15-1.22 g / cm 3 .

[0021] Preferably, the average particle size of the carbon black is 5-200 nm, and the oil absorption value is 50-400 mL / 100 g.

[0022] Preferably, the elastomer is butadiene rubber, more preferably methyl acrylate-butadiene-styrene copolymer.

[0023] Preferably, the laser marking material further comprises 0.5-1.5 parts of other additives.

[0024] Preferably, the other auxiliary agents include at least one of an antioxidant, a lubricant, and a light stabilizer.

[0025] More preferably, the antioxidant includes antioxidant YFK-1010 and antioxidant YFK-168.

[0026] More preferably, the lubricant is N,N'-ethylene bisstearamide.

[0027] More preferably, the light stabilizer includes at least one of a light shielding agent, an ultraviolet absorber, a quencher, a free radical scavenger, and a hydroperoxide decomposer.

[0028] In a second aspect, the present invention further discloses a method for preparing a laser marking material, comprising the following steps:

[0029] The components are mixed and added into a twin-screw extruder, and the laser marking material is obtained after granulation and cooling.

[0030] Preferably, the extrusion temperature of the twin-screw extruder is 200-210° C., and the screw speed is 300-400 RPM.

[0031] On the third aspect, the present invention also discloses an application of laser marking materials in consumer electronics, household appliances, and electronic and electrical products. Specifically, it can be used for electronic products: marking trademarks, bar codes, models and other information on electronic products such as mobile phone cases and TV cases; automotive industry: marking part numbers, warning signs, etc. on internal parts of automobiles to ensure product traceability and safety; consumer goods: such as plastic products, daily necessities, etc., laser marking machines can provide them with clear and lasting identification.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] The present invention uses a colorant and carbon black together to color MABS to obtain a bright green resin, and then uses laser marking to mark the MABS. Under the action of the laser, the color of the marked area changes to a bright yellow, thereby achieving a color marking effect of different hues. At the same time, the present invention is beneficial to improving the scratch resistance of the material by adding SAN resin and PMMA resin. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 This is a physical picture of the laser marking material of the present invention after marking. DETAILED DESCRIPTION

[0035] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments, but the protection scope and implementation methods of the present invention are not limited thereto.

[0036] Unless otherwise specified, the materials and reagents used in the following examples are commercially available.

[0037] Examples 1-10

[0038] The embodiments of the laser marking material and the preparation method thereof of the present invention, the components of the laser marking material are shown in Table 1.

[0039] The method for preparing the laser marking material comprises the following steps:

[0040] The components are mixed and added into a twin-screw extruder, and the laser marking material is obtained after granulation and cooling.

[0041] Wherein, the temperature of the twin-screw extruder is 200-210°C, and the screw speed is 300-400RPM.

[0042] Comparative Examples 1-11

[0043] The difference between each comparative example and the embodiment is only in the type and proportion of components, as shown in Table 2.

[0044] Among the components described in each embodiment and comparative example:

[0045] The MABS resin 1 was purchased from LG Company, with a brand name of MABS TR557 and a melt mass flow rate of 21 g / 10 min (220° C. / 10 kg);

[0046] The MABS resin 2 was purchased from LG Company, with a brand name of MABS TR552 and a melt mass flow rate of 11 g / 10 min (220° C. / 10 kg);

[0047] The MABS resin 3 is purchased from LG Company, with the brand name MABS TR551 and a melt mass flow rate of 8 g / 10 min (220° C. / 10 kg).

[0048] The SAN resin 1: purchased from Korea Kumho Petrochemical Company, brand SAN 310NTR, melt mass flow rate of 10g / 10min (230°C / 3.8kg);

[0049] The SAN resin 2 is purchased from KUMHO PETROCHEMICAL CO., LTD., with a brand name of SAN 350C HW and a melt mass flow rate of 5.5 g / 10 min (230° C. / 3.8 kg).

[0050] The PMMA resin 1: purchased from Sumitomo Chemical Singapore Pte. Ltd., brand PMMALG, melt mass flow rate of 10g / 10min (230°C / 3.8kg);

[0051] The PMMA resin 2 was purchased from Sinochem Plastics Co., Ltd. with a brand name of PMMA C-205 and a melt mass flow rate of 1.8 g / 10 min (230° C. / 3.8 kg).

[0052] The elastomer is butadiene rubber: purchased from LG Company, brand EM500.

[0053] The black pigment 1 is carbon black: purchased from Shanghai Huazhongrong Industry and Trade Co., Ltd., brand acetylene carbon black DENKA;

[0054] The black pigment 2 is phenylethylamine, and the solvent-based dye is purchased from Guangzhou Haolong New Materials Co., Ltd. with the brand name AB833.

[0055] The colorant 1: purchased from Guangzhou Xinxinghui Chemical Co., Ltd., solvent yellow 160;

[0056] The colorant 2: purchased from Guangzhou Xinghui Trading Co., Ltd., solvent yellow 114;

[0057] The colorant 3: purchased from Shenzhen Tianlaibao Pigment Co., Ltd., Pigment Yellow 180;

[0058] The colorant 4: purchased from Dormade (Shanghai) Fine Chemical Co., Ltd., pigment brown 24;

[0059] The colorant 5 was purchased from Shanghai MacLean Biochemical Technology Co., Ltd., coumarin 6, CAS: 38215-36-0.

[0060] The antioxidant 1 is antioxidant YFK-1010;

[0061] The antioxidant 2 is antioxidant YFK-168.

[0062] The auxiliary agent includes a lubricant: N,N'-ethylene bisstearamide, purchased from Guangzhou Runfeng Chemical Co., Ltd., brand EBS B50.

[0063] Unless otherwise specified, the components and raw materials used in the embodiments and comparative examples of the present invention are all commercially available raw materials, and the components and raw materials used in each parallel experiment are all of the same kind.

[0064] Table 1

[0065]

[0066] Table 2

[0067]

[0068]

[0069] In order to verify the performance of the laser marking material of the present invention, the laser marking material prepared in each embodiment and comparative example was injection molded into a specimen to test the following properties.

[0070] Performance testing method:

[0071] 1. Laser marking method: semiconductor pump TETE TFL-M20 fiber laser marking machine is used for marking, laser wavelength is 1064nm, marking parameters: power 40%-60%, speed 1200-1600mm / s, frequency 20kHz. Color measurement is tested by spectrophotometer datacolor 1050. Definition:

[0072] (1) Color difference ΔE: refers to the difference in color perception between two samples, which includes lightness difference, chroma difference and hue difference. The larger the color difference value, the greater the color difference. The following formula is used to calculate the product using a spectrophotometer. The calculation formula is as follows:

[0073]

[0074] Among them, L represents the brightness of the color, a represents the redness and greenness, and b represents the yellowness and blueness.

[0075] (2) Hue (h): Hue h represents color information, that is, the position of the spectral color. This parameter is expressed as an angle, ranging from 0° to 360°. If calculated counterclockwise from red, red is 0°, green is 120°, and blue is 240°. Their complementary colors are: yellow is 60°, cyan is 180°, and purple is 300°. They are tested using a spectrophotometer.

[0076] (3) Chroma (c): Chroma c indicates the purity of color, also called saturation or color saturation. It usually ranges from 0-100%. The higher the chroma value, the brighter the color. It is tested using a spectrophotometer.

[0077] 2. Scratch resistance:

[0078] A friction color fastness meter was selected for testing. The test method was: under a pressure of 9N and a reciprocating speed of 60 times / min, the gauze was rubbed back and forth 100 times, and the gloss change before and after the test was compared (in order to eliminate the gloss difference of the material itself, the gloss change multiple was used to evaluate the scratch resistance: the smaller the change multiple, the better the scratch resistance; conversely, the larger the change multiple, the worse the scratch resistance).

[0079] The performance parameters obtained from the above tests are shown in Tables 3 and 4.

[0080] Table 3

[0081]

[0082] Table 4

[0083]

[0084]

[0085] According to Table 3, the color before marking is green, and the hue is between 142-152; the color after marking is yellow, and the hue is between 107-118, and the color saturation is high, which shows that the present invention can realize color marking of different hues, such as Figure 1 As shown, the technical solution of the present invention is used to achieve the yellow mark on the green workpiece. At the same time, the laser marking material also has excellent scratch resistance.

[0086] According to Table 4, when comparing Comparative Examples 2-4 with Example 1, when other yellow organic dyes, organic pigments or inorganic pigments are used, the chromaticity value before marking is very low, indicating that the color is almost black, and color marking of different hues cannot be achieved.

[0087] According to Table 4, by comparing Comparative Examples 5-7 with Example 1, no SAN resin and PMMA resin were added in Comparative Example 5, no SAN resin was added in Comparative Example 6, and no PMMA resin was added in Comparative Example 7. The scratch resistance of the laser marking materials in Comparative Examples 5-7 was not as good as that in Example 1, indicating that the addition of SAN resin and PMMA resin in the present invention is beneficial to improving the scratch resistance of the laser marking material.

[0088] According to the comparison between Comparative Examples 8-9 in Table 4 and Example 1, the higher the carbon black content, the lower the chromaticity value before and after marking, which shows that the carbon black content will affect the brightness, and too low or too high a carbon black dosage is not conducive to improving the color difference.

[0089] According to the comparison of Comparative Examples 10-11 in Table 4 with Example 1, it can be seen that the amount of colorant used has an effect on hue, chroma and color difference.

[0090] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A laser marking material, characterized in that: The composition comprises the following components in parts by weight: MABS resin 10-95 parts; SAN resin 5-30 parts; PMMA resin 10-70 parts; elastomer 0-25 parts; black pigment 0.01-0.5 parts; colorant 0.01-0.8 parts; The black pigment is carbon black; the colorant is solvent yellow 160 or coumarin 6.

2. The laser marking material according to claim 1, characterized in that: The melt mass flow rate of the MABS resin measured at 220° C. and 10 kg load is 5-30 g / 10 min.

3. The laser marking material according to claim 1, characterized in that: The melt mass flow rate of the SAN resin measured at 230° C. and 3.8 kg load is 5-20 g / 10 min.

4. The laser marking material according to claim 1, characterized in that: The melt mass flow rate of the PMMA resin measured at 230° C. and 3.8 kg load is 1-20 g / 10 min.

5. The laser marking material according to claim 1, characterized in that: The density of the PMMA resin is 1.15-1.22 g / cm 3 .

6. The laser marking material according to claim 1, characterized in that: The laser marking material comprises the following components in parts by weight: 12-90 parts of MABS resin; 6-29 parts of SAN resin; 12-64 parts of PMMA resin; 5-20 parts of elastomer; 0.1-0.4 parts of black pigment; 0.1-0.5 parts of colorant.

7. The laser marking material according to claim 1, characterized in that: The elastomer is butadiene rubber.

8. The laser marking material according to claim 1, characterized in that: The laser marking material further comprises 0.5-1.5 parts of other additives, and the other additives comprise at least one of an antioxidant, a lubricant, and a light stabilizer.

9. The method for preparing a laser marking material according to any one of claims 1 to 8, characterized in that: The following steps are involved: The components are mixed and added into a twin-screw extruder, and the laser marking material is obtained after granulation and cooling.

10. Application of the laser marking material according to any one of claims 1 to 8 in consumer electronics, household appliances, and electronic and electrical appliances.

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