Nylon composite material and preparation method and application thereof

Abstract

The application discloses a nylon composite material and a preparation method and application thereof, and relates to the technical field of laser marking materials. The nylon composite material comprises the following components in parts by weight: nylon resin 61-99 parts; bis(p-chlorophenyl)-1,4-diketopyrrolopyrrole 0.1-0.8 parts; and laser marking additive 0.2-0.8 parts. The laser marking additive is carbon black. The nylon resin is used as a base material, a chemical reaction between the nylon and bis(p-chlorophenyl)-1,4-diketopyrrolopyrrole is utilized, and a marking area is made to have a luminescent effect through a laser marking method.

Description

Technical Field

[0001] This invention relates to the technical field of laser marking materials, and in particular to a nylon composite material, its preparation method, and its application. Background Technology

[0002] Laser marking is a method that uses high-energy-density laser light to locally irradiate a workpiece, causing the surface material to vaporize or undergo a color-changing chemical reaction, thus leaving a permanent mark. It is a clean and pollution-free, environmentally friendly processing technology. Current research focuses primarily on marking effects such as black-to-white, white-to-black, and black-to-color, while research on marking effects with luminescent properties is limited. Furthermore, current resin materials require the addition of luminescent powder to produce a luminescent effect. However, the luminescent performance of the luminescent powder decreases significantly after being subjected to twin-screw shearing, resulting in a less distinct contrast between the marked and unmarked areas. This limits the promotion and application of laser marking materials with luminescent properties.

[0003] CN113845744A discloses a color-coded laser marking material with luminescent effect and its application. This technology uses coupling agents and fluorides to treat and protect the luminescent powder during processing, effectively solving the compatibility problem between the luminescent powder and ABS resin, and avoiding the problem of luminescent powder easily being worn away and turning black and discolored during processing, which is common in existing technologies. However, the protective effect of the additives on the luminescent powder is limited, and the problems of luminescent powder turning black and discoloring and reduced luminous intensity cannot be completely avoided. Furthermore, the contrast in luminous intensity between the marked and unmarked areas is not obvious.

[0004] CN114196158A discloses a laser engraving masterbatch with luminescent color markings and its preparation method. This technology endows the laser engraving masterbatch with luminescent functionality by adding organic composite luminescent powder. Its advantages lie in the good compatibility of the masterbatch carrier with resins such as PP, ABS, PA, and PC. The dispersant in the formulation ensures good dispersibility of the masterbatch in the base resin, and the heat resistance and processing stabilizer of each component of the masterbatch together ensure the stability of the masterbatch at different resin processing temperatures. However, the luminescent powder is subject to strong shearing by the twin-screw extruder, leading to a decrease in luminescence performance. Furthermore, the luminescent powder undergoes two twin-screw shearing processes, resulting not only in shear damage but also in less noticeable luminescence due to being encapsulated by the material.

[0005] CN113736247A discloses a laser-engravable polyamide composite material and its preparation method. This technology, by adding ABS resin, acrylonitrile-styrene copolymer resin, and laser engraving additives to the polyamide resin, enables the laser-engravable polyamide composite material to be used directly as a colored laser engraving material, capable of laser engraving text or patterns of various colors. However, PA materials can only be laser-engraved in different colors, but cannot produce a luminescent effect. Summary of the Invention

[0006] The purpose of this invention is to overcome the shortcomings of existing technologies and provide a nylon composite material, its preparation method, and its applications. This invention uses nylon resin as the matrix material and utilizes the chemical reaction between nylon and DPP pigment to create a luminescent effect in the marked area through laser marking.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0008] In a first aspect, the present invention provides a nylon composite material comprising the following components in parts by weight:

[0009] The composition includes 61-99 parts of nylon resin; 0.1-0.8 parts of bis(p-chlorophenyl)-1,4-dionepyrrolopyrrole; 0.2-0.8 parts of laser marking agent; and 0.1-1.5 parts of functional additives. The laser marking agent is carbon black.

[0010] This invention selects bis(p-chlorophenyl)-1,4-diketonepyrrolopyrrole as the DPP pigment. DPP pigment itself is non-fluorescent, but when used in PA (polyacrylamide), a chemical reaction occurs. The hydrogen bonds in DPP are broken by the amide bonds in PA, forming small molecules that produce fluorescence. Before marking, the DPP pigment concentration is high, and the pigment itself is not easily destroyed, thus existing primarily in pigment form with weak fluorescence. However, after marking, foaming occurs in the marked area. The pigment concentration decreases in the foamed area, and the intermolecular hydrogen bonds are more easily broken by the amide bonds, forming small molecules and resulting in stronger fluorescence. Furthermore, since the laser marking agent can absorb 1064nm infrared laser light, under laser irradiation, the marking agent can undergo photothermal conversion to generate high temperatures, causing the material to degrade and produce small molecule gases, forming foam. The pigment concentration decreases in the foamed area, thus producing fluorescence.

[0011] Preferably, the carbon black includes at least one of acetylene black, furnace black, channel black, gas black, lamp black, and pyrolysis black.

[0012] Preferably, the oil absorption value of the carbon black is 50-250 mL / 100 g.

[0013] Preferably, the nylon resin includes at least one of PA6, PA66, PA12, PA56, PA11, PA612, PA1010, and PA1212.

[0014] Preferably, the relative viscosity (RV96%H2SO4) of the nylon resin is 1.8-3.6, more preferably 2-3.4.

[0015] More preferably, the relative viscosity of the nylon resin is any one or a combination of 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, and 3.4.

[0016] Preferably, the melting point of the nylon resin is 210-230℃, and more preferably 215-220℃.

[0017] More preferably, the melting point of the nylon resin is any one or a combination of 215°C, 216°C, 217°C, 218°C, 219°C, and 220°C.

[0018] Preferably, the density of the nylon resin is 1.02-1.15 g / cm³. 3 The preferred value is 1.135-1.145 g / cm³. 3 .

[0019] Preferably, the nylon composite material comprises the following components in parts by weight:

[0020] 65-99 parts of nylon resin; 0.2-0.6 parts of bis(p-chlorophenyl)-1,4-dione pyrrolopyrrole; 0.3-0.6 parts of laser marking additive.

[0021] Preferably, the nylon composite material further includes 20-35 parts of glass fiber and 1-10 parts of toughening agent.

[0022] Preferably, the glass fiber has an average diameter of 8-15 μm and a length of 3-5 mm.

[0023] Preferably, the toughening agent is maleic anhydride-grafted ethylene-octene copolymer elastomer (POE-g-MAH).

[0024] Preferably, the nylon composite material further includes 0.1-1.5 parts of functional additives.

[0025] Preferably, the functional additives include at least one of antioxidants, lubricants, and light stabilizers.

[0026] Preferably, the antioxidant includes antioxidant 1098 and antioxidant 608.

[0027] Preferably, the lubricant comprises esters and sodium tannate salts.

[0028] More preferably, the esters include at least one of butyl stearate, glyceryl monostearate, and pentaerythritol stearate.

[0029] Preferably, the light stabilizer includes at least one of light shielding agents, ultraviolet absorbers, quenchers, free radical scavengers, and hydroperoxide decomposers.

[0030] Secondly, the present invention also discloses a method for preparing a nylon composite material, comprising the following steps:

[0031] After the components are mixed evenly, they are added to a twin-screw extruder and extruded to obtain a nylon composite material.

[0032] Preferably, the twin-screw extruder has an extrusion temperature of 250-270℃, a rotation speed of 300-350rpm, and a feed rate of 80-95kg / h.

[0033] Thirdly, the present invention also discloses the application of nylon composite materials in consumer electronics and electrical and electronic systems. Specifically, it can be used in structural parts, impellers, fans, wear-resistant fittings and snap-fit ​​components in the consumer electronics field; insulating materials (for insulation layers of wires and cables) in the electronics and electrical industries; or the housing of electronic devices, such as certain components of mobile phones and computers.

[0034] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0035] This invention produces a luminescent effect under laser irradiation without the need for luminescent material additives, avoiding the problem of luminescent materials being sheared and damaged. This invention only requires DPP pigment to achieve the luminescent effect, reducing costs. Furthermore, this effect can still be achieved in glass fiber reinforced systems, making it widely applicable. In addition to infrared laser marking, ultraviolet laser marking can also achieve this effect, as long as the marking area uses a foaming principle (black marking white effect). Carbonization principles cannot achieve this effect (white marking black effect). Detailed Implementation

[0036] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments, but the scope of protection and implementation of the present invention are not limited thereto.

[0037] Unless otherwise specified, the materials and reagents used in the following examples are commercially available.

[0038] Examples 1-14

[0039] Examples of the nylon composite material and its preparation method according to the present invention are shown in Table 1.

[0040] The preparation method of the nylon composite material includes the following steps:

[0041] (1) Dry the nylon resin thoroughly at a temperature of 120°C for 2 hours.

[0042] (2) After the components are mixed evenly, they are added to a twin-screw extruder and extruded to obtain a nylon composite material.

[0043] The temperature of the twin-screw extruder is 250-270℃, and the rotation speed is 300-350rpm.

[0044] Comparative Examples 1-11

[0045] The only difference between the comparative examples and the embodiments is the type and ratio of components, as shown in Table 2.

[0046] In the components described in each embodiment and comparative example:

[0047] The nylon resin 1 has a relative viscosity (RV 96% H2SO4) of 2.45 ± 0.04, a melting point of 215-220℃, and a density of 1.135-1.145 g / cm³. 3 Purchased from Jiangsu Haiyang Technology Co., Ltd., brand name HY-2500A;

[0048] The nylon resin 2 has a relative viscosity (RV96%H2SO4) of 2.00±0.04, a melting point of 215-220℃, and a density of 1.135-1.145 g / cm³. 3 Purchased from Jiangsu Haiyang Technology Co., Ltd., brand name HY-2000A;

[0049] The nylon resin 3 has a relative viscosity (RV 96% H2SO4) of 2.80 ± 0.04, a melting point of 215-220℃, and a density of 1.135-1.145 g / cm³. 3 Purchased from Jiangsu Haiyang Technology Co., Ltd., brand name HY-2800A;

[0050] The nylon resin 4 has a relative viscosity (RV96%H2SO4) of 3.43±0.04, a melting point of 215-220℃, and a density of 1.135-1.145 g / cm³. 3 Purchased from Jiangsu Haiyang Technology Co., Ltd., brand name HY-3400A.

[0051] The nylon resin 5: PA12 has a density of 1.03 g / cm³. 3 Melting point 183-193℃, purchased from Shandong Dongchen Ruisen New Material Technology Co., Ltd., grade TPA12.

[0052] The nylon resin 6, PA1010, has a relative viscosity (RV96%H2SO4) of 2.10-2.30 and a melting point of 198-210℃. It was purchased from Wuxi Yinda Nylon Co., Ltd., and its grade is PA1010 type 9.

[0053] The PC resin was purchased from Liaocheng Luxi Polycarbonate Co., Ltd., grade LXZY1920-01, with a melt flow rate of 18.38 g / 10 min.

[0054] The DPP pigment is bis(p-chlorophenyl)-1,4-dionepyrrolopyrrole, purchased from BASF, brand name: Red K 3840SQ.

[0055] The glass fiber has an average diameter of 10 μm and a length of 3 mm. It was purchased from Jushi Group Co., Ltd. and its grade is ECS10-03-568H.

[0056] The toughening agent was purchased from Foshan Nanhai Baichen Polymer New Materials Co., Ltd., and its brand name is PC-28.

[0057] The colorant 1 was purchased from Guangzhou Xinxinghui Chemical Co., Ltd., and the solvent was Orange 63.

[0058] The colorant 2 was purchased from Guangzhou Xinxinghui Chemical Co., Ltd., and the solvent yellow is 160.

[0059] The colorant 3 was purchased from Guangzhou Xinxinghui Chemical Co., Ltd., and the solvent is Red 197.

[0060] The colorant 4 was purchased from Guangzhou Xinxinghui Chemical Co., Ltd., and the solvent is Red 196.

[0061] The colorant 5 was purchased from Tongling Tsinghua Technology Co., Ltd., and the solvent is Red 149.

[0062] The laser marking additive 1 is acetylene black with an oil absorption value of 175ml / 100g, purchased from Shanghai Huazhongrong Industry and Trade Co., Ltd., and its brand name is DENKA acetylene black.

[0063] The laser marking additive 2 is copper chromium black, purchased from Zhongshan Huashan High-tech Ceramic Materials Co., Ltd., brand name Black DB-1.

[0064] The laser marking additive 3 is furnace black, purchased from Guangzhou Runfeng Chemical Co., Ltd., with an oil absorption value of 72ml / 100g and a grade of HIBLACK 600L;

[0065] The laser marking additive 4 is lamp-processed carbon black, purchased from Guangzhou Runfeng Chemical Co., Ltd., with an oil absorption value of 140ml / 100g and the grade LAMP BLACK 101.

[0066] The antioxidant 1, a hindered phenolic antioxidant, was purchased from Tianjin Lianlong New Material Co., Ltd., with the brand name RIANOX 1098.

[0067] Antioxidant 2, a spirophosphite antioxidant, was purchased from CBITEC, brand name [missing information]. 608.

[0068] The lubricant 1 was purchased from Emery Oleochemicals, brand name LOXIOL G 32;

[0069] The lubricant 2 was purchased from Clariant, brand name Licomont NAV101 PWD.

[0070] Unless otherwise specified, all components and raw materials used in the embodiments and comparative examples of this invention are commercially available, and the same type of components and raw materials are used in each parallel experiment.

[0071] Table 1

[0072]

[0073]

[0074] Table 2

[0075]

[0076] To verify the performance of the nylon composite material described in this invention, the nylon composite materials prepared in each embodiment and comparative example were injection molded into specimens for testing the following properties.

[0077] Performance testing methods:

[0078] 1. Fluorescence testing was performed using a Shimadzu RF-6000 fluorescence spectrophotometer with an excitation bandwidth of 5 nm and an emission bandwidth of 10 nm. Fluorescence intensity was compared under the same testing conditions, and the intensity of the unmarked area on the color plate was recorded as unit 1.

[0079] (1) Laser marking method: Marking is performed using a semiconductor-pumped TETE TFL-M20 fiber laser marking machine with a laser wavelength of 1064nm.

[0080] (2) Color measurements were performed using a Datacolor 1050 colorimeter:

[0081] Definition: Color difference ΔE: refers to the difference in color perception between two samples. It includes three aspects: lightness difference, chroma difference, and hue difference. The larger the color difference value, the greater the color difference. It is calculated using the following formula and the product is tested using a spectrophotometer.

[0082]

[0083] Where L represents the brightness of the color, a represents the red-green hue, and b represents the yellow-blue hue.

[0084] 2. Tensile strength test

[0085] Tensile strength tests were conducted using an electronic universal testing machine (model CMT4204).

[0086] The performance parameters obtained from the above tests are shown in Tables 3 and 4.

[0087] Table 3

[0088]

[0089]

[0090] Table 4

[0091]

[0092] As shown in Table 1, the nylon composite material of the present invention can produce a luminescent effect under laser action without the addition of luminescent material additives, thus avoiding the problem of luminescent material being sheared and destroyed.

[0093] As can be seen from Examples 7-8, the present invention enhances fluorescence after laser marking by adding glass fiber and toughening agent to nylon composite material, indicating that the present invention can still achieve fluorescence in the marking area in glass fiber reinforced system, and has wide applicability.

[0094] Comparing Comparative Examples 1-5 with Example 1, it can be seen that adding colorant 1-5 to the PA resin in Comparative Examples 1-5 respectively did not enhance the fluorescence after laser marking. This is because the other colorants do not react with the PA resin and therefore do not form small molecules to produce fluorescence, so the fluorescence is not enhanced after marking.

[0095] Comparing Comparative Example 6 with Example 1, it can be seen that in Comparative Example 6, when copper chromate black was used instead of carbon black, there was no obvious fluorescence in the marked area, indicating that carbon black is a necessary condition for the generation of fluorescence, and that adding only copper chromate black for marking cannot produce a significant luminescence effect.

[0096] According to the comparison between Comparative Example 7 and Example 1, after replacing PA resin with PC resin in Comparative Example 7, the marking area had almost no fluorescence. This is because PC contains benzene rings, is easy to carbonize, and is not easy to foam. After carbonization, it may mask the luminescence of DPP.

[0097] According to the comparison between Comparative Examples 8-9 and Example 1, if the content of DPP pigment is too low or too high, it cannot produce a significant luminescence effect, indicating that the content of DPP pigment has a significant impact on the luminescence effect.

[0098] According to the comparison between Comparative Examples 10-11 and Example 1, if the content of the laser marking agent is too low or too high, it cannot produce a significant luminescence effect, indicating that the content of the laser marking agent has a significant impact on the luminescence effect.

[0099] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A nylon composite, characterized by, comprising the following components by weight: nylon resin 61-99 parts; bis(p-chlorophenyl)-1,4-diketopyrrolopyrrole 0.1-0.8 parts; laser marking aid 0.2-0.8 parts; the laser marking aid is carbon black.

2. The nylon composite of claim 1, wherein, the relative viscosity, RV96%H2SO4, of the nylon resin is 1.8-3.

6.

3. The nylon composite of claim 1, wherein, the melting point of the nylon resin is 210-230°C.

4. The nylon composite of claim 1, wherein, The density of the nylon resin is 1.02-1.15 g / cm 3 .

5. The nylon composite of claim 1, wherein, the nylon composite comprises the following components by weight: nylon resin 65-99 parts; bis(p-chlorophenyl)-1,4-diketopyrrolopyrrole 0.2-0.6 parts; laser marking aid 0.3-0.6 parts.

6. The nylon composite of claim 1, wherein, the nylon composite further comprises 20-35 parts of glass fiber and 1-10 parts of toughening agent.

7. The nylon composite of claim 6, wherein the polyamide is nylon 6,6. the diameter of the glass fiber is 8-15 μm, the length is 3-5 mm, and / or the toughening agent is maleic anhydride grafted ethylene-octene copolymer elastomer.

8. The nylon composite of claim 1, wherein, the nylon composite further comprises 0.1-1.5 parts of functional aid; and the functional aid comprises at least one of antioxidant, lubricant, light stabilizer.

9. The method of making a nylon composite of any one of claims 1-8, wherein, comprising the following steps: after the components are mixed uniformly, they are added into a twin-screw extruder, and after extrusion molding, the nylon composite is obtained.

10. Use of the nylon composite according to any one of claims 1-8 in consumer electronics.

11. Use of the nylon composite according to any one of claims 1-8 in electronic and electrical.

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