Nylon composite material as well as preparation method and application thereof

Abstract

The invention discloses a nylon composite material as well as 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: 61-99 parts of nylon resin; 0.1 to 0.8 part of bis (p-chlorphenyl)-1, 4-diketopyrrolopyrrole; 0.2 to 0.8 part of a laser marking auxiliary agent; and the laser marking auxiliary agent is carbon black. According to the invention, nylon resin is used as a matrix material, and a marking area generates a luminous effect through a laser marking method by utilizing a chemical reaction between nylon and bis (p-chlorphenyl)-1, 4-diketopyrrolopyrrole.

Description

Technical Field

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

[0002] Laser marking is a marking method that uses a laser with a high energy density to locally irradiate a workpiece, causing the surface material to vaporize or undergo a chemical reaction with a color change, thereby leaving a permanent mark. It belongs to a highly environmentally friendly processing technology that is clean and pollution-free. Currently, the marking effects studied more are mainly black-on-white, white-on-black, and black-on-color, etc., while the research on the marking effect with luminescent function is less. In addition, currently, resin materials need to add corresponding luminescent powders to produce a luminescent effect. However, after the luminescent powders are subjected to twin-screw shear damage, the luminescent performance will be significantly reduced, and the contrast between the marked area and the unmarked area is not obvious, thus limiting the popularization and application of laser marking materials with luminescent characteristics.

[0003] CN113845744A discloses a colored marking laser marking material with a night-light effect and its application. This technology effectively solves the compatibility problem between the night-light powder and the ABS resin by adding a coupling agent and a fluoride for surface treatment and processing protection of the night-light powder, and avoids the problem that the night-light powder is easily worn and blackened and discolored during processing in the prior art. However, the protective effect of the auxiliary agent on the night-light powder is limited, and the problems of blackening and discoloration of the night-light powder and reduction of the luminescent intensity cannot be completely avoided, and the contrast of the luminescent intensity between the marked area and the unmarked area is not obvious.

[0004] CN114196158A discloses a laser engraving masterbatch with a night-light effect color marking and a preparation method thereof. This technology endows the engraving masterbatch with the functionality of a night-light effect by adding an organic composite night-light powder. The advantage is that the carrier of the masterbatch has good compatibility with resins such as PP, ABS, PA, and PC, and the dispersant in the formula composition ensures good dispersibility of the masterbatch in the base resin. The heat resistance and processing stabilizer of each component of the masterbatch jointly ensure the stability of the color masterbatch at the processing temperatures of different resins. However, the night-light powder will be subjected to strong shear of the twin-screw, resulting in a decrease in the luminescent performance. At the same time, the night-light powder needs to undergo twin-screw shear twice. In addition to being subjected to shear damage, it will also have unclear luminescence due to being wrapped and covered by the material.

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

[0006] The object of the present invention is to overcome the deficiencies of the prior art and provide a nylon composite material, its preparation method and application. The present invention uses nylon resin as the matrix material, utilizes the chemical reaction between nylon and DPP pigment, and makes the marked area produce a light-emitting effect through laser marking method.

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

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

[0009] 61 - 99 parts of nylon resin; 0.1 - 0.8 parts of bis(p-chlorophenyl)-1,4-diketopyrrolo[3,4-c]pyrrole; 0.2 - 0.8 parts of laser marking aid; 0.1 - 1.5 parts of functional aid; the laser marking aid is carbon black.

[0010] The present invention selects bis(p-chlorophenyl)-1,4-diketopyrrolo[3,4-c]pyrrole as the DPP pigment. The DPP pigment itself has no fluorescence, but when used in PA, a chemical reaction will occur. The hydrogen bond in DPP will be destroyed by the amide bond in PA, thereby forming small molecules to produce fluorescence: when not marked, the concentration of DPP pigment is very high, and the pigment itself is not easily destroyed, so it exists more in the form of pigment and the fluorescence is weak; but when marked, foaming occurs in the marked area, the color powder concentration in the foaming area decreases, and the intermolecular hydrogen bond is more easily destroyed by the amide bond to form small molecules, thereby forming stronger fluorescence. And because the laser marking aid can absorb the infrared laser of 1064 nm, under the action of the laser, the laser marking aid can undergo photothermal conversion to generate high temperature, thereby causing the material to degrade to produce small molecule gas, forming foaming, and the color powder concentration in the foaming area decreases, thereby producing fluorescence.

[0011] Preferably, the carbon black includes at least one of acetylene carbon black, furnace carbon black, channel carbon black, gas carbon black, lamp black, thermal cracking carbon 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, PA1212.

[0014] Preferably, the relative viscosity (RV96%H 2 SO 4 ) of the nylon resin is 1.8 - 3.6, preferably 2 - 3.4.

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

[0016] Preferably, the melting point of the nylon resin is 210 - 230 °C, preferably 215 - 220 °C.

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

[0018] Preferably, the density of the nylon resin is 1.02 - 1.15 g / cm 3 , preferably 1.135 - 1.145 g / cm 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 part of bis(p-chlorophenyl)-1,4-diketopyrrolo[3,4-c]pyrrole; 0.3 - 0.6 part of laser marking aid.

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

[0022] Preferably, the average diameter of the glass fiber is 8 - 15 μm and the length is 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 comprises 0.1 - 1.5 parts of functional aid.

[0025] Preferably, the functional aid includes at least one of antioxidant, lubricant, and light stabilizer.

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

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

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

[0029] Preferably, the light stabilizer includes at least one of light screening agent, ultraviolet absorber, quencher, free radical scavenger, and hydroperoxide decomposer.

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

[0031] After mixing all components evenly, add them to a twin-screw extruder, and obtain a nylon composite material after extrusion molding.

[0032] Preferably, the extrusion temperature of the twin-screw extruder is 250 - 270 °C, the rotation speed is 300 - 350 rpm, and the feeding rate is 80 - 95 kg / h.

[0033] In a third aspect, the present invention also discloses an application of the nylon composite material in consumer electronics and electronics and electrics. Specifically, it can be used for structural parts, impellers, fans, wear-resistant fittings, and snap components in the field of consumer electronics; insulating materials (for the insulating layer of wires and cables) in the electronics and electrics industries, or the outer shells 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] The present invention can produce a light-emitting effect under the action of laser without adding a light-emitting material additive, avoiding the problem of shear damage of the light-emitting material. The present invention only needs to use DPP pigments to achieve the light-emitting effect, reducing the cost. And this effect can still be achieved in the glass fiber reinforced system, with wide applicability. At the same time, in addition to infrared laser marking, ultraviolet laser marking can also achieve this effect, as long as the marking area is based on the foaming principle (black-on-white effect), and the carbonization principle cannot achieve this effect (white-on-black effect). Specific Embodiments

[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 protection scope and implementation manner of the present invention are not limited thereto.

[0037] The materials, reagents, etc. used in the following embodiments are commercially available reagents and materials unless otherwise specified.

[0038] Examples 1 - 14

[0039] Embodiments of the nylon composite material and its preparation method of the present invention, the composition components of the nylon composite material are shown in Table 1.

[0040] The method for preparing the nylon composite material comprises the following steps:

[0041] (1) Thoroughly dry the nylon resin at a drying temperature of 120 °C for 2 hours;

[0042] (2) After mixing all components evenly, add them to a twin-screw extruder, and obtain a nylon composite material after extrusion molding.

[0043] Among them, the temperature of the twin-screw extruder is 250 - 270 °C, and the rotational speed is 300 - 350 rpm.

[0044] Comparative Examples 1 - 11

[0045] The differences between each comparative example and the example are only the types and ratios of the components, as shown in Table 2.

[0046] In the components of each example and comparative example:

[0047] The nylon resin 1: The relative viscosity (RV96% H 2 SO 4 ) is 2.45 ± 0.04, the melting point is 215 - 220 °C, and the density is 1.135 - 1.145 g / cm 3 , purchased from Jiangsu Haiyang Technology Co., Ltd., brand HY - 2500A;

[0048] The nylon resin 2: The relative viscosity (RV96% H 2 SO 4 ) is 2.00 ± 0.04, the melting point is 215 - 220 °C, and the density is 1.135 - 1.145 g / cm 3 , purchased from Jiangsu Haiyang Technology Co., Ltd., brand HY - 2000A;

[0049] The nylon resin 3: The relative viscosity (RV96% H 2 SO 4 ) is 2.80 ± 0.04, the melting point is 215 - 220 °C, and the density is 1.135 - 1.145 g / cm 3 , purchased from Jiangsu Haiyang Technology Co., Ltd., brand HY - 2800A;

[0050] The nylon resin 4: The relative viscosity (RV96% H 2 SO 4 ) is 3.43 ± 0.04, the melting point is 215 - 220 °C, and the density is 1.135 - 1.145 g / cm 3 , purchased from Jiangsu Haiyang Technology Co., Ltd., brand HY - 3400A.

[0051] The nylon resin 5: PA12, density 1.03 g / cm 3 , melting point 183 - 193 °C, purchased from Shandong Dongchen Ruisen New Material Technology Co., Ltd., brand TPA12.

[0052] The nylon resin 6: PA1010, relative viscosity (RV96% H 2 SO 4) is 2.10 - 2.30, the melting point is 198 - 210 °C, purchased from Wuxi Yinda Nylon Co., Ltd., grade PA1010 9 type.

[0053] The described PC resin: purchased from Liaocheng Luxi Polycarbonate Co., Ltd., grade LXZY1920 - 01, melt mass flow rate: 18.38 g / 10 min.

[0054] The described DPP pigment is bis(p - chlorophenyl)-1,4 - diketopyrrolo[3,4 - c]pyrrole, purchased from BASF, grade Red K 3840SQ.

[0055] The described glass fiber: the average diameter of the fiber is 10 μm, the length is 3 mm, purchased from Jushi Group Co., Ltd., grade glass fiber ECS10 - 03 - 568H.

[0056] The described toughening agent: purchased from Foshan Nanhai Baichen New Polymer Materials Co., Ltd., grade PC - 28.

[0057] The described colorant 1, purchased from Guangzhou Xinxinghui Chemical Co., Ltd., solvent orange 63;

[0058] The described colorant 2, purchased from Guangzhou Xinxinghui Chemical Co., Ltd., solvent yellow 160;

[0059] The described colorant 3, purchased from Guangzhou Xinxinghui Chemical Co., Ltd., solvent red 197;

[0060] The described colorant 4, purchased from Guangzhou Xinxinghui Chemical Co., Ltd., solvent red 196;

[0061] The described colorant 5, purchased from Tongling Qinghua Technology Co., Ltd., solvent red 149.

[0062] The described laser marking aid 1 is acetylene carbon black, the oil absorption value is 175 ml / 100 g, purchased from Shanghai Huazhongrong Industry and Trade Co., Ltd., grade acetylene carbon black DENKA;

[0063] The described laser marking aid 2 is copper chromite black, purchased from Zhongshan Huashan High - tech Ceramic Materials Co., Ltd., grade Black DB - 1.

[0064] The described laser marking aid 3 is furnace - black, purchased from Guangzhou Runfeng Chemical Co., Ltd., the oil absorption value is 72 ml / 100 g, grade HIBLACK 600L;

[0065] The described laser marking aid 4 is lamp - black, purchased from Guangzhou Runfeng Chemical Co., Ltd., the oil absorption value is 140 ml / 100 g, grade LAMP BLACK 101.

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

[0067] The antioxidant 2, a spirophosphite antioxidant, was purchased from CBITEC, brand 608.

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

[0069] The lubricant 2 is purchased from Clariant and has the brand name Licomont NAV101 PWD.

[0070] 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.

[0071] Table 1

[0072]

[0073]

[0074] Table 2

[0075]

[0076] In order to verify the performance of the nylon composite material of the present invention, the nylon composite material prepared in each embodiment and comparative example was injection molded into a specimen to test the following properties.

[0077] Performance testing method:

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

[0079] (1) Laser marking method: A semiconductor-pumped TETE TFL-M20 fiber laser marking machine is used for marking, with a laser wavelength of 1064 nm.

[0080] (2) Color measurement is performed using a colorimeter, Datacolor 1050:

[0081] Definition: 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 and the product is tested with a spectrophotometer;

[0082]

[0083] Among them, L represents the brightness of the color, a represents the red-green degree, and b represents the yellow-blue degree.

[0084] 2. Tensile strength test

[0085] The tensile strength test was carried out 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] According to Table 1, it can be seen that the nylon composite material described in the present invention can produce a light-emitting effect under the action of laser without adding a light-emitting material additive, avoiding the problem of shear damage of the light-emitting material.

[0093] According to Examples 7-8, it can be seen that by adding glass fiber and toughening agent to the nylon composite material in the present invention, the fluorescence is enhanced after laser marking, indicating that the present invention can still achieve the effect of fluorescence in the marking area in the glass fiber reinforced system, with wide applicability.

[0094] By comparing Comparative Examples 1-5 with Example 1 respectively, it can be obtained that in Comparative Examples 1-5, colorants 1-5 are respectively added to the PA resin, and the fluorescence will not be enhanced after laser marking. This is because other colorants will not react with the PA resin, and thus small molecules will not be formed to produce fluorescence, so the fluorescence will not be enhanced after marking.

[0095] By comparing Comparative Example 6 with Example 1, it can be obtained that in Comparative Example 6, copper chromite black is used to replace carbon black, and there is no obvious fluorescence in the marking area, indicating that carbon black is a necessary condition for producing fluorescence, and only adding copper chromite black cannot produce a significant light-emitting effect after marking.

[0096] By comparing Comparative Example 7 with Example 1, it can be obtained that after replacing the PA resin with PC resin in Comparative Example 7, there is almost no fluorescence in the marking area. This is because PC contains benzene rings and is easy to carbonize and not easy to foam, and the carbonization may cover up the luminescence of DPP instead.

[0097] By comparing Comparative Examples 8-9 with Example 1 respectively, it can be obtained that if the content of DPP pigment is too low or too high, a significant light-emitting effect cannot be produced, indicating that the content of DPP pigment has a great influence on the light-emitting effect.

[0098] Comparing Comparative Examples 10-11 with Example 1 respectively, it can be seen that if the content of the laser marking additive is too low or too high, a significant light-emitting effect cannot be produced, indicating that the content of the laser marking additive has a great influence on the light-emitting effect.

[0099] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A nylon composite material, characterized in that: The composition comprises the following components in parts by weight: 61-99 parts of nylon resin; 0.1-0.8 parts of bis(p-chlorophenyl)-1,4-diketopyrrolopyrrole; 0.2-0.8 parts of laser marking auxiliary agent; the laser marking auxiliary agent is carbon black.

2. The nylon composite material according to claim 1, characterized in that: The relative viscosity (RV96% H2SO4) of the nylon resin is 1.8-3.

6.

3. The nylon composite material according to claim 1, characterized in that: The melting point of the nylon resin is 210-230°C.

4. The nylon composite material according to claim 1, characterized in that: The density of the nylon resin is 1.02-1.15 g / cm 3 .

5. The nylon composite material according to claim 1, characterized in that: The nylon composite material comprises the following components in parts by weight: 65-99 parts of nylon resin; 0.2-0.6 parts of bis(p-chlorophenyl)-1,4-diketopyrrolopyrrole; and 0.3-0.6 parts of laser marking auxiliary agent.

6. The nylon composite material according to claim 1, characterized in that: The nylon composite material also includes 20-35 parts of glass fiber and 1-10 parts of toughening agent.

7. The nylon composite material according to claim 6, characterized in that: The glass fiber has a diameter of 8-15 μm and a length of 3-5 mm, and / or the toughening agent is maleic anhydride grafted ethylene-octene copolymer elastomer.

8. The nylon composite material according to claim 1, characterized in that: The nylon composite material further comprises 0.1-1.5 parts of a functional additive; and the functional additive comprises at least one of an antioxidant, a lubricant, and a light stabilizer.

9. The method for preparing the nylon composite material according to any one of claims 1 to 8, characterized in that: The following steps are involved: After the components are evenly mixed, they are added into a twin-screw extruder, and the nylon composite material is obtained after extrusion molding.

10. Application of the nylon composite material according to any one of claims 1 to 8 in consumer electronics and electrical and electronic applications.

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