CN111171559B

CN111171559B - Light-color laser marking composite material and preparation method thereof

Info

Publication number: CN111171559B
Application number: CN202010092367.6A
Authority: CN
Inventors: 罗烈君; 秦立杰
Original assignee: Guangdong Huatong New Material Technology Co ltd
Current assignee: Guangdong Huatong New Material Technology Co ltd
Priority date: 2020-02-14
Filing date: 2020-02-14
Publication date: 2022-12-06
Anticipated expiration: 2040-02-14
Also published as: CN111171559A

Abstract

The invention provides a light-color laser marking composite material and a preparation method thereof. The preparation method of the light-color laser marking composite material comprises the following steps: respectively adding the following components in parts by weight into a mixer and stirring to obtain a mixture, namely 40-50 parts of nylon 6 resin; 15-20 parts of glass fiber; 3-8 parts of a chromogenic filler; 30-40 parts of functional filler; 0.01-0.05 part of coloring pigment; 0.2-0.5 part of friction-resistant auxiliary agent; 0.1-0.6 part of antioxidant; 0.5-5 parts of other functional additives; wherein the color development filler is a mixture of zinc oxide, titanium dioxide and zirconium oxide; and adding the mixture into an extruder to prepare the light-color laser marked composite material. After the composite material prepared by the invention is subjected to laser engraving, a light-color or white mark can be engraved on a dark-color material, and the mark has the advantages of clear and firm effect, high durability and difficult erasing. In addition, the mechanical performance of the composite material marked by the light-colored laser is not influenced by the colored filler, and the composite material has wider application.

Description

Light-color laser marking composite material and preparation method thereof

Technical Field

The invention relates to the technical field of laser carving composite material preparation, in particular to a light-color laser marking composite material and a preparation method thereof.

Background

Laser carving, also called laser sculpture or laser marking, be the industrial marking method that develops comparatively rapidly in recent years, along with the continuous development of two-dimensional code technique, promote, the application face is also wider and wider, adopts laser carving technique to carve two-dimensional code laser at the product surface and becomes more and more common, also has very high requirement to glyptic definition simultaneously.

Laser engraving identification generally refers to a method for marking a workpiece by irradiating a surface layer of the workpiece by laser to enable the material of the surface layer of the workpiece to generate chemical or physical changes and generate color changes. For white laser marking on the surface of a black or other dark material, when the laser etching processing power exceeds 30%, the mark becomes black and yellow, and is close to the color of the product, so that the mark is difficult to distinguish or even cannot be distinguished, for example, when a two-dimensional code is laser etched on the surface of the product, the two-dimensional code is difficult to scan and identify; when the laser engraving processing power is low, the engraved white is unclear and is easy to erase.

Disclosure of Invention

The invention solves the problem that the prior art is lack of a preparation method of a dark color material, and clear white marks can be radium-carved on the dark color material by a radium carving technology.

In order to solve the problems, the invention provides a preparation method of a light-color laser marking composite material, which comprises the following steps:

respectively adding the following components in parts by weight into a mixer, and stirring to obtain a mixture;

40-50 parts of nylon 6 resin;

15-20 parts of glass fiber;

3-8 parts of a color development filler;

30-40 parts of functional filler;

0.01-0.05 part of coloring pigment;

0.2-0.5 part of friction-resistant auxiliary agent;

0.1-0.6 part of antioxidant;

0.5-5 parts of other functional additives;

wherein the color development filler is a mixture of zinc oxide, titanium dioxide and zirconium oxide;

and adding the mixture into an extruder to prepare the light-color laser marked composite material.

Preferably, the mass ratio of the zinc oxide, the titanium dioxide and the zirconium oxide is 6-8.

Preferably, the mix comprises:

50 parts of nylon 6 resin; 17.5 parts of glass fiber; 3-8 parts of a color development filler; 35 parts of functional filler; 0.02 part of coloring pigment; 0.35 part of friction-resistant auxiliary agent; 0.35 part of antioxidant; 0.25 part of other functional auxiliary agents.

Preferably, the particle sizes of the zinc oxide, the titanium dioxide and the zirconium oxide are all 20-30nm.

Preferably, the coloring pigment includes black sand, carbon black or iron red.

Preferably, the glass fiber is alkali-free glass fiber, and the diameter of the glass fiber is 5-24 μm.

Preferably, the other functional auxiliary agent comprises at least one of a coupling agent, an antistatic auxiliary agent, an antioxidant, a compatilizer and a toughening agent.

Preferably, the temperature of the twin-screw extruder from the feeding port to the die head is 210-250 ℃, 250-290 ℃, 240-280 ℃, 200-240 ℃, 190-230 ℃, 170-210 ℃ and 210-250 ℃ respectively.

Preferably, the stirring time of the nylon 6 resin, the glass fiber, the color developing filler, the functional filler, the coloring pigment, the friction-resistant auxiliary agent, the antioxidant and the other functional auxiliary agents in the mixer is 15-20min.

Compared with the prior art, the preparation method of the light-color laser marking composite material provided by the invention has the following beneficial effects:

according to the invention, when the light-color laser marking composite material is prepared, the color development filler comprising the mixture of zinc oxide, titanium dioxide and zirconium oxide is added, and the prepared composite material can be engraved with a light-color or white mark on a dark-color material after laser engraving, and the mark has the advantages of clear and firm effect, high durability and difficulty in erasing. In addition, the mechanical property of the light-color laser marked composite material prepared by the invention is not influenced by the color developing filler, and the composite material has wider application.

The invention also provides a light-color laser marking composite material which is prepared by adopting the preparation method of the light-color laser marking composite material.

Compared with the prior art, the light-color laser marking composite material provided by the invention has the following beneficial effects, and is the same as the preparation method of the light-color laser marking composite material, and the details are not repeated.

Detailed Description

In order to make the aforementioned objects, features and advantages of the present invention comprehensible, specific embodiments thereof are described in detail below.

The embodiment of the invention provides a preparation method of a light-color laser marking composite material, which comprises the following steps:

respectively adding the following components in parts by weight into a mixer to obtain a mixture;

40-50 parts of nylon 6 resin;

15-20 parts of glass fiber;

3-8 parts of a chromogenic filler;

30-40 parts of functional filler;

0.01-0.05 part of coloring pigment;

0.2-0.5 part of friction-resistant auxiliary agent;

0.1-0.6 part of antioxidant;

0.5-5 parts of other functional additives;

wherein, the color development filler is a mixture of zinc oxide, titanium dioxide and zirconium oxide.

And adding the mixture into an extruder to prepare the light-color laser marked composite material. Specifically, nylon 6 resin, a color developing filler, glass fiber, a functional filler, a coloring pigment, a friction-resistant auxiliary agent, an antioxidant and other functional auxiliary agents are respectively added into a high-speed mixer according to parts by weight and stirred for 15-20min at normal temperature.

And plasticizing and extruding the uniformly stirred mixture by a co-rotating double-screw extruder, and dragging and granulating to obtain the light-color laser marked composite material. Wherein the length-diameter ratio of the double-screw extruder is more than or equal to 42. The temperatures of the screws of each section of the double-screw extruder from the feeding port to the die head are 210-250 ℃, 250-290 ℃, 240-280 ℃, 200-240 ℃, 190-230 ℃, 170-210 ℃ and 210-250 ℃ respectively. The die head plate has a heating function, the vacuumizing pressure of the barrel of the extruder is greater than or equal to 0.06Mpa, the water passing length is controlled to be 0.1-0.3m, and the cooling length is greater than 4m.

And further, injecting the light-color laser marked composite material into a required product by using an injection molding machine, and then placing the product under a laser engraving machine for marking and engraving.

The composite material prepared by the method provided by the embodiment contains the color developing filler, and the color developing filler is used for displaying a light-colored or white mark on the surface of the material when the composite material is subjected to laser etching. The zinc oxide, titanium dioxide and zirconium oxide contained in the color development filler are white powdery substances, the purity is more than or equal to 99.9 percent, and the color development filler is preferably a nano-grade material, and the particle size is preferably 20-30nm. In the embodiment, the particle sizes of all components in the color development filler are nano-scale, so that the roughness of the color development surface can be reduced, and the color development effect is more exquisite.

The zinc oxide has the functions of enabling the laser carving surface of the material to be hard, preventing mildew, resisting pulverization and preventing rust, and the service life of developing light color of the color developing filler can be prolonged. Titanium dioxide is a core material in the color-developing filler, when the surface of the material is carbonized or the surface high molecular components are decomposed due to the high energy of laser engraving, organic matters are remained on the surface of the material, and the white color of the titanium dioxide can be well displayed. Since zirconia has a melting point of more than 2500 ℃, which is a high temperature resistant material, it can protect the remaining inorganic substances well, but since it has too high hardness, the addition of too much will accelerate the wear of the equipment, and also will increase the cost. Therefore, the mass ratio of zinc oxide, titanium dioxide and zirconium oxide in this example is 6-8.

The composite material prepared by the embodiment contains glass fibers, and the glass fibers mainly play a role in enhancing physical properties of products such as impact, bending and stretching. The glass fiber is alkali-free glass fiber, and can be short fiber or long fiber, and the diameter of the fiber is 5-24 μm.

In the composite material prepared by the embodiment, the functional filler is used for enabling the composite material to obtain the functions of flame retardance, heat conduction, heat dissipation, electric conduction, insulation and the like. The coloring pigment is used to provide a coloring effect to the composite material itself, and is preferably black sand, carbon black or iron red. The main component of the friction-resistant auxiliary agent is polytetrafluoroethylene, and the main component is injection molding-grade polytetrafluoroethylene. The antioxidant is an active organic copper compound, also called as a nylon copper salt heat stabilizer, and the antioxidant can also be N, N' -bis- (3- (35-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine or tris (2, 4-di-tert-butylphenyl) phosphite. The other functional auxiliary agent comprises at least one of a coupling agent, an antistatic auxiliary agent, a compatilizer and a toughening agent.

The composite material prepared by the embodiment has the advantages that under the action of laser engraving, the color developing filler displays white or light-color marks on the surface of the material, so that laser marking is realized, the marking effect is clear and firm, and the durability are realized.

The details are described below with reference to specific examples.

Example 1

The embodiment provides a preparation method of a light-color laser marking composite material.

Adding 50g of nylon 6 resin, 17.5g of glass fiber, 3g of color development filler, 35g of functional filler, 0.02g of coloring pigment, 0.35g of friction-resistant auxiliary agent, 0.35g of antioxidant and 2.5g of other functional auxiliary agents into a high-speed mixer, and mixing for 15min to obtain a mixture; wherein, the granularity of zinc oxide, titanium dioxide and zirconia in the color development filler is 20nm, 25nm and 30nm respectively, and the mass ratio of zinc oxide to titanium dioxide to zirconia is 8.

And adding the mixture into a co-rotating double-screw extruder, wherein the temperatures of the screws of all sections of the double-screw extruder from a feeding port to a die head are 230 ℃, 270 ℃, 260 ℃, 220 ℃, 210 ℃, 190 ℃ and 230 ℃, and the light-color laser marking composite material is obtained after melting plasticization, extrusion, traction, grain cutting and cooling of the double-screw extruder.

Example 2

The difference between the present example and example 1 is that the weight parts of the components in the mixture are different, and in the present example, 50g of nylon 6 resin, 17.5g of glass fiber, 5g of color developing filler, 35g of functional filler, 0.02g of coloring pigment, 0.35g of friction-resistant auxiliary agent, 0.35g of antioxidant and 2.5g of other functional auxiliary agent are added into a high-speed mixer and mixed for 15min to obtain a mixture.

Example 3

The difference between the embodiment and the embodiment 1 is that the weight parts of the components in the mixture are different, in the embodiment, 50g of nylon 6 resin, 17.5g of glass fiber, 7g of color development filler, 35g of functional filler, 0.02g of coloring pigment, 0.35g of friction-resistant auxiliary agent, 0.35g of antioxidant and 2.5g of other functional auxiliary agent are added into a high-speed mixer to be mixed for 15min, and the mixture is obtained.

Example 4

The difference between the present example and example 1 is that the weight parts of the components in the mixture are different, and in the present example, 50g of nylon 6 resin, 17.5g of glass fiber, 8g of color developing filler, 35g of functional filler, 0.02g of coloring pigment, 0.35g of friction-resistant auxiliary agent, 0.35g of antioxidant and 2.5g of other functional auxiliary agent are added into a high-speed mixer and mixed for 15min to obtain a mixture.

Example 5

The difference between the present example and example 1 is that the ratio of each component in the color-developing filler is different, and in the present example, the mass ratio of zinc oxide, titanium dioxide and zirconium oxide in the color-developing filler is 6.

Example 6

The difference between the present example and example 2 is that the ratio of each component in the color-developing filler is different, and in the present example, the mass ratio of zinc oxide, titanium dioxide and zirconium oxide in the color-developing filler is 6.

Example 7

The difference between the present example and example 3 is that the ratio of each component in the color-developing filler is different, and in the present example, the mass ratio of zinc oxide, titanium dioxide and zirconium oxide in the color-developing filler is 6.

Example 8

The difference between the present example and example 4 is that the ratio of each component in the color-developing filler is different, and in the present example, the mass ratio of zinc oxide, titanium dioxide and zirconium oxide in the color-developing filler is 6.

Example 9

This example compares the performance of light-colored laser-marked composites made in examples 1-8 and provides two sets of comparative examples. Comparative example 1 is different from example 1 in that no color developing filler is added to comparative example 1. Comparative example 2 differs from example 5 in that no chromogenic filler was added to comparative example 2. The component pair ratios of examples 1 to 8 and comparative examples 1 to 2 are shown in tables 1 and 2;

table 1:

table 2:

the composites prepared in examples 1 to 4 and comparative example 1 were subjected to whiteness tests, respectively, and the composites prepared in examples 1 to 4 and comparative example 1 were subjected to logo-engraving at different laser engraving powers, respectively, and the engraved logos were subjected to whiteness tests, and similarly, the composites prepared in examples 5 to 8 and comparative example 2 were also subjected to the above tests, and the results are shown in table 3.

Wherein, the model that the radium carving machine originated from Shenzhen, precious good luck laser technology Limited is 20W-laser type radium carving machine, and operating parameter is: the laser wattage is 20W, the spot size is 0.050mm, the speed is 2000.00 mm/s, the frequency is 20kHz, the jump speed is 4000 mm/s, and the dotting time is 0.100ms. The whiteness meter is a whiteness meter with the model of HK-01A produced by Hengke automated equipment Limited company in Dongguan city, and the working parameters are as follows: white WB = R457 for blue, LED light source, aperture 30, resolution 0.1.

Table 3:

according to the whiteness of the composite material prepared in the comparative example 1, the whiteness of the engraved mark is reduced along with the increase of the laser etching power under the laser etching power of 40%, 60% and 90%. While the whiteness of the engraved marks of the composite materials prepared according to the examples 1 to 4 is respectively obtained under 40%, 60% and 90% of laser engraving power, the whiteness of the engraved marks is increased along with the increase of the laser engraving power. The reason is that the composite materials prepared in examples 1-4 contain the color development filler, the titanium dioxide in the color development filler has a good whitening effect, the inorganic substances remained on the surface of the materials can be well protected due to the addition of the zirconium oxide, so that the displayed white is not easy to erase, and in addition, the material has light color development and durability due to the addition of the zinc oxide, so that the service life of the light color development of the functional materials is prolonged. Therefore, the whiteness of the prepared composite material can be improved by improving the laser etching power, and the mode is simple and controllable.

As can be seen from Table 3, the composite materials prepared in examples 1-4 have gradually increased or decreased content of the chromogenic filler, and the whiteness of the composite material is higher as the addition amount of the chromogenic filler in the composite material is increased under the same laser etching power. Therefore, the whiteness of the engraved mark after laser etching of the composite material can be controlled by controlling the amount of the color developing filler added into the composite material.

The whiteness test of the engraved markings made on the composites made in examples 5-8 was similar to the analysis of the results of the tests made on the composites made in examples 1-4 and will not be described in detail here.

In addition, as can be seen from table 3, the mass ratio of zinc oxide, titanium dioxide and zirconium oxide in the color-developing fillers in examples 1 to 4 is 8.

Further, the composite materials prepared in the embodiments 1 to 4 and the comparative example 1 are subjected to engraving of the two-dimensional code identification under a laser engraving machine, and the two-dimensional code is scanned by a mobile phone to detect whether the engraved two-dimensional code mark is clear or not. The composites obtained in examples 5 to 8 and comparative example 2 were also subjected to the above-mentioned tests, and the results are shown in Table 4:

table 4:

the composite materials prepared in examples 1 to 4 and the comparative example are all engraved under 60% of laser engraving power, the two-dimensional code marks are respectively engraved on the surfaces of the composite materials, and the engraved two-dimensional codes on each composite material are respectively scanned and identified by using four mobile phones, namely P30, P9, OPPO15X and red rice 6A.

As can be seen from table 4, the composite material prepared in comparative example 1 does not contain a color developing filler, so that the two-dimensional code engraved on the composite material prepared in comparative example 1 has low identification definition and is not easy to distinguish, and no two-dimensional code is identified by scanning with four mobile phones.

The composite materials prepared in the embodiments 1 to 4 all contain the color developing filler, and the two-dimensional code marks obtained by laser etching are easy to be scanned and identified by a mobile phone, so that the marks etched by the laser etching of the composite materials prepared by the invention have high definition and identification degree.

The clear identification test of the engraved two-dimensional code performed on the composite materials prepared in examples 5 to 8 is similar to the analysis of the results of the test performed on the composite materials prepared in examples 1 to 4, and is not described herein again.

The composites prepared in the above examples were tested for mechanical properties as shown in table 5.

Table 5:

according to Table 5, the composite materials obtained in examples 1 to 4 all contained a colored filler, but the notched impact strength, tensile strength, flexural strength and elongation at break of the composite materials were not much different from those of the composite material obtained in comparative example 1. The invention improves the definition, durability and the like of the carved marks of the composite material by adding the color developing filler, but the mechanical performance of the composite material is not influenced by the addition of the color developing filler.

The analysis of the results of the mechanical property tests carried out on the composites obtained in examples 5 to 8 is similar to that carried out on the composites obtained in examples 1 to 4 and will not be described in detail here.

In addition, comparing examples 1 and 5, examples 2 and 6, examples 3 and 7, and examples 4 and 8, respectively, it can be seen that changing the mass ratio of zinc oxide, titanium dioxide and zirconium oxide in the color-developing filler has less influence on the mechanical properties of the resulting composite material. Therefore, the light-color laser marked composite material prepared by the invention is not influenced by the color development filler and has wider application.

Example 10

The embodiment provides a preparation method of laser etching master batch for light color identification.

50g of nylon 6 resin, 15g of glass fiber, 3g of color development filler, 40g of functional filler, 0.01g of coloring pigment, 0.5g of friction-resistant auxiliary agent, 0.1g of antioxidant and 0.5g of other functional auxiliary agents are added into a high-speed mixer to be mixed for 15min, so as to obtain a mixture.

And adding the mixture into a co-rotating double-screw extruder, wherein the temperatures of the screws of all sections of the double-screw extruder from a feeding port to a die head are respectively 210 ℃, 250 ℃, 240 ℃, 200 ℃, 190 ℃, 170 ℃ and 210 ℃, and the light-color laser marked composite material is obtained after melting plasticization, extrusion, traction granulation and cooling of the double-screw extruder.

Example 11

Adding 40g of nylon 6 resin, 20g of glass fiber, 8g of color development filler, 30g of functional filler, 0.05g of coloring pigment, 0.2g of friction-resistant auxiliary agent, 0.6g of antioxidant and 5g of other functional auxiliary agents into a high-speed mixer, and mixing for 20min to obtain a mixture.

And adding the mixture into a co-rotating double-screw extruder, wherein the temperatures of the screws in each section of the double-screw extruder from a feeding port to a die head are respectively 250 ℃, 290 ℃, 280 ℃, 240 ℃, 230 ℃, 210 ℃ and 250 ℃, and the light-color laser marking composite material is obtained after melting plasticization, extrusion, traction, grain cutting and cooling of the double-screw extruder.

Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Various changes and modifications may be made by those skilled in the art without departing from the spirit and scope of the disclosure, and these changes and modifications are intended to fall within the scope of the invention.

Claims

1. A preparation method of a light-color laser marking composite material is characterized by comprising the following steps:

40-50 parts of nylon 6 resin;

15-20 parts of glass fiber;

3-8 parts of a color development filler;

30-40 parts of functional filler;

0.01-0.05 part of coloring pigment;

0.2-0.5 part of friction-resistant auxiliary agent;

0.1-0.6 part of antioxidant;

0.5-5 parts of other functional additives;

wherein the color development filler is a mixture of zinc oxide, titanium dioxide and zirconia, the mass ratio of the zinc oxide to the titanium dioxide to the zirconia is 6-8;

and adding the mixture into an extruder to prepare the light-color laser marking composite material.

2. The method of making a light-colored laser marked composite material according to claim 1, wherein the compound comprises:

50 parts of nylon 6 resin; 17.5 parts of glass fiber; 3-8 parts of a chromogenic filler; 35 parts of functional filler; 0.02 part of coloring pigment; 0.35 part of friction-resistant auxiliary agent; 0.35 part of antioxidant; 0.25 part of other functional auxiliary agents.

3. The method of making a light-colored laser marked composite according to claim 1 wherein the colored pigment comprises black sand, carbon black or iron red.

4. The method for preparing the light-colored laser marked composite material according to claim 1, characterized in that the glass fiber is alkali-free glass fiber, and the diameter of the glass fiber is 5-24 μm.

5. The method of claim 1, wherein the other functional additives include at least one of coupling agents, antistatic additives, antioxidants, compatibilizers, and toughening agents.

6. The method of claim 1, wherein the extruder is a twin screw extruder, and the temperatures of the screws in the sections of the twin screw extruder from the feed port to the die are 210-250 ℃, 250-290 ℃, 240-280 ℃, 200-240 ℃, 190-230 ℃, 170-210 ℃ and 210-250 ℃.

7. The method of preparing a light-colored laser marked composite according to claim 1, characterized in that the stirring time of the nylon 6 resin, the glass fiber, the color developing filler, the functional filler, the coloring pigment, the friction-resistant assistant, the antioxidant and the other functional assistant in the mixer is 15-20min.

8. A light-colored laser-marked composite, characterized in that it is produced by a process for the preparation of a light-colored laser-marked composite according to any of claims 1 to 7.