CN111320799B - Auxiliary agent composition for color change in light-colored base polymer and preparation method thereof - Google Patents

Auxiliary agent composition for color change in light-colored base polymer and preparation method thereof Download PDF

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CN111320799B
CN111320799B CN202010209778.9A CN202010209778A CN111320799B CN 111320799 B CN111320799 B CN 111320799B CN 202010209778 A CN202010209778 A CN 202010209778A CN 111320799 B CN111320799 B CN 111320799B
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laser marking
ethylene
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copolymer
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CN111320799A (en
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周涛
冯金
陈佳骏
彭小燕
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Sichuan University
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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    • C08L2207/066—LDPE (radical process)

Abstract

The invention provides an auxiliary agent composition for color change in a light-colored base polymer and a preparation method thereof, belonging to the field of polymer material auxiliary agents. The auxiliary agent composition comprises the following raw materials in parts by weight: 41.0 to 90.0 parts of mixture, 0.5 to 6.0 parts of compatibilizer and 4.0 to 58.5 parts of carrier polymer; the mixture comprises metal powder, metal oxide, thermoplastic polymer and accelerant; the weight ratio of the metal powder, the metal oxide, the thermoplastic polymer and the accelerator is (0.3-3.0): (70-90): (2.0-29.6): (0.1-5.0). The color change auxiliary agent composition has high color difference contrast and light color, and can be applied to marking of light-colored base polymers. In addition, the color change auxiliary composition is simple and convenient in preparation method, easy to operate and good in application prospect.

Description

Auxiliary agent composition for color change in light-colored base polymer and preparation method thereof
Technical Field
The invention belongs to the field of polymer material additives, and particularly relates to an additive composition for color change in a light-colored base polymer and a preparation method thereof.
Background
Currently, there are many techniques for marking commercial products, such as: screen printing, ink printing, stamping, and the like. However, the marks obtained by the above marking techniques are easily blurred and difficult to be identified due to friction, mechanical damage, chemical action and the like during storage and transportation; meanwhile, the mark is easy to alter, and the permanent mark and the anti-counterfeiting function of the product are difficult to realize.
In order to overcome the defects of the marking technology, researchers develop a novel method for marking the polymer material according to the characteristics of the marked object, the method utilizes high-energy of laser to irradiate the material to cause carbonization, foaming, color change reaction and the like to generate a mark with a color different from that of a base material, and the method is mainly applied to the aspects of permanent marking of the polymer material, product anti-counterfeiting, tracking of important parts and the like.
However, most polymer matrix materials have insufficient ability to absorb energy, and it is difficult to form a color difference of high contrast. In order to improve the color difference contrast of the polymer matrix material, it is often necessary to select suitable components as additives (also referred to as adjuvants) of the matrix material and to change the physical state of the additives, etc., for example: the world patent WO2009/003976 adopts microspheres formed by components such as laser absorbent, thermoplastic polymer, compatibilizer, carrier polymer and the like as laser marking additives, and the laser absorbent of the microsphere can form higher chromatic aberration contrast only by selecting at least two different metal oxides and metal hydroxides; engghard, usa for Nd: YAG laser develops a material composed of tin oxide and Sb2O3A laser absorber consisting of calcined powder of (A), but separately added tin oxide or Sb2O3No good marking effect can be obtained (see: fengchi, wu wenjing, li s source, zhangyong. laser marking plastic research progress, chinese plastic, 2011, 9 months, volume 25, phase 9.); world patent WO2011/050934 also needs to adopt Bi2O3And the bismuth citrate is compatible with two laser absorbers. In addition, the metal particles are independently selected as the laser absorbent, so that flow marks or stripes are easily generated during marking, the color difference contrast is not clear, and the polymer is easily degraded and foamed, so that the marking effect is seriously influenced.
In the prior art, the single use of metal particles or the single use of marking additives of metal oxides is difficult to form color difference with higher contrast, even though the Iriotec 8208 of Merck, a patent product of world patent WO2009/003976, adopts two laser absorbers of antimony trioxide and antimony tin oxide, the formed color difference contrast is still limited, and the marking application requiring higher contrast is difficult to meet. In patent CN104610642, a novel additive composition is reported, which is characterized in that metal particles, metal oxide and color change promoter are used together, thereby greatly improving the color difference contrast during polymer marking and solving the industrial problem. However, although the novel additive makes a breakthrough in laser marking effect, it is darker (dark gray) in color, probably because the color change promoter undergoes a color change in advance at a high temperature in the preparation process. This is why, in patent CN104610642, the amount of the mixture is strictly controlled to be less than 40 parts, since after more than 40 parts, the additive composition is produced in light black. When such dark-colored additives are added to polymeric materials, their undertones are significantly darkened and grayed, and thus do not meet basic color requirements, and are therefore of limited use. With the popularization and application of laser marking technology in polymer materials in recent years, additives with light color and high color difference contrast are needed in many fields. Therefore, there is a need for a new additive material that can achieve both high contrast and low color for laser marking of polymer products.
Disclosure of Invention
The invention aims to provide an auxiliary agent composition for color change in light-colored base polymer and a preparation method thereof.
The invention provides an auxiliary agent composition for color change in light-colored base polymer, which comprises the following raw materials in parts by weight: 41.0 to 90.0 parts of mixture, 0.5 to 6.0 parts of compatibilizer and 4.0 to 58.5 parts of carrier polymer;
the mixture comprises metal powder, metal oxide, thermoplastic polymer and accelerant; the weight ratio of the metal powder, the metal oxide, the thermoplastic polymer and the accelerator is (0.3-3.0): (70-90): (2.0-29.6): (0.1-5.0).
The adjuvant composition comprises a core-shell structure; the core is metal powder and metal oxide, the first shell from inside to outside is a thermoplastic polymer containing an accelerant, and the second shell is a compatibilizer;
preferably, the particle size of the core-shell structure is 0.5 to 20.0 microns.
The core-shell structure consists of a core and two shells wrapped from inside to outside, wherein the core is metal powder and metal oxide (serving as a laser photosensitizer), the first shell from inside to outside is a thermoplastic polymer or a thermoplastic polymer containing an accelerant, and the second shell is a compatibilizer; the carrier polymer may allow the compatibilizer to interact with the thermoplastic polymer of the first shell to form the core-shell structure in situ.
The accelerator is selected from one or more of phosphate, phosphonate, phosphinate, borate, triazine nitrogen-containing heterocyclic organic compounds and organic polyols;
among them, typical examples of the phosphate ester are dipentaerythritol phosphate ester, bisphenol a bis (diphenyl phosphate ester), phenyl t-butylphenyl phosphate, diphenyl (xylene) phosphate, tri (toluene) phosphate; typical examples of the phosphonate are neopentyl phosphinate trimethyl phosphonate, diethyl succinate diethyl phosphonate; the phosphinate has the structural formula: (R)1R2P(O)O-)nMn+Wherein R is1、R2Is C1-C6Alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl) or aryl (e.g., phenyl) of (a), and the like, and M is a metal ion (e.g., zinc, calcium, aluminum, and the like), and specific examples thereof are zinc diethylphosphinate, zinc methylethylphosphinate, and the like; typical examples of borates are zinc borate; typical examples of the triazine-based nitrogen-containing heterocyclic organic compounds are 1,3, 5-triazine-2, 4, 6-triamine and 2, 4-diamino-6-phenyl-1, 3, 5-triazine; typical examples of the organic polyol are tetramethylolmethane, dipentaerythritol and 2-hydroxymethane-2-methyl-1, 3-propanediol.
Preferably, the accelerator is selected from any one or more of dipentaerythritol phosphate, bisphenol a bis (diphenyl phosphate), phenyl tert-butylphenyl phosphate, diphenyl (xylene) phosphate, tri (toluene) phosphate, tripentyl nitrilotrimethyl phosphonate, diethoxydiethyl succinate, dialkylphosphinates, zinc borate, 1,3, 5-triazine-2, 4, 6-triamine, 2, 4-diamino-6-phenyl-1, 3, 5-triazine, tetramethylolmethane, dipentaerythritol, 2-hydroxymethane-2-methyl-1, 3-propanediol.
Preferably, the dialkyl phosphinate is selected from any one or more of zinc methyl ethyl phosphinate, zinc diethyl phosphinate, aluminum methyl ethyl phosphinate, aluminum diethyl phosphinate, calcium methyl ethyl phosphinate and calcium diethyl phosphinate.
The metal powder is selected from any one or more of copper, iron, tin, tungsten, titanium, chromium, vanadium, nickel, silver, gold, indium, zinc, antimony, lead, aluminum, magnesium or alloy thereof; the metal oxide is selected from any one or more of titanium dioxide, aluminum oxide, bismuth trioxide, antimony trioxide, tin dioxide, tin antimony oxide, tungsten oxide and indium tin oxide.
Preferably, the particle diameter D of the metal powder500.01 to 15.0 microns; particle diameter D of the metal oxide50Is 0.01-15.0 microns.
Preferably, the thermoplastic polymer is selected from any one or more of aromatic polyester, polycarbonate, polyamide, polystyrene resin, polyphenylene oxide, acrylic resin, polysulfone, polyarylether, polyarylene sulfide sulfone, polyarylene sulfide ketone, polyarylene sulfide nitrile, polyvinyl chloride, polyvinyl alcohol, thermoplastic cellulose and thermoplastic starch.
Preferably, the compatibilizer is one or more selected from thermoplastic resin containing maleic anhydride units, thermoplastic resin containing glycidyl ether units, ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer and ethylene-acrylic ester copolymer;
the carrier polymer is selected from any one or more of polyethylene, polypropylene, ethylene-propylene copolymer, propylene-octene copolymer, propylene-butene copolymer, ethylene-octene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-propylene-octene terpolymer, ethylene-propylene-butene terpolymer, polyolefin elastomer and styrene resin.
Thermoplastic resins containing maleic anhydride units, typical examples of which are ethylene-butyl acrylate-maleic anhydride copolymers, polyethylene-grafted maleic anhydride, polypropylene-grafted maleic anhydride, POE-grafted maleic anhydride, styrene-maleic anhydride copolymers; typical examples of the thermoplastic resin containing glycidyl ether units are ethylene-methyl acrylate-glycidyl methacrylate copolymer, polyethylene-grafted glycidyl methacrylate, polypropylene-grafted glycidyl methacrylate, and POE-grafted glycidyl methacrylate. The selection of the compatibilizer is directly related to the variety of the thermoplastic polymer, and the compatibilizer is an amphoteric polymer, and molecular chains of the amphoteric polymer comprise repeating units or functional groups which are physically compatible with the thermoplastic polymer, form hydrogen bonds or chemically react with the thermoplastic polymer, and also comprise molecular chain segments compatible with the carrier polymer.
The invention also provides a preparation method of the auxiliary composition, which comprises the following steps:
a. taking 0.3 to 3.0 parts of metal powder, 70.0 to 90.0 parts of metal oxide, 2.0 to 29.6 parts of thermoplastic polymer and 0.1 to 5.0 parts of accelerant, and uniformly blending to obtain a mixture;
b. and (b) taking 41.0-90.0 parts of the mixture obtained in the step (a), 0.5-6.0 parts of compatibilizer and 4.0-58.5 parts of carrier polymer, blending and granulating to obtain the high-performance high-density polyethylene.
Preferably, the first and second electrodes are formed of a metal,
in the step a, the blending method is extrusion or banburying, and the blending temperature is 150-350 ℃;
in the step b, the blending method is extrusion or banburying, and the blending temperature is 100-330 ℃.
The invention adopts an extrusion method or an internal mixing method to prepare the color change auxiliary agent composition; when an extrusion method is adopted, a single-screw extruder, a double-screw extruder or other similar equipment can be selected.
The basic procedure for preparing the auxiliary composition of the invention by internal mixing is readily known to those skilled in the art.
The invention also provides the use of the aforementioned adjuvant composition as a laser discoloration adjuvant in light base polymers;
preferably, the adjuvant composition is added in an amount of 0.1wt.% to 30 wt.% in the light colored base polymer.
Laser color change additives, also known as laser color change additives, laser marking additives, laser additives, and the like; laser discoloration, also known as laser discoloration, laser marking, laser printing, and the like.
The color change auxiliary composition can be conveniently applied to laser marking matrix materials, and can specifically adopt methods such as injection molding, blow molding, extrusion and the like, and the addition amount of the color change auxiliary composition in the matrix materials is 0.1-30.0 wt%.
The color change auxiliary composition disclosed by the invention is suitable for laser with the wavelength of 157nm to 10.6 mu m; the laser emitting the above wavelength has CO2Laser (10.6 μm), Nd: YAG or Nd: YVO4 laser (1064, 532, 355 and 266nm), excimer laser: f2(157nm), ArF (193nm), KrCl (222nm), KrF (248nm), XeCl (308nm) and XeF (351nm), FAYb fiber lasers, diode array lasers, diode lasers and the like, preferably pulsed Nd: YAG lasers and pulsed fiber lasers are used, with 1064nm and 532nm pulsed lasers being particularly suitable.
The invention provides a novel color change auxiliary composition, which can greatly improve the color difference contrast ratio of a mark and a matrix material, is suitable for marking different polymer matrix materials and has consistent marking effect; particularly, after dipentaerythritol phosphate, methyl ethyl zinc phosphinate, 1,3, 5-triazine-2, 4, 6-triamine and the like are added as the accelerating agent, the contrast of color difference is higher, the marking application requiring higher contrast can be met, and the light color has the advantage of light color; meanwhile, the invention also provides a method for preparing the color change auxiliary composition, which is simple and convenient, is easy to operate and has good product quality. These polymeric matrix materials include, but are not limited to, PP, PE, PC, PA6, PA66, SAN, ABS, PS, PBT, PET, PVC, POM, SEBS, TPU, TPE, and TPV.
In summary, the present invention provides a novel colour change adjuvant composition which defines the weight ratio of metal oxide and the mixture consisting of metal powder, metal oxide, thermoplastic polymer, accelerator. Under the weight ratio, the color change auxiliary agent composition not only has high color difference contrast, but also can meet the marking application needing higher contrast; meanwhile, the color change auxiliary agent composition is light in color, does not obviously change the ground color (grey or dark) of the polymer material when being applied to the polymer material, can be applied to laser marking of light-colored base polymers, and solves the industrial problem. In addition, the color change auxiliary composition is simple and convenient in preparation method, easy to operate and good in application prospect.
Obviously, many modifications, substitutions, and variations are possible in light of the above teachings of the invention, without departing from the basic technical spirit of the invention, as defined by the following claims.
The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Detailed Description
The raw materials and equipment used in the embodiment of the present invention are known products and obtained by purchasing commercially available products.
1. The specific information of the device of the invention is as follows:
parallel twin-screw extruder: the diameter of the screw is 50mm, the length-diameter ratio of the screw is 40:1, and the screw is produced by Nanjing Jennett electromechanical limited company;
precision injection molding machine: model K-TEC 40, manufactured by Milacklong International Inc.;
laser marking machine: an MK-GQ10B type pulse fiber laser marking machine has the laser power of 10W, the infrared laser wavelength of 1064nm and a high-speed digital galvanometer;
standard colorimeter: x-rite Ci7860, produced by Pantone LLC.
2. The test method in the embodiment of the invention comprises the following steps:
the particle size of the metal powder was measured using a Mastersizer 2000 laser particle size, and D50 (the particle size corresponding to 50% cumulative particle size distribution for one sample) was taken.
The average particle size of the core-shell structure is observed and determined by a scanning electron microscope (SEM, JEOL JSM-5900LV), and the method comprises the following steps: the core-shell structure material is subjected to brittle fracture under liquid nitrogen, the section is slightly etched by dilute acid to expose the core-shell structure, the section is observed by SEM, and the average particle size of the core-shell structure is calculated statistically.
The chromaticity difference of the plastic sample plate is tested by a standard colorimeter, and the black and white degree of the ground color of the plastic sample plate is evaluated by a standard L value, wherein the L value ranges from 0 to 100, 0 represents pure black, and 100 represents pure white.
The contrast of laser marking was evaluated according to the following criteria:
poor contrast: *
Medium contrast ratio: **
High contrast ratio: ***
Very high contrast: ****
Ultra-high contrast: *****
Example 1 preparation of the laser marking aid of the invention
(1) Raw materials
Metal powder (core): ag, particle diameter (D)50) 0.5 μm;
metal oxide (core): antimony tin oxide, particle size (D)50) 0.2 μm;
thermoplastic polymer of the first shell: PA MDX6 (polyamide MDX 6), mitsubishi engineering 1022H;
compatibilizer of second shell: ethylene-butyl acrylate-maleic anhydride copolymer, akama, Lotader 3210;
accelerator (b): dipentaerythritol phosphate (chemical ltd, ruidao, guangzhou);
carrier polymer (b): high density polyethylene, melt index 0.5g/10min (190 ℃).
(2) Preparation method
The first step is as follows: uniformly mixing 29.6 parts of PA MDX6, 0.3 part of Ag powder, 70.0 parts of tin antimony oxide and 0.1 part of dipentaerythritol phosphate (in parts by weight), and blending into a uniform mixture by using a double-screw extruder, wherein the blending temperature is 240-260 ℃;
the second step is that: then, continuously mixing 90.0 parts of the mixture with 6.0 parts of ethylene-butyl acrylate-maleic anhydride copolymer and 4.0 parts of high-density polyethylene (by weight) by using a double-screw extruder at the temperature of 180-200 ℃; the core shell is formed in situ in the carrier high-density polyethylene, and the laser marking auxiliary agent master batch is obtained by extrusion granulation and is marked as S-1.
The average particle size of the core-shell structure measured by SEM was 3.2 μm.
Adding 2wt.% of laser marking aid master batch S-1 into Low Density Polyethylene (LDPE), and making into a plate with the thickness of 3mm by injection molding; carrying out chromaticity test on the sample plate to obtain an L value; and evaluating the laser marking effect of the sample plate by using a laser marking machine, wherein the marking speed is 1500mm/s, the laser power is 8W, and the pulse frequency is 20 kHz.
Example 2 preparation of the laser marking aid of the invention
(1) Raw materials
Metal powder (core): zn, particle diameter (D)50) Is 10 μm;
metal oxide (core): antimony trioxide, particle size (D)50) Is 10 μm;
thermoplastic polymer of the first shell: PC (polycarbonate), SABIC 241R;
compatibilizer of second shell: ethylene-methyl acrylate-glycidyl methacrylate copolymer, akama, Lotader AX 8900;
accelerator (b): zinc methyl ethyl phosphinate (guangzhou Ruidao chemical Co., Ltd.);
carrier polymer (b): POE (ethylene-octene copolymer), Dupont 8150.
(2) Preparation method
The first step is as follows: uniformly mixing 2.0 parts of PC, 3.0 parts of Zn powder, 90.0 parts of antimony trioxide and 5.0 parts of methyl ethyl zinc phosphinate (by weight), and then blending into a uniform mixture by using a double-screw extruder, wherein the blending temperature is 250-270 ℃;
the second step is that: then, 41.0 parts of the mixture is taken to be mixed with 0.5 part of ethylene-methyl acrylate-glycidyl methacrylate copolymer and 58.5 parts of POE (parts by weight) by a double-screw extruder at the temperature of 190-220 ℃; and extruding and granulating to obtain the laser marking auxiliary master batch, which is marked as S-2.
The average particle size of the core-shell structure measured by SEM was 13.3 μm.
Adding 2wt.% of laser marking aid master batch S-2 into TPU (thermoplastic polyurethane elastomer), and making into a plate with the thickness of 3mm by injection molding; carrying out chromaticity test on the sample plate to obtain an L value; the laser marking effect of the plate is evaluated by using a laser marking machine, wherein the marking speed is 1500mm/s, the laser power is 7W, and the pulse frequency is 50 kHz.
Example 3 preparation of the laser marking aid of the invention
(1) Raw materials
Metal powder (core): al, particle diameter (D)50) Is 15 μm;
metal oxide (core): tin dioxide, particle diameter (D)50) Is 15 μm;
thermoplastic polymer of the first shell: PPS (polyphenylene sulfide), Philips R-7-02;
compatibilizer of second shell: grafting glycidyl methacrylate onto polypropylene in grafting rate of 0.5wt% and melt index of 11g/10min (230 deg.c);
accelerator (b): aluminum diethylphosphinate (Guangzhou Ruiduo chemical Co., Ltd.);
carrier polymer (b): iPP (isotactic polypropylene), medium petrochemical T30S.
(2) Preparation method
The first step is as follows: uniformly mixing 13.0 parts of PPS (SH group exists at the tail end of a PPS molecular chain), 1.0 part of Al powder, 84.0 parts of stannic oxide and 2.0 parts of aluminum diethylphosphinate (by weight), and then blending into a uniform mixture by using a double-screw extruder, wherein the blending temperature is 290-320 ℃;
the second step is that: then, continuously mixing 50.0 parts of the mixture, 3.0 parts of polypropylene grafted glycidyl methacrylate and 47.0 parts of iPP (parts by weight) by using a double-screw extruder at the temperature of 250-270 ℃; and (3) forming a core-shell structure in situ in the carrier iPP, and extruding and granulating to obtain laser marking auxiliary agent master batch, which is marked as S-3.
The average particle size of the core-shell structure measured by SEM was 16.9 μm.
Adding 2wt.% of laser marking aid master batch S-3 into PBT (polybutylene terephthalate), and making a plate with the thickness of 3mm by injection molding; carrying out chromaticity test on the sample plate to obtain an L value; the laser marking effect of the plate is evaluated by using a laser marking machine, wherein the marking speed is 1800mm/s, the laser power is 7W, and the pulse frequency is 90 kHz.
Example 4 preparation of the laser marking aid of the invention
(1) Raw materials
Metal powder (core): sb, particle diameter (D)50) Is 5 μm;
metal oxide (core): tin dioxide, particle diameter (D)50) Is 5 μm;
thermoplastic polymer of the first shell: PPS (polyphenylene sulfide), Philips R-7-02;
compatibilizer of second shell: grafting glycidyl methacrylate onto polypropylene in grafting rate of 0.5wt% and melt index of 11g/10min (230 deg.c);
accelerator (b): 1,3, 5-triazine-2, 4, 6-triamine (chemical industry, Inc., Rui Dai, Guangzhou);
carrier polymer (b): iPP (isotactic polypropylene), medium petrochemical T30S.
(2) Preparation method
The first step is as follows: uniformly mixing 18.0 parts of PPS (SH group exists at the tail end of a PPS molecular chain), 2.0 parts of Sb powder, 76.0 parts of stannic oxide and 4.0 parts of 1,3, 5-triazine-2, 4, 6-triamine (in parts by weight), and then blending into a uniform mixture by using a double-screw extruder, wherein the blending temperature is 290-320 ℃;
the second step is that: then, 60.0 parts of the mixture is taken to be mixed with 3.0 parts of polypropylene grafted glycidyl methacrylate and 37.0 parts of iPP (parts by weight) by a double-screw extruder at the temperature of 250-270 ℃; and (3) forming a core-shell structure in situ in the carrier iPP, and extruding and granulating to obtain laser marking auxiliary agent master batch, which is marked as S-4.
The average particle size of the core-shell structure measured by SEM was 6.7 μm.
Adding 2wt.% of laser marking aid master batch S-4 into iPP (isotactic polypropylene), and making into a plate with the thickness of 3mm by injection molding; carrying out chromaticity test on the sample plate to obtain an L value; the laser marking effect of the plate is evaluated by using a laser marking machine, wherein the marking speed is 1800mm/s, the laser power is 7W, and the pulse frequency is 90 kHz.
Example 5 preparation of the laser marking aid of the invention
(1) Raw materials
Metal powder (core): au, particle size (D)50) Is 2 μm;
metal oxide (core): tungsten oxide, particle diameter (D)50) Is 4 μm;
thermoplastic polymer of the first shell: PC (polycarbonate), SABIC 241R;
compatibilizer of second shell: ethylene-methyl acrylate-glycidyl methacrylate copolymer, akama, Lotader AX 8900;
accelerator (b): 2-hydroxymethane-2-methyl-1, 3-propanediol (Guangzhou Rui Daizhou chemical Co., Ltd.);
carrier polymer (b): POE (ethylene-octene copolymer), Dupont 8150.
(2) Preparation method
The first step is as follows: uniformly mixing 24.0 parts of PC, 0.6 part of Au powder, 72.0 parts of tungsten oxide and 3.4 parts of 2-hydroxymethyl-2-methyl-1, 3-propanediol (by weight), and then blending into a uniform mixture by using a double-screw extruder, wherein the blending temperature is 250-270 ℃;
the second step is that: then, 70.0 parts of the mixture is taken to be mixed with 4.0 parts of ethylene-methyl acrylate-glycidyl methacrylate copolymer and 26.0 parts of POE (parts by weight) by a double-screw extruder at the temperature of 190-220 ℃; and extruding and granulating to obtain the laser marking auxiliary master batch which is marked as S-5.
The average particle size of the core-shell structure measured by SEM was 5.1 μm.
Adding 2wt.% of laser marking aid master batch S-5 into iPP (isotactic polypropylene), and making into a plate with the thickness of 3mm by injection molding; carrying out chromaticity test on the sample plate to obtain an L value; the laser marking effect of the plate is evaluated by using a laser marking machine, wherein the marking speed is 1500mm/s, the laser power is 7W, and the pulse frequency is 50 kHz.
To illustrate the advantageous effects of the present invention, the present invention provides the following test examples:
comparative example 1 preparation of other laser marking aids
When preparing the laser marking aid, the only difference between the comparative example 1 and the example 1 is the proportion of the raw materials in the second step:
after the first step is finished, continuously mixing 30.0 parts of mixture, 6.0 parts of ethylene-butyl acrylate-maleic anhydride copolymer and 64 parts of high-density polyethylene (by weight) by using a double-screw extruder at the temperature of 180-200 ℃; and obtaining the laser marking auxiliary agent master batch which is marked as P-1.
The average particle size of the core-shell structure measured by SEM was 3.7 μm.
The chromaticity test and the evaluation of the laser marking effect of the sample were performed in the same manner as in example 1.
Comparative example 2 preparation of other laser marking aids
When preparing the laser marking aid, the only difference between the comparative example 2 and the example 1 is the proportion of the raw materials in the first step:
the mixture ratio is 39.6 parts of PA MDX6, 0.3 part of Ag powder, 60.0 parts of tin antimony oxide and 0.1 part of dipentaerythritol phosphate (parts by weight).
And obtaining the laser marking auxiliary agent master batch which is marked as Q-1.
The average particle size of the core-shell structure measured by SEM was 7.9 μm.
The chromaticity test and the evaluation of the laser marking effect of the sample were performed in the same manner as in example 1.
Comparative example 3 preparation of other laser marking aids
When the laser marking aid is prepared, the difference between the comparative example 3 and the example 1 is that the proportion of the raw materials in the first step is respectively different from that in the second step:
the first step is as follows: uniformly mixing 39.6 parts of PA MDX6, 0.3 part of Ag powder, 60.0 parts of tin antimony oxide and 0.1 part of dipentaerythritol phosphate (in parts by weight), and blending into a uniform mixture by using a double-screw extruder, wherein the blending temperature is 240-260 ℃;
the second step is that: then, continuously mixing 40.0 parts of the mixture, 10.0 parts of ethylene-butyl acrylate-maleic anhydride copolymer and 50.0 parts of high-density polyethylene (by weight) by using a double-screw extruder at the temperature of 180-200 ℃; and obtaining the laser marking auxiliary agent master batch which is marked as M-1.
The average particle size of the core-shell structure measured by SEM was 1.5 μm.
The chromaticity test and the evaluation of the laser marking effect of the sample were performed in the same manner as in example 1.
Comparative example 4 preparation of other laser marking aids
The only difference between comparative example 4 and example 1 when preparing a laser marking aid is that: no accelerator was used (no dipentaerythritol phosphate was added in the first step), and a laser marking aid masterbatch was obtained, which was designated as N-1.
The average particle size of the core-shell structure measured by SEM was 2.7 μm.
The chromaticity test and the evaluation of the laser marking effect of the sample were performed in the same manner as in example 1.
Comparative example 5 preparation of other laser marking aids
When preparing the laser marking aid, the only difference between the comparative example 5 and the example 2 is the proportion of the raw materials in the second step:
after the first step is finished, taking 20.0 parts of mixture, 0.5 part of ethylene-methyl acrylate-glycidyl methacrylate copolymer and 79.5 parts of POE (parts by weight) to continue mixing by using a double-screw extruder, wherein the temperature is 190-220 ℃; and extruding and granulating to obtain the laser marking auxiliary master batch, which is marked as P-2.
The average particle size of the core-shell structure measured by SEM was 15.2 μm.
The chromaticity test and the evaluation of the laser marking effect of the sample were performed in the same manner as in example 2.
Comparative example 6 preparation of other laser marking aids
When preparing the laser marking aid, the only difference between the comparative example 6 and the example 2 is the proportion of the raw materials in the first step:
the mixture ratio is 42.0 portions of PC, 3.0 portions of Zn powder, 50.0 portions of antimony trioxide and 5.0 portions of methyl ethyl zinc phosphinate (weight portions).
And obtaining the laser marking auxiliary agent master batch which is marked as Q-2.
The average particle size of the core-shell structure measured by SEM was 24.2 μm.
The chromaticity test and the evaluation of the laser marking effect of the sample were performed in the same manner as in example 2.
Comparative example 7 preparation of other laser marking aids
When the laser marking aid is prepared, the difference between the comparative example 7 and the example 2 is that the proportion of the raw materials in the first step is respectively different from that in the second step:
the first step is as follows: uniformly mixing 10.0 parts of PC, 10.0 parts of Zn powder, 75.0 parts of antimony trioxide and 5.0 parts of methyl ethyl zinc phosphinate (by weight), and then blending into a uniform mixture by using a double-screw extruder, wherein the blending temperature is 250-270 ℃;
the second step is that: then, continuously mixing 5.0 parts of the mixture, 0.2 part of ethylene-methyl acrylate-glycidyl methacrylate copolymer and 94.8 parts of POE (parts by weight) by using a double-screw extruder at the temperature of 190-220 ℃; and extruding and granulating to obtain the laser marking auxiliary master batch, and marking as M-2.
The average particle size of the core-shell structure measured by SEM was 67 μm.
The chromaticity test and the evaluation of the laser marking effect of the sample were performed in the same manner as in example 2.
Comparative example 8 preparation of other laser marking aids
The only difference between comparative example 8 and example 2 when preparing a laser marking aid is that: no accelerator was used (no zinc methyl ethyl phosphinate was added in the first step) to obtain a master batch of laser marking aid, which was designated as N-2.
The average particle size of the core-shell structure measured by SEM was 13.0. mu.m.
The chromaticity test and the evaluation of the laser marking effect of the sample were performed in the same manner as in example 2.
Comparative example 9 preparation of other laser marking aids
When preparing the laser marking aid, the only difference between the comparative example 9 and the example 3 is the proportion of the raw materials in the second step:
after the first step is finished, taking 35.0 parts of the mixture, 3.0 parts of polypropylene grafted glycidyl methacrylate and 62.0 parts of iPP (parts by weight) and continuously mixing the mixture by using a double-screw extruder at the temperature of 250-270 ℃; and (3) forming a core-shell structure in situ in the carrier iPP, and extruding and granulating to obtain laser marking auxiliary agent master batch, which is marked as P-3.
The average particle size of the core-shell structure measured by SEM was 19.5 μm.
The chromaticity test and the evaluation of the laser marking effect of the sample were performed in the same manner as in example 3.
Comparative example 10 preparation of other laser marking aids
When preparing the laser marking aid, the only difference between the comparative example 10 and the example 3 is the proportion of the raw materials in the first step:
the mixture ratio is 29.0 parts of PPS, 1.0 part of Al powder, 68.0 parts of stannic oxide and 2.0 parts of aluminum diethylphosphinate (parts by weight).
And obtaining the laser marking auxiliary agent master batch which is marked as Q-3.
The average particle size of the core-shell structure measured by SEM was 28.5 μm.
The chromaticity test and the evaluation of the laser marking effect of the sample were performed in the same manner as in example 3.
Comparative example 11 preparation of other laser marking aids
When the laser marking aid is prepared, the difference between the comparative example 11 and the example 3 is that the proportion of the raw materials in the first step is respectively different from that in the second step:
the first step is as follows: uniformly mixing 23.0 parts of PPS (SH groups exist at the tail end of a PPS molecular chain), 7.0 parts of Al powder, 68.0 parts of stannic oxide and 2.0 parts of aluminum diethylphosphinate (by weight), and then blending into a uniform mixture by using a double-screw extruder, wherein the blending temperature is 290-320 ℃;
the second step is that: then, 25.0 parts of the mixture is taken to be mixed with 3.0 parts of polypropylene grafted glycidyl methacrylate and 72.0 parts of iPP (parts by weight) by a double-screw extruder at the temperature of 250-270 ℃; and (3) forming a core-shell structure in situ in the carrier iPP, and extruding and granulating to obtain laser marking auxiliary master batch, which is marked as M-3.
The average particle size of the core-shell structure measured by SEM was 22 μm.
The chromaticity test and the evaluation of the laser marking effect of the sample were performed in the same manner as in example 3.
Comparative example 12 preparation of other laser marking aids
The only difference between comparative example 12 and example 3 when preparing a laser marking aid is that: no accelerator was used (aluminum diethylphosphinate was not added in the first step) to obtain a laser marking aid masterbatch, which was designated as N-3.
The average particle size of the core-shell structure measured by SEM was 17.2 μm.
The chromaticity test and the evaluation of the laser marking effect of the sample were performed in the same manner as in example 3.
Comparative example 13 preparation of other laser marking aids
When preparing the laser marking aid, the only difference between the comparative example 13 and the example 4 is the ratio of the raw materials in the second step:
after the first step is finished, taking 37.0 parts of the mixture, 3.0 parts of polypropylene grafted glycidyl methacrylate and 60.0 parts of iPP (parts by weight) and continuously mixing the mixture by using a double-screw extruder at the temperature of 250-270 ℃; and (3) forming a core-shell structure in situ in the carrier iPP, and extruding and granulating to obtain laser marking auxiliary agent master batch, which is marked as P-4.
The average particle size of the core-shell structure measured by SEM was 7.6 μm.
The chromaticity test and the evaluation of the laser marking effect of the sample were performed in the same manner as in example 4.
Comparative example 14 preparation of other laser marking aids
When preparing the laser marking aid, the only difference between the comparative example 14 and the example 4 is the ratio of the raw materials in the first step:
the proportioning is 44.0 parts of PPS (SH group exists at the end of PPS molecular chain), 2.0 parts of Sb powder, 50.0 parts of stannic oxide and 4.0 parts of 1,3, 5-triazine-2, 4, 6-triamine (parts by weight).
And obtaining the laser marking auxiliary agent master batch which is marked as Q-4.
The average particle size of the core-shell structure measured by SEM was 17.6 μm.
The chromaticity test and the evaluation of the laser marking effect of the sample were performed in the same manner as in example 4.
Comparative example 15 preparation of other laser marking aids
When the laser marking aid is prepared, the difference between the comparative example 15 and the example 4 is that the proportion of the raw materials in the first step is respectively different from that in the second step:
the first step is as follows: uniformly mixing 44.0 parts of PPS (SH group exists at the tail end of a PPS molecular chain), 2.0 parts of Sb powder, 50.0 parts of stannic oxide and 4.0 parts of 1,3, 5-triazine-2, 4, 6-triamine (in parts by weight), and then blending into a uniform mixture by using a double-screw extruder, wherein the blending temperature is 290-320 ℃;
the second step is that: then, continuously mixing 50.0 parts of the mixture, 3.0 parts of polypropylene grafted glycidyl methacrylate and 47.0 parts of iPP (parts by weight) by using a double-screw extruder at the temperature of 250-270 ℃; and (3) forming a core-shell structure in situ in the carrier iPP, and extruding and granulating to obtain laser marking auxiliary agent master batch, which is marked as M-4.
The average particle size of the core-shell structure measured by SEM was 59 μm.
The chromaticity test and the evaluation of the laser marking effect of the sample were performed in the same manner as in example 4.
Comparative example 16 preparation of other laser marking aids
Comparative example 16 differs from example 4 only in the preparation of the laser marking aid: no accelerator was used (1, 3, 5-triazine-2, 4, 6-triamine was not added in the first step) to obtain a laser marking aid masterbatch, denoted as N-4.
The average particle size of the core-shell structure measured by SEM was 7.2 μm.
The chromaticity test and the evaluation of the laser marking effect of the sample were performed in the same manner as in example 4.
Comparative example 17 preparation of other laser marking aids
When preparing the laser marking aid, the only difference between the comparative example 17 and the example 5 is the ratio of the raw materials in the second step:
after the first step is finished, taking 15.0 parts of the mixture, 4.0 parts of ethylene-methyl acrylate-glycidyl methacrylate copolymer and 81.0 parts of POE (parts by weight) and continuously mixing the mixture by using a double-screw extruder, wherein the temperature is 190-220 ℃; and extruding and granulating to obtain the laser marking auxiliary master batch, which is marked as P-5.
The average particle size of the core-shell structure measured by SEM was 6.8 μm.
The chromaticity test and the evaluation of the laser marking effect of the sample were performed in the same manner as in example 5.
Comparative example 18 preparation of other laser marking aids
When preparing the laser marking aid, the only difference between the comparative example 18 and the example 5 is the proportion of the raw materials in the first step:
the mixture ratio is 31.0 portions of PC, 0.6 portion of Au powder, 65.0 portions of tungsten oxide and 3.4 portions of 2-hydroxymethyl-2-methyl-1, 3 propylene glycol (weight portions).
And obtaining the laser marking auxiliary agent master batch which is marked as Q-5.
The average particle size of the core-shell structure measured by SEM was 15.8 μm.
The chromaticity test and the evaluation of the laser marking effect of the sample were performed in the same manner as in example 5.
Comparative example 19 preparation of other laser marking aids
When the laser marking aid is prepared, the difference between the comparative example 19 and the example 5 is that the ratio of the raw materials in the first step and the second step is respectively different:
the first step is as follows: uniformly mixing 31.0 parts of PC, 0.6 part of Au powder, 65.0 parts of tungsten oxide and 3.4 parts of 2-hydroxymethyl-2-methyl-1, 3-propanediol (by weight), and then blending into a uniform mixture by using a double-screw extruder, wherein the blending temperature is 250-270 ℃;
the second step is that: then, mixing 38.0 parts of the mixture, 4.0 parts of ethylene-methyl acrylate-glycidyl methacrylate copolymer and 58.0 parts of POE (parts by weight) by using a double-screw extruder at the temperature of 190-220 ℃; and extruding and granulating to obtain the laser marking auxiliary master batch, which is marked as M-5.
The average particle size of the core-shell structure measured by SEM was 10.9 μm.
The chromaticity test and the evaluation of the laser marking effect of the sample were performed in the same manner as in example 5.
Comparative example 20 preparation of other laser marking aids
Comparative example 20 differs from example 5 only in the preparation of the laser marking aid in that: no accelerator was used (2-hydroxymethane-2-methyl-1, 3-propanediol was not added in the first step) to obtain a master batch of laser marking aid, noted N-5.
The average particle size of the core-shell structure measured by SEM was 6.8 μm.
The chromaticity test and the evaluation of the laser marking effect of the sample were performed in the same manner as in example 5.
The L value test results and the laser marking effects of the sample chromaticity of examples 1 to 5 and comparative examples 1 to 20 are shown in Table 1.
TABLE 1 sample color L value test results and laser marking effect
Figure DEST_PATH_IMAGE001
In the table:
poor contrast: *
Medium contrast ratio: **
High contrast ratio: ***
Very high contrast: ****
Ultra-high contrast: *****
The test result shows that: compared with the color change additive in the patent CN104610642, the color change additive composition provided by the invention has the advantages that not only the high color difference contrast effect of laser marking is not changed when the color change additive composition is applied to a polymer material, but also the ground color of the polymer material is not obviously darkened and grayed.
Compared with patent CN104610642, the invention only controls the dosage of the metal oxide in the first step at 70.0-90.0 parts and the dosage of the mixture in the second step at 41.0-90.0 parts under the condition of unchanged preparation method and process, thus achieving the above effect and obtaining unexpected technical effect. It can be seen that the amount of the metal oxide in the first step and the amount of the mixture in the second step must be controlled within the above ranges to achieve the effects, and the above objects cannot be achieved by the single control.
In summary, the present invention provides a novel color change aid composition that defines the weight ratio of metal oxide to the mixture of metal powder, metal oxide, thermoplastic polymer, accelerator. Under the weight ratio, the color change auxiliary agent composition not only has high color difference contrast, but also can meet the marking application needing higher contrast; meanwhile, the color change auxiliary agent composition is light in color, does not obviously change the ground color (grey or dark) of the polymer material when being applied to the polymer material, can be applied to laser marking of light-colored base polymers, and solves the industrial problem. In addition, the color change auxiliary composition is simple and convenient in preparation method, easy to operate and good in application prospect.

Claims (11)

1. An auxiliary composition for effecting a colour change in a light coloured base polymer, characterised in that: the composite material comprises the following raw materials in parts by weight: 41.0 to 90.0 parts of mixture, 0.5 to 6.0 parts of compatibilizer and 4.0 to 58.5 parts of carrier polymer;
the mixture comprises metal powder, metal oxide, thermoplastic polymer and accelerant; the weight ratio of the metal powder, the metal oxide, the thermoplastic polymer and the accelerator is (0.3-3.0): (70-90): (2.0-29.6): (0.1 to 5.0);
the adjuvant composition comprises a core-shell structure; the core is metal powder and metal oxide, the first shell from inside to outside is a thermoplastic polymer containing an accelerant, and the second shell is a compatibilizer;
the accelerator is selected from one or more of phosphate, phosphonate, phosphinate, borate, triazine nitrogen-containing heterocyclic organic compounds and organic polyols;
the particle size D50 of the metal powder is 0.01-15.0 microns; the particle size D50 of the metal oxide is 0.01-15.0 microns;
the thermoplastic polymer is selected from any one or more of aromatic polyester, polycarbonate, polyamide, polystyrene resin, polyphenyl ether, acrylic resin, polysulfone, polyarylether, polyarylene sulfide sulfone, polyarylene sulfide ketone, polyarylene sulfide nitrile, polyvinyl chloride, polyvinyl alcohol, thermoplastic cellulose and thermoplastic starch.
2. An auxiliary composition according to claim 1, characterized in that: the particle size of the core-shell structure is 0.5-20.0 microns.
3. An auxiliary composition according to claim 1, characterized in that: the accelerant is selected from any one or more of dipentaerythritol phosphate, bisphenol A bis (diphenyl phosphate), phenyl tert-butylphenyl phosphate, diphenyl (xylene) phosphate, tri (toluene) phosphate, tripentyl nitrilotrimethyl phosphonate, diethoxydiethyl succinate, dialkylphosphinates, zinc borate, 1,3, 5-triazine-2, 4, 6-triamine, 2, 4-diamino-6-phenyl-1, 3, 5-triazine, tetramethylolmethane, dipentaerythritol and 2-hydroxymethane-2-methyl-1, 3-propanediol.
4. An auxiliary composition according to claim 3, characterized in that: the dialkyl phosphinate is selected from one or more of zinc methyl ethyl phosphinate, zinc diethyl phosphinate, aluminum methyl ethyl phosphinate, aluminum diethyl phosphinate, calcium methyl ethyl phosphinate and calcium diethyl phosphinate.
5. An auxiliary composition according to claim 1, characterized in that: the metal powder is selected from any one or more of copper, iron, tin, tungsten, titanium, chromium, vanadium, nickel, silver, gold, indium, zinc, antimony, lead, aluminum, magnesium or alloy thereof; the metal oxide is selected from any one or more of titanium dioxide, aluminum oxide, bismuth trioxide, antimony trioxide, tin dioxide, tin antimony oxide, tungsten oxide and indium tin oxide.
6. An auxiliary composition according to claim 1, characterized in that: the compatibilizer is one or more selected from thermoplastic resin containing maleic anhydride units, thermoplastic resin containing glycidyl ether units, ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer and ethylene-acrylic ester copolymer;
the carrier polymer is selected from any one or more of polyethylene, polypropylene, ethylene-propylene copolymer, polyolefin elastomer and styrene resin.
7. An auxiliary composition according to claim 6, characterized in that: the polyolefin elastomer is selected from any one or more of propylene-octene copolymer, propylene-butene copolymer, ethylene-octene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-propylene-octene terpolymer or ethylene-propylene-butene terpolymer.
8. A process for the preparation of an adjuvant composition according to any one of claims 1 to 7, characterized in that: the method is characterized by comprising the following steps:
a. taking 0.3 to 3.0 parts of metal powder, 70.0 to 90.0 parts of metal oxide, 2.0 to 29.6 parts of thermoplastic polymer and 0.1 to 5.0 parts of accelerant, and uniformly blending to obtain a mixture;
b. and (b) taking 41.0-90.0 parts of the mixture obtained in the step (a), 0.5-6.0 parts of compatibilizer and 4.0-58.5 parts of carrier polymer, blending and granulating to obtain the high-performance high-density polyethylene.
9. The method of claim 8, wherein:
in the step a, the blending method is extrusion or banburying, and the blending temperature is 150-350 ℃;
in the step b, the blending method is extrusion or banburying, and the blending temperature is 100-330 ℃.
10. Use of an adjuvant composition according to any of claims 1 to 7 as a laser discolouration adjuvant in a light base polymer.
11. Use according to claim 10, characterized in that: the additive amount of the auxiliary composition in the light-colored base polymer is 0.1wt.% to 30 wt.%.
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