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CN104592618B - A kind of discoloration assistant composition and preparation method and application - Google Patents

A kind of discoloration assistant composition and preparation method and application Download PDF

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Publication number
CN104592618B
CN104592618B CN201510076502.7A CN201510076502A CN104592618B CN 104592618 B CN104592618 B CN 104592618B CN 201510076502 A CN201510076502 A CN 201510076502A CN 104592618 B CN104592618 B CN 104592618B
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copolymer
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CN104592618A (en
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周涛
胡友亮
张集海
文亮
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Sichuan University
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Sichuan University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2310/00—Masterbatches

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a kind of discoloration assistant composition, it includes the component of following parts by weight：5.0 parts~40.0 parts of mixture, 0.2 part~10.0 parts of bulking agent, 50.0 parts~94.8 parts of carrier polymer；In the mixture, include the component of following parts by weight：60.0 parts~85.0 parts of metal dust, 10.0 parts~39.9 parts of thermoplastic polymer.The invention provides a kind of new discoloration assistant composition, it is only necessary to which a kind of Photosensitizer can just increase substantially the aberration contrast of mark and matrix material；Particularly, after adding dipentaerythritol phosphate, Methylethyl phosphinic acids zinc etc. as accelerator, the contrast of aberration is higher；Meanwhile, present invention also offers a kind of method of easy, easy to operate, good product quality preparation discoloration assistant composition.

Description

Color change auxiliary agent composition and preparation method and application thereof
Technical Field
The invention relates to a color change auxiliary agent composition, a preparation method and application thereof.
Background
Currently, there are many techniques for marking commercial products, such as: the marks of the silk screen printing, the ink printing, the stamping and the like are easily blurred and difficult to identify due to friction, mechanical damage, chemical action and the like in the storage and transportation processes; meanwhile, the mark is easy to alter, and can bring a good opportunity for lawless persons to manufacture fake and fake products, 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 general, in order to improve the contrast of color difference of a polymer matrix material, it is often necessary to select suitable components as additives (also referred to as auxiliaries) of the matrix material and to change the physical state of the additives, etc., for example: world patent WO2009/003976 discloses the use of microspheres formed from laser absorbers, thermoplastic polymers, compatibilizers, carrier polymers, etc. as laser marking additives, wherein the laser absorbers are selected from at least two different metal oxides and metal hydroxides to form a high color difference contrast, while the color difference contrast is lower when one laser absorber is used alone (WO 2004/050766); 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, a single laser absorber is difficult to form high-contrast color difference, 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 technical difficulty of component compatibility selection is increased, the raw material cost and the manufacturing cost are increased, and the formed color difference contrast is still limited.
Therefore, there is a need to find a new additive material that simply and conveniently allows a sufficiently high contrast in color difference between the finally formed mark and the matrix material.
Disclosure of Invention
The invention aims to provide a color change assistant composition.
The invention provides a color change auxiliary composition which comprises the following components in parts by weight: 5.0 to 40.0 portions of mixture, 0.2 to 10.0 portions of compatibilizer and 50.0 to 94.8 portions of carrier polymer; the mixture comprises the following components in parts by weight: 60.0 to 85.0 parts of metal powder and 10.0 to 39.9 parts of thermoplastic polymer.
Preferably, the mixture further comprises the following components in parts by weight: 0.1 to 5.0 portions of accelerant; the accelerator is selected from any one or more of phosphate, phosphonate, phosphinate and borate.
Phosphate, phosphonate, phosphinate, borate, etc., are commonly used flame retardants in polymer materials (see: authors: Masluwa, publishers: Shanghai science and technology literature publishers, published time: 1985), and no reports have been made to improve the contrast of color difference using phosphate, phosphonate, phosphinate, borate, etc., as components of a color-change assistant.
Typical examples of phosphates are: dipentaerythritol phosphate, bisphenol a bis (diphenyl phosphate), phenyl tert-butylphenyl phosphate, diphenyl (xylene) phosphate, tri (toluene) phosphate; typical examples of phosphonates are trineopentyl phosphinate, diethoxydiethylphosphonate succinate. 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; typical examples of borates are zinc borate.
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, diethyldiethyl phosphonate succinate, dialkylphosphinate, zinc borate.
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.
Preferably, the color change assistant composition is of a core-shell structure; the core is metal powder, the first shell layer from inside to outside is thermoplastic polymer or thermoplastic polymer containing accelerator, and the second shell layer is compatibilizer.
Preferably, the particle size of the core-shell structure is 0.5-64 microns; more preferably, the particle size of the core-shell structure is 1.1 to 61 micrometers or 1.2 to 64 micrometers; more preferably, the particle size of the core-shell structure is 1.5-22 micrometers or 1.5-20 micrometers.
The core-shell structure consists of a core and two shells wrapped from inside to outside, wherein the core is metal powder (as a laser photosensitizer and also called a laser absorber), 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.
Preferably, 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 alloys thereof; still preferably, the metal powder is selected from any one or more of tin, nickel, silver, zinc, antimony, and aluminum.
Preferably, the particle diameter D of the metal powder500.01-80.0 microns; still preferably, the particle diameter D of the metal powder500.5 to 55 microns; more preferably, the particle diameter D of the metal powder50Is 0.6 to 15 μm.
Preferably, 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; the compatibilizer is selected from one or more of 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, and the carrier polymer is selected from one or more of polyethylene, polypropylene, ethylene-propylene copolymer, propylene-octene copolymer, propylene-butene copolymer, ethylene-octene copolymer, ethylene-hexene copolymer, ethylene-propylene-octene terpolymer, ethylene-propylene-butene terpolymer, polyolefin elastomer and styrene resin.
Aromatic ring-containing polymers such as: aromatic polyesters, polycarbonates, polystyrene resins, polyphenylene oxides, polyamides, polysulfones, polyarylene sulfides, polyarylene sulfide nitriles, and the like; typical examples of aromatic polyesters are PEN, and polycarbonates are generally those of the bisphenol A type; typical examples of polyarylene sulfides are polyphenylene sulfide (PPS); the polyamide can be common or semi-aromatic polyamide, and typical examples are PA6, PA6T, PA610, PA66, PA6/6T, PA9T and PA MXD 6.
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.
Preferably, the thermoplastic polymer is selected from any one or more of polycarbonate, polyphenylene sulfide and polyamide; the compatibilizer is selected from any one or more of ethylene-butyl acrylate-maleic anhydride copolymer, ethylene-methyl acrylate-glycidyl methacrylate copolymer and polypropylene grafted glycidyl methacrylate; the carrier polymer is selected from any one or more of high density polyethylene, polyolefin elastomer and polypropylene.
Preferably, the color change assistant composition is prepared by a method comprising the following steps:
a. taking 60.0 to 85.0 parts of metal powder and 10.0 to 39.9 parts of thermoplastic polymer, and uniformly blending to obtain a mixture;
or,
taking 60.0 to 85.0 parts of metal powder, 10.0 to 39.9 parts of thermoplastic polymer and 0.1 to 5.0 parts of accelerant, and uniformly blending to obtain a mixture;
b. and (b) taking 5.0-40.0 parts of the mixture obtained in the step (a), 0.2-10.0 parts of a compatibilizer and 50.0-94.8 parts of a carrier polymer, blending and granulating to obtain the modified polypropylene.
The invention also provides a method for preparing the color change auxiliary agent composition. 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 invention provides a method for preparing a color change auxiliary composition, which comprises the following steps:
i. taking 60.0 to 85.0 parts of metal powder and 10.0 to 39.9 parts of thermoplastic polymer, and uniformly blending to obtain a mixture;
or,
taking 60.0 to 85.0 parts of metal powder, 10.0 to 39.9 parts of thermoplastic polymer and 0.1 to 5.0 parts of accelerant, and uniformly blending to obtain a mixture;
ii. And (e) taking 5.0-40.0 parts of the mixture obtained in the step (i), 0.2-10.0 parts of compatibilizer and 50.0-94.8 parts of carrier polymer, blending and granulating to obtain the composite material.
Preferably, the first and second liquid crystal materials are,
in the step i, the blending method is extrusion or banburying, and the blending temperature is 150-350 ℃;
in the step ii, the blending method is extrusion or banburying, and the blending temperature is 100-330 ℃.
The basic procedure for preparing the laser marking aid composition of the present invention by banburying is readily known to those skilled in the art.
The use of the above composition as a laser colour change aid.
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.
Preferably, the composition is added in an amount of 0.1 wt.% to 30.0 wt.%.
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 between a mark and a base material by only one laser photosensitizer, is suitable for marking different polymer base materials, and has consistent marking effect; particularly, after dipentaerythritol phosphate, methyl ethyl zinc phosphinate and the like are added as the accelerating agents, the contrast of color difference is higher, and the marking application requiring higher contrast can be met; 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.
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. For terms not specifically defined herein, the meanings that would be given to them by a person skilled in the art are to be given in light of the disclosure and the context.
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.
The test method comprises the following steps:
the particle size of the metal powder was measured by a Mastersizer 2000 laser particle size, and D was measured50(particle size corresponding to the cumulative percent particle size distribution of 50% for one sample).
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 specific information of the device of the invention is as follows:
a parallel double-screw extruder with a screw diameter of 50mm and a screw length-diameter ratio of 40:1, produced by Nanjing Jeiente electromechanical Co., Ltd;
a precision injection molding machine, model K-TEC 40, manufactured by Miracolon International Inc.;
the specific information of the laser marking machine is as follows:
MK-GQ10B type pulse fiber laser marking machine, laser power 10W, infrared laser wavelength 1064nm, high-speed digital galvanometer.
The contrast of laser marking was evaluated according to the following criteria:
poor contrast
Medium contrast
High contrast
Very high contrast
Ultra-high contrast
Example 1
Metal powder (core): ag, particle diameter (D)50) 0.5 μm;
thermoplastic polymer of the first shell: PA MDX6 (polyamide MDX6), mitsubishi engineering 1022H;
compatibilizer of second shell: ethylene-butyl acrylate-maleic anhydride copolymer, akama, Lotader 3210;
accelerator (b): dipentaerythritol phosphate (Guangzhou Ruiduo chemical Co., Ltd.)
Carrier polymer (b): high density polyethylene, melt index 0.5g/10min (190 ℃);
uniformly mixing 39.9 parts of PA MDX6, 60 parts of Ag powder 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 ℃;
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 ℃; the core-shell structure is formed in situ in the carrier high density polyethylene, and the color change additive master batch is obtained by extrusion granulation and is marked as A-1.
The average particle size of the core-shell structure measured by SEM was 1.2 μm.
Adding 2 wt.% of color change additive master batch A-1 into Low Density Polyethylene (LDPE), and making into a plate with the thickness of 3mm by injection molding; 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 8W, and the pulse frequency is 20 kHz.
Example 2
Metal powder (core): zn, particle diameter (D)50) Is 55 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 Ruiduo chemical Co., Ltd.)
Carrier polymer (b): POE (ethylene-octene copolymer), Dupont 8150;
uniformly mixing 10.0 parts of PC, 85.0 parts of Zn powder 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 ℃;
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 ℃; the core-shell structure is formed in situ in the carrier POE, and extruded and granulated to obtain the color-change additive master batch, which is marked as A-2.
The average particle size of the core-shell structure measured by SEM was 64 μm.
Adding 2 wt.% of color change additive master batch A-2 into TPU (thermoplastic polyurethane elastomer), and preparing a plate with the thickness of 3mm by injection molding; 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
Metal powder (core): al, 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 0.5 wt% 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 petro T30S
Uniformly mixing 28.0 parts of PPS (SH groups exist at the tail end of a PPS molecular chain), 70.0 parts of Al powder 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 ℃;
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 ℃; the core-shell structure is formed in situ in the carrier iPP, and the color change additive master batch is obtained by extrusion granulation and is marked as A-3.
The average particle size of the core-shell structure measured by SEM was 20 μm.
Adding 2 wt.% of color change additive master batch A-3 into PBT, and preparing a plate molded into a thickness of 3mm by injection molding; 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
The only difference from example 1 is that: no accelerator was used to obtain a color change aid masterbatch, denoted as B-1.
The average particle size of the core-shell structure measured by SEM was 1.1 μm.
Adding 2 wt.% of color change additive master batch B-1 into low-density polyethylene, and preparing a plate molded into a thickness of 3mm by injection molding; 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 8W, and the pulse frequency is 20 kHz.
Example 5
The only difference from example 2 is that: no accelerator was used, and a color change aid masterbatch was obtained, denoted as B-2.
The average particle size of the core-shell structure measured by SEM was 61 μm.
Adding 2 wt.% of color change additive master batch B-2 into TPU, and preparing a plate with the thickness of 3mm by injection molding; 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 6
The only difference from example 3 is that: no accelerator was used, and a color change aid masterbatch was obtained, denoted as B-3.
The average particle size of the core-shell structure measured by SEM was 22 μm.
Adding 2 wt.% of color change additive master batch B-3 into PBT (polybutylene terephthalate, which is one kind of polyester), and making into a plate molded to a thickness of 3mm by injection molding; 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.
To illustrate the advantageous effects of the present invention, the present invention provides the following test examples:
comparative example 1
2 wt.% of Iriotec 8208 from Merck (a proprietary product: laser marking additive, see world patent WO2009/003976) was added to low density polyethylene and injection molded into a sheet with a thickness of 3 mm; 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 8W, and the pulse frequency is 20 kHz.
Comparative example 2
2 wt.% of Iriotec 8208 from Merck was added to the TPU and injection molded into a plate 3mm thick; 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.
Comparative example 3
2 wt.% of Iriotec 8208 from Merck was added to PBT and injection molded into a plate 3mm thick; 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.
The evaluation results of the laser marking are shown in table 1:
TABLE 1 evaluation results of laser marking effects
Description of the drawings:
poor contrast
Medium contrast
High contrast
Very high contrast
Ultra-high contrast
Test results show that the color change auxiliary composition can greatly improve the color difference contrast between the mark and the matrix material by only one laser photosensitizer, is suitable for marking different polymer matrix materials, and has consistent marking effect; particularly, after dipentaerythritol phosphate, methyl ethyl zinc phosphinate and the like are added as the accelerating agents, the contrast of color difference is higher, and the marking application requiring higher contrast can be met.
In conclusion, the invention provides a novel color change auxiliary composition, which can greatly improve the color difference contrast ratio of a mark and a base material only by one laser photosensitizer, is suitable for marking different polymer base materials, and has consistent marking effect; particularly, after dipentaerythritol phosphate, methyl ethyl zinc phosphinate and the like are added as the accelerating agents, the contrast of color difference is higher, and the marking application requiring higher contrast can be met; 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.

Claims (12)

1. A color change aid composition characterized by: the paint comprises the following components in parts by weight: 5.0 to 40.0 portions of mixture, 0.2 to 10.0 portions of compatibilizer and 50.0 to 94.8 portions of carrier polymer; the mixture comprises the following components in parts by weight: 60.0 to 85.0 parts of metal powder, 10.0 to 39.9 parts of thermoplastic polymer and 0.1 to 5.0 parts of accelerant; wherein the colour-change aid composition comprises a core-shell structure; the core is metal powder, the first shell from inside to outside is a thermoplastic polymer containing an accelerator, and the second shell is a compatibilizer; the accelerator is selected from any one or more of phosphate, phosphonate, phosphinate and borate.
2. The color change aid composition according to claim 1, wherein: the promoter 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, dialkylphosphinate and zinc borate.
3. The color change aid composition according to claim 2, wherein: 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.
4. The color change aid composition according to claim 1, wherein: the particle size of the core-shell structure is 0.5-64 microns.
5. A colour-change additive composition according to any one of claims 1 to 3, 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 alloys thereof.
6. A colour-change additive composition according to any one of claims 1 to 3, characterized in that: particle diameter D of the metal powder50Is 0.01-80.0 microns.
7. A colour-change additive composition according to any one of claims 1 to 3, characterized in that: 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; the compatibilizer is selected from one or more of 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, and the carrier polymer is selected from 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.
8. A colour-change additive composition according to any one of claims 1 to 3, characterized in that: the method is characterized by comprising the following steps:
a. taking 60.0 to 85.0 parts of metal powder, 10.0 to 39.9 parts of thermoplastic polymer and 0.1 to 5.0 parts of accelerant, and uniformly blending to obtain a mixture;
b. and (b) taking 5.0-40.0 parts of the mixture obtained in the step (a), 0.2-10.0 parts of a compatibilizer and 50.0-94.8 parts of a carrier polymer, blending and granulating to obtain the modified polypropylene.
9. A process for preparing a colour-change adjuvant composition according to any of claims 1 to 8, characterized in that: it comprises the following steps:
i. taking 60.0 to 85.0 parts of metal powder, 10.0 to 39.9 parts of thermoplastic polymer and 0.1 to 5.0 parts of accelerant, and uniformly blending to obtain a mixture;
ii. And (e) taking 5.0-40.0 parts of the mixture obtained in the step (i), 0.2-10.0 parts of compatibilizer and 50.0-94.8 parts of carrier polymer, blending and granulating to obtain the composite material.
10. The method of preparing a color change aid composition according to claim 9, wherein:
in the step i, the blending method is extrusion or banburying, and the blending temperature is 150-350 ℃;
in the step ii, the blending method is extrusion or banburying, and the blending temperature is 100-330 ℃.
11. Use of a composition according to any one of claims 1 to 8 as a laser colour change aid.
12. Use according to claim 11, characterized in that: the addition amount of the composition is 0.1-30.0 wt.%.
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CN110408165B (en) * 2019-08-09 2022-04-05 四川大学 Color change additive for manufacturing white or light-colored mark and preparation method thereof
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