CN109337356B - Composition capable of being subjected to laser color marking and used for fiber laser - Google Patents

Composition capable of being subjected to laser color marking and used for fiber laser Download PDF

Info

Publication number
CN109337356B
CN109337356B CN201811241399.7A CN201811241399A CN109337356B CN 109337356 B CN109337356 B CN 109337356B CN 201811241399 A CN201811241399 A CN 201811241399A CN 109337356 B CN109337356 B CN 109337356B
Authority
CN
China
Prior art keywords
laser
marking
photosensitizer
parts
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811241399.7A
Other languages
Chinese (zh)
Other versions
CN109337356A (en
Inventor
许韬
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Youkeli New Material Co ltd
Original Assignee
Zhejiang Youkeli New Material Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang Youkeli New Material Co ltd filed Critical Zhejiang Youkeli New Material Co ltd
Priority to CN201811241399.7A priority Critical patent/CN109337356B/en
Publication of CN109337356A publication Critical patent/CN109337356A/en
Application granted granted Critical
Publication of CN109337356B publication Critical patent/CN109337356B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/36—Removing material
    • B23K26/361—Removing material for deburring or mechanical trimming
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/36—Removing material
    • B23K26/362—Laser etching
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Plasma & Fusion (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)

Abstract

The invention discloses a composition capable of being marked by laser color, which contains up-conversion nanoparticles and a photosensitizer, wherein the up-conversion nanoparticles can emit emission light of 530-550nm and 630-662nm under the irradiation of 1064nm excitation light, and the emission light can excite the photosensitizer at the moment to enable the photosensitizer to generate a photothermal effect. The composition is suitable for fiber lasers, laser marking is realized under low-power laser, and the laser marking has good definition, high resolution and good color marking. Meanwhile, the laser efficiency is high, and the burning mark depth is deep, so that the stability is good, the durability is high, and the mark cannot disappear quickly along with time and use.

Description

Composition capable of being subjected to laser color marking and used for fiber laser
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a composition capable of being subjected to laser color marking, which is suitable for laser marking of a fiber laser.
Background
Laser marking is a technique that uses the thermal effect of a laser to ablate away surface material of an object, leaving a permanent mark. Compared with the traditional marking methods such as electrochemistry, machinery and the like, the method has the advantages of no pollution, high speed, high quality, high flexibility, no contact with work and the like. In recent years, laser marking has become a conventional processing method in many fields instead of a conventional marking method, and even has become a new industry standard. The laser marking machine is an electromechanical integrated device integrating the technologies of laser, optics, precision machinery, computers and the like. Wherein the laser is the core device of laser marking, and is currently in the laser marking fieldThe laser marking machine commonly used in the field mainly comprises: CO 22Laser marking machine, semiconductor laser marking machine, optic fibre laser marking machine, Nd: YAG laser marking machine. Among the most widely used at present is CO2Laser marking machine, the laser is CO2The laser wavelength of the gas laser tube is 10.64um, the power is high, the heat quantity is high, and the printing effect and the marking speed can meet the requirements of high efficiency, high speed and high reliability of modern mass production. But due to the characteristics of high power and high efficiency, CO is generated2The laser marking machine has low marking fineness and is not suitable for production with high marking precision requirement. The fiber laser marking machine adopts a fiber laser, has good beam quality, the output wavelength of 1064nm, thin laser beam, low consumption of processing materials and small processing heat affected zone, has the advantages of fine marking, power saving, maintenance free and the like, and is suitable for processing and marking fine workpieces such as integrated circuit chips, computer accessories, clocks, electronic communication products, aerospace devices and the like.
In daily production, in the process of machining or marking a workpiece which is small in size, low in hardness and high in brittleness, in order to reduce thermal damage of a laser to the workpiece as much as possible, relatively low power is selected for marking, and at the moment, the situation that the mark is not clear or not crisp may occur, and the situation that the laser burning depth is not enough, the mark disappears soon along with daily use, friction and the like may also occur. In order to avoid this without thermal damage to the machined workpiece, the usual solution is to add agents to the workpiece production which convert light energy into heat energy efficiently, thereby enabling efficient laser marking even with lower power lasers.
Patent document CN106566068A discloses a polymer composition capable of laser color marking, which is added with 0.05-2 parts of laser marking powder and 0.1-10 parts of temperature-sensitive substance, the heat generated in the laser marking process can make the temperature-sensitive substance generate thermal decomposition, oxidation and other reactions at a certain temperature, these reactions can destroy the original substance structure or generate a new substance, and at the same time generate a new color, the color change is unidirectional and irreversible, and after cooling, the original color can not be recovered, so that a stable permanent mark can be formed on the product. The temperature-sensitive substance is at least one of phthalocyanine pigments, and the phthalocyanine pigments are known to those skilled in the art to belong to one of organic pigments, so that although the color change phenomenon may occur under heating conditions, the color change is irreversible, and the color change is difficult to be stable for a long time. In addition, the control of heat in the heating color change process is also related to the change degree of color, and if mass production is required, the color is difficult to be consistent, the process difficulty is high, and the method is not suitable for mass industrial production.
Patent document CN101927626A discloses a plastic laser marking functional masterbatch, which comprises: the invention discloses a master batch containing a photosensitizer, a black pigment and an organic polymer carrier, wherein the photosensitizer comprises 10-25% of a photosensitizer, 10-15% of a white pigment, 20-30% of a black pigment and 38.5% -53.5% of the organic polymer carrier, the organic polymer carrier is preferably polypropylene plastics, the photosensitizer LS is added in the master batch preparation process, has a strong absorption effect on laser, generates heat energy after effectively absorbing laser beam energy, releases the heat energy to change the surface black pigment into gas to evaporate so as to expose the deep white pigment, and accordingly, white writings or patterns with strong contrast are generated on the surface of the black polypropylene plastics. In this application, the light conversion efficiency of the photosensitizer is high and good, but the photosensitizer LS mentioned in this application is not common in the market, is expensive to purchase, has too high cost in production, and sometimes has more defects than good in the aspect of measuring the whole production and sale.
In order to overcome the defects of the prior art, the invention provides a composition which is suitable for marking an optical fiber laser, a black pigment and a color pigment are added in the preparation process of the composition, the substrate color of the composition is black, and the black pigment is burnt off under the action of laser to leave the color pigment, so that a permanent colored mark is formed on a marked part. Meanwhile, the upconversion nanoparticles and the photosensitizer are added in the preparation process, and the upconversion nanoparticles and the photosensitizer are matched with each other, so that the laser efficiency is enhanced, and the optical fiber laser can realize clear marking patterns, high resolution and good durability under lower power.
Disclosure of Invention
The invention aims to provide a composition capable of being marked by laser color and a preparation method thereof. Meanwhile, the laser efficiency is high, and the burning mark depth is deep, so that the stability is good, the durability is high, and the mark cannot disappear quickly along with time and use. In addition, preferably, the present application first prepares a part of the polyamide resin, the upconversion nanoparticles, the photosensitizer, the black pigment component and the color pigment component into the resin master batch, so that the photo-thermal particles and the pigment are uniformly dispersed in the resin, and the marking effect is better.
A composition capable of being color-marked by laser comprises up-conversion nanoparticles and a photosensitizer, wherein the up-conversion nanoparticles can emit emitted light at 530-550nm and 630-662nm under the irradiation of 1064nm exciting light, and the photosensitizer can be excited by the emitted light, so that the photosensitizer generates a photothermal effect.
The up-conversion nanoparticles are NaYF 4: er and Yb with the grain diameter of 20-150 nm.
Preferably, the size of the upconversion nanoparticles is 20-100 nm.
The photosensitizer is selected from: one or more of dihydroporphin, hematoporphyrin, bihematoporphyrin ether and hypocrellin.
Preferably, the photosensitizer is selected from the group consisting of chlorins and hypocrellins.
Preferably, in the laser-markable composition, the proportion of up-converting nanoparticles is between 2 and 5.5% and the proportion of photosensitizer is between 0.5 and 1.5%.
More preferably, the proportion of the up-conversion nanoparticles is 3-4.5% and the proportion of the photosensitizer is 0.6-0.8%.
A composition capable of laser color marking comprises the following raw materials, by mass, 40-80 parts of polyamide resin, 0.1-5 parts of up-conversion nanoparticles, 0.1-3 parts of a photosensitizer, 0.1-1 part of a black pigment, 0.2-3 parts of a color pigment, 0.3-0.6 part of an antioxidant, 0.5-1 part of a lubricant and 0-20 parts of a filler, wherein in the preparation process, 4-8 parts of polyamide resin, 0.1-5 parts of up-conversion nanoparticles, 0.1-3 parts of a photosensitizer, 0.1-1 part of a black pigment and 0.2-3 parts of a color pigment are prepared into resin master batches, and then the resin master batches, the rest of polyamide resin, 0.3-0.6 part of an antioxidant, 0.5-1 part of a lubricant and 0-20 parts of a filler are mixed and extruded and processed.
The black pigment is preferably carbon black, and the carbon black is classified into furnace black, channel black, pyrolytic carbon black, lamp black, gas black, and the like according to the production method, and acetylene black, ketjen black, oil black, soot black, and the like according to the raw material.
The color pigment may be an inorganic pigment, an organic pigment, a dye, and in the present invention, the color pigment is preferably an organic pigment, including azo pigments, phthalocyanine pigments, quinacridone pigments, and lake pigments, and specifically, the color pigment is selected from the group consisting of: one or more of acetyl arylamine, 2-naphthol, pyrazolone, 2-hydroxy-3-naphthoic acid, 2-hydroxy-3-naphthoyl arylamine, isoindolinone, phthalocyanine blue and phthalocyanine red.
The oxidant is selected from: one or a combination of more than two of pentaerythritol ester or phosphite ester.
The lubricant is selected from: pentaerythritol stearate or magnesium stearate.
The filler is selected from: one or more of glass fiber, glass beads, calcium carbonate, talcum powder, barium sulfate, kaolin and clay.
A method of preparing a laser color markable composition comprising the steps of:
(1) melting and mixing 5-10% of the expected dosage of polyamide resin with the up-conversion nanoparticles, the photosensitizer, the black pigment and the color pigment to prepare resin master batches, putting the rest polyamide resin and the prepared resin master batches into a high-speed mixer to be uniformly mixed, adding the antioxidant and the lubricant, and continuously mixing until the mixture is uniform;
(2) feeding the uniformly mixed materials into a double-screw extruder, extruding, and adding a filler into the middle part of the extruder;
(3) cooling by an ultra-cold roller;
(4) laser marking was performed on the composition prepared in the above step.
Preferably, the processing temperature of the extruder in the step (2) is 210-.
Preferably, the laser for laser marking in step (4) is selected from: the fiber laser marking machine has the laser wavelength of 1064nm, the laser energy of 3-10W, the marking frequency of 20-100KHz and the marking speed of 600-1000 mm/s.
More preferably, the laser energy is 3-5W, the marking frequency is 40-60KHz, and the marking speed is 700-800 mm/s.
The application of the composition capable of being color-marked by laser in preparing high-precision devices, wherein the high-precision devices are integrated circuit chips, computer accessories, electronic communication products or aerospace devices.
The upconversion nanoparticles NaYF4 provided by the invention are as follows: er, Yb may be derived from commercial products or prepared according to methods of preparation common in the art.
The invention provides an upconversion nanoparticle NaYF 4: the preparation method of Er and Yb comprises the following steps:
(1) dissolving a rare earth raw material in methanol, adding a high-temperature solvent, evaporating the methanol solvent to dryness, reacting at the temperature of 150 ℃ and 170 ℃ for 30-40min in a nitrogen atmosphere, and cooling to room temperature;
(2) adding the product obtained in the previous step into dissolved NaOH and NH4Stirring the methanol solution of F, evaporating the methanol solvent to dryness, heating to the temperature of 300-320 ℃ in the nitrogen atmosphere, carrying out heat preservation reaction, and then cooling to the room temperature;
(3) precipitating with ethanol, centrifuging, and washing to obtain an upconversion precursor;
(4) the precursor is formed into superfine powder through a jet microwave combustion synthesis method, and up-conversion nano particles are obtained.
Preferably, the rare earth raw material in the step (1) is selected from: YCl3、YbCl3And ErCl3Wherein YCl3The concentration of (A) is 0.9-2.7 mol%, YbCl3In a concentration of 0.1 to 1.5 mol%, ErCl3The concentration of (B) is 0.1-0.9 mol%.
The high temperature solvent is selected from: one or the combination of more than two of oleic acid, octadecene, oleylamine, tri-n-octylphosphine oxide and trioctylphosphine.
Preferably, NaOH and NH are used in the step (2)4The concentration of F is 1-1.5mol/L and 1.2-3mol/L respectively.
Preferably, the jet microwave combustion synthesis method in the step (4) is to form a spray by microwave ignition in a microwave spray combustion synthesizer.
The composition capable of being color-marked by laser is suitable for optical fiber lasers, and is suitable for preparing more precise elements such as electronic elements, communication equipment and the like. CO 22The laser has high laser power but can cause thermal damage to precision elements, the laser wavelength of the fiber laser is 1064nm, and the laser wavelength is in combination with CO2Compared with a laser, the laser has lower power, so that a precision element cannot be thermally damaged in the laser marking process, the laser adopts a fiber laser with lower power for marking, and simultaneously, the upconversion nanoparticles and the photosensitizer are added into the composition to improve the laser efficiency, so that the laser marking has good definition, high resolution and better color generation of the color mark. In addition, the photosensitizers required by the present invention are more readily available than those mentioned in patent CN101927626A, and are simpler to synthesize either commercially or by themselves.
Drawings
FIG. 1 emission spectra of upconverting nanoparticles prepared according to the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1 preparation of upconversion nanoparticles
Mixing YCl3、YbCl3And ErCl3Dissolving in methanol to form concentrations of 1.5 mol%, 0.7 mol% and 0.4 mol%, respectively, adding high temperature solvent oleic acid, evaporating methanol solvent, reacting at 170 deg.C for 40min under nitrogen atmosphere, and cooling to room temperature; the product was added to a solution of NaOH (0.7 mol/L) and NH4Stirring the solution of F (the concentration is 2.0mol/L) in methanol, evaporating the methanol solvent to dryness, heating to 300 ℃ in nitrogen atmosphere, carrying out heat preservation reaction for 2h, and cooling to room temperature; precipitating with ethanol, centrifuging, and washing to obtain an upconversion precursor; spraying the precursor with a jet microwave combustion synthesis method to form superfine powder to obtain upconversion nanoparticles with the particle size range of 30-110 nm. The emission spectrum of the upconverting nanoparticles under excitation light at 1064nm was measured as shown in figure 1.
Example 2 preparation of composition 1 (upconverting nanoparticles + photosensitizer).
Fully melting and mixing 7.5 parts of polyamide resin, 2 parts of up-conversion nano particles, 0.5 part of hypocrellin, 0.3 part of chlorin, 0.5 part of black pigment furnace carbon black and 2 parts of color pigment phthalocyanine red to prepare resin master batch; putting the remaining 67.5 parts of polyamide resin and the resin master batch prepared in the previous step into a high-speed mixer to be mixed uniformly, adding 0.4 part of antioxidant pentaerythritol ester and 0.8 part of lubricant magnesium stearate, and continuously mixing until the mixture is uniform; putting the uniformly mixed materials into a double-screw extruder, extruding at the processing temperature of 250 ℃ and the rotating speed of a main machine of 600 revolutions per minute, and adding 5 parts of filler glass fiber in the middle of the extruder; cooling the mixture by an ultra-cold roller to obtain a composition capable of being subjected to laser color marking; and then, carrying out laser marking by using a fiber laser marking machine, wherein the laser energy is 3W, the marking frequency is 50KHz, and the marking speed is 800 mm/s.
Comparative example 1 preparation of composition 2 (upconversion nanoparticles)
In the process of preparing the composition, compared with the example 2, the photosensitizer is not added, and the rest components and the preparation method are the same as the example 2. The prepared composition is subjected to laser marking by a fiber laser marking machine, the laser energy is 10W, the marking frequency is 100KHz, and the marking speed is 800 mm/s.
Comparative example 2 preparation of composition 3 (photosensitizer)
In the preparation of the composition, compared to example 2, no upconverting nanoparticles were added, and the remaining components and preparation method were the same as example 2. The prepared composition is subjected to laser marking by a fiber laser marking machine, the laser energy is 10W, the marking frequency is 100KHz, and the marking speed is 800 mm/s.
COMPARATIVE EXAMPLE 3 preparation of composition 4 (none)
In the process of preparing the composition, compared with example 2, the up-conversion nanoparticles and the photosensitizer are not added, and the rest of the components and the preparation method are the same as example 2. The prepared composition is subjected to laser marking by a fiber laser marking machine, the laser energy is 10W, the marking frequency is 100KHz, and the marking speed is 800 mm/s.
Effect comparative example 1 Effect of conversion nanoparticles and photosensitizer on laser marking Effect
The compositions prepared in example 2 and comparative examples 1 to 3 were laser-marked and the pattern effects after marking were compared, and the results are shown in the following table.
TABLE 1 Effect of converting nanoparticles with photosensitizers on laser marking Effect
Figure BDA0001839416020000071
It can be seen from the above comparison that when only the up-conversion nanoparticles or the photosensitizer is added or neither is added in the process of preparing the composition, the laser marking effect is not ideal even at higher laser power, and the marking definition is not high. Only the up-conversion nano particles and the photosensitizer are added simultaneously, the laser marking effect is good, the definition is high, and the color marking color is bright. For analysis reasons, because the upconversion nanoparticles and the photosensitizer are in complementary relationship, the photosensitizer can convert part of light energy into heat energy, and the laser marking efficiency is improved, but the wavelength of the fiber laser is 1064nm, the photosensitizer cannot be excited, and only when the upconversion nanoparticles are added, the upconversion nanoparticles can absorb 1064nm light and emit emitted light of 530-. Therefore, the up-conversion nano particles and the photosensitizer are not available, the laser marking efficiency is increased together, and the laser marking effect is doubled.
Effect of the type of photosensitizer on the laser marking Effect
EXAMPLE 3 preparation of composition 5 (chlorin)
In contrast to example 2, the photosensitizer during the preparation of the composition was selected from: 0.8 part of chlorin, the dose of the photosensitizer is the same as that of the embodiment 2, and other components and preparation methods are also the same as that of the embodiment 2. The prepared composition is subjected to laser marking by using a fiber laser marking machine, wherein the laser energy is 3W, the marking frequency is 50KHz, and the marking speed is 800 mm/s.
EXAMPLE 4 preparation of composition 6 (hypocrellin)
In contrast to example 2, the photosensitizer during the preparation of the composition was selected from: 0.8 part of hypocrellin, the dosage of the photosensitizer is the same as that of the embodiment 2, and other components and the preparation method are also the same as that of the embodiment 2. The prepared composition is subjected to laser marking by using a fiber laser marking machine, wherein the laser energy is 3W, the marking frequency is 50KHz, and the marking speed is 800 mm/s.
EXAMPLE 5 preparation of composition 7 (chlorin + hematoporphyrin)
In contrast to example 2, the photosensitizer during the preparation of the composition was selected from: 0.4 part of chlorin and 0.4 part of hematoporphyrin, the total dose of the photosensitizer is the same as that of the embodiment 2, and other components and preparation methods are also the same as that of the embodiment 2. The prepared composition is subjected to laser marking by using a fiber laser marking machine, wherein the laser energy is 3W, the marking frequency is 50KHz, and the marking speed is 800 mm/s.
EXAMPLE 6 preparation of composition 8 (hematoporphyrin + hypocrellin)
In contrast to example 2, the photosensitizer during the preparation of the composition was selected from: 0.5 part of hypocrellin and 0.3 part of hematoporphyrin, the total dose of the photosensitizer is the same as that in the embodiment 2, and other components and the preparation method are also the same as that in the embodiment 2. The prepared composition is subjected to laser marking by using a fiber laser marking machine, wherein the laser energy is 3W, the marking frequency is 50KHz, and the marking speed is 800 mm/s.
Effect comparative example 2 Effect of the type of photosensitizer on laser marking Effect
The compositions prepared in examples 2 to 6 were laser-marked with the same laser power, and the effects of laser marking were compared, and the results are shown in the following table.
TABLE 2 Effect of the type of photosensitizer on laser marking Effect
Figure BDA0001839416020000081
Figure BDA0001839416020000091
According to the comparison result, the selection of the photosensitizer can influence the laser marking effect, and as can be seen from the emission spectrum of the converted nanoparticles in FIG. 1, although the emission wavelengths are 530-550nm and 630-662nm, the emission intensity around 540nm is stronger than that around 650nm, the absorption wavelength of hypocrellin in the photosensitizer is around 545nm, and the absorption wavelengths of chlorin and hematoporphyrin are between 630-660 nm. Therefore, when hypocrellin is contained in the photosensitizer, the laser efficiency is higher. As is clear from comparison of example 2 with example 6, chlorin is more efficient than hematoporphyrin, and therefore, in the present invention, the optimal combination of photosensitizers is hypocrellin and chlorin.
Effect of the proportion of upconverting nanoparticles and photosensitizer in the composition on the laser labeling effect
EXAMPLE 7 preparation of composition 9
Compared with the embodiment 2, 5 parts of up-conversion nano particles, 0.6 part of hypocrellin and 0.4 part of chlorin are added in the preparation process of the composition, and other components and the preparation method are the same as the embodiment 2. The prepared composition is subjected to laser marking by using a fiber laser marking machine, wherein the laser energy is 3W, the marking frequency is 50KHz, and the marking speed is 800 mm/s.
EXAMPLE 8 preparation of composition 10
Compared with the embodiment 2, 4 parts of up-conversion nano particles, 0.4 part of hypocrellin and 0.1 part of chlorin are added in the preparation process of the composition, and other components and the preparation method are the same as the embodiment 2. The prepared composition is subjected to laser marking by using a fiber laser marking machine, wherein the laser energy is 3W, the marking frequency is 50KHz, and the marking speed is 800 mm/s.
EXAMPLE 9 preparation of composition 11
Compared with the embodiment 2, 10 parts of up-conversion nano particles, 0.05 part of hypocrellin and 0.05 part of chlorin are added in the preparation process of the composition, and other components and the preparation method are the same as the embodiment 2. The prepared composition is subjected to laser marking by using a fiber laser marking machine, wherein the laser energy is 3W, the marking frequency is 50KHz, and the marking speed is 800 mm/s.
EXAMPLE 10 preparation of composition 12
Compared with the embodiment 2, 0.1 part of up-conversion nano-particles, 3 parts of hypocrellin and 2 parts of chlorin are added in the preparation process of the composition, and other components and the preparation method are the same as the embodiment 2. The prepared composition is subjected to laser marking by using a fiber laser marking machine, wherein the laser energy is 3W, the marking frequency is 50KHz, and the marking speed is 800 mm/s.
Effect example 3 Effect of the proportion of the conversion nanoparticles and the photosensitizer in the composition on the laser labeling Effect
The compositions prepared in example 2 and examples 7 to 10 were laser-marked and the marking effects were compared, and the results are shown in the following table.
TABLE 3 Effect of the proportion of conversion nanoparticles and photosensitizer in the composition on the laser labeling effect
Upconversion nanoparticle mass fraction Mass ratio of photosensitizer Definition of Marking effect
Example 2 2.3％ 0.9％ Bright color and high definition ++++++
Example 7 5.5％ 1.1％ Bright color and high definition ++++++
Example 8 4.5％ 0.6％ Bright color and high definition +++++++
Example 9 10.7％ 0.1％ Definition in general +++
Example 10 0.1％ 5.6％ Definition in general +++
From the comparison results, it can be seen that the ratio of the up-conversion nanoparticles to the photosensitizer in the composition affects the clarity of the mark and the color of the colored mark. Specifically, when the mass fraction of the up-conversion nanoparticles in the composition is 2.3-5.5% and the mass fraction of the photosensitizer is 0.6-1.1%, the color of the color laser mark is bright, the definition is good, and the overall marking effect is good; when the up-conversion nanoparticles are too many or the photosensitizer is too many, the laser marking effect is not good, because the relationship between the up-conversion nanoparticles and the photosensitizer complements each other, emitted light formed by a proper amount of up-conversion nanoparticles is absorbed by a proper amount of photosensitizer, and the efficiency of laser efficiency is increased to the maximum extent, so that a good laser marking effect can be realized.
EXAMPLE 11 preparation of composition 13
Putting 75 parts of polyamide resin, 2 parts of up-conversion nano particles, 0.5 part of hypocrellin, 0.3 part of chlorin, 0.5 part of black pigment furnace carbon black and 2 parts of color pigment phthalocyanine red into a high-speed mixer, uniformly mixing, adding 0.4 part of antioxidant pentaerythritol ester and 0.8 part of lubricant magnesium stearate, and continuously mixing until uniform; putting the uniformly mixed materials into a double-screw extruder, extruding at the processing temperature of 250 ℃ and the rotating speed of a main machine of 600 revolutions per minute, and adding 5 parts of filler glass fiber in the middle of the extruder; cooling the mixture by an ultra-cold roller to obtain a composition capable of being subjected to laser color marking; and then, carrying out laser marking by using a fiber laser marking machine, wherein the laser energy is 3W, the marking frequency is 50KHz, and the marking speed is 800 mm/s.
EXAMPLE 12 preparation of composition 14
Putting 75 parts of polyamide resin, 4 parts of up-conversion nano particles, 1 part of hypocrellin, 0.6 part of chlorin, 0.5 part of black pigment furnace carbon black and 2 parts of color pigment phthalocyanine red into a high-speed mixer, uniformly mixing, adding 0.4 part of antioxidant pentaerythritol ester and 0.8 part of lubricant magnesium stearate, and continuously mixing until uniform; putting the uniformly mixed materials into a double-screw extruder, extruding at the processing temperature of 250 ℃ and the rotating speed of a main machine of 600 revolutions per minute, and adding 5 parts of filler glass fiber in the middle of the extruder; cooling the mixture by an ultra-cold roller to obtain a composition capable of being subjected to laser color marking; and then, carrying out laser marking by using a fiber laser marking machine, wherein the laser energy is 3W, the marking frequency is 50KHz, and the marking speed is 800 mm/s.
Effect example 4 Effect of resin mother particle on laser marking Effect
The compositions prepared in example 2 and examples 7 to 10 were laser-marked and the marking effects were compared, and the results are shown in the following table.
TABLE 4 influence of resin masterbatch on laser marking effect
Definition of Marking effect
Example 2 Bright color and high definition ++++++
Example 11 The color is visible and the definition is general +++
Example 12 The color is visible and the definition is general ++++
In contrast to example 2, examples 11-12 were prepared by mixing the polyamide resin and the upconverting nanoparticles with the photosensitizer, the black pigment, and the color pigment in a high mixing machine, unlike example 2 in which a small amount of the polyamide resin and the upconverting nanoparticles are melt-mixed with the photosensitizer, the black pigment, and the color pigment, and then the mixture is prepared into a resin masterbatch and then mixed with the remaining polyamide resin. From the test results in the table above, it can be seen that the resin masterbatch is prepared from a small amount of polyamide resin, the upconversion nanoparticles, the photosensitizer, the black pigment and the color pigment, and the laser marking effect is better. The conversion nanoparticles, the photosensitizer and the pigment can be uniformly dispersed in the resin master batch at the beginning, and the additive has better dispersibility and higher uniformity in the resin when being mixed and redispersed with a large amount of polyamide resin subsequently, so that the marking effect is better.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (6)

1. A composition capable of laser color marking comprises the following raw materials, by mass, 40-80 parts of polyamide resin, 0.1-5 parts of up-conversion nanoparticles, 0.1-3 parts of a photosensitizer, 0.1-1 part of a black pigment, 0.2-3 parts of a color pigment, 0.3-0.6 part of an antioxidant, 0.5-1 part of a lubricant and 0-20 parts of a filler, wherein in the preparation process, 4-8 parts of polyamide resin, 0.1-5 parts of up-conversion nanoparticles, 0.1-3 parts of a photosensitizer, 0.1-1 part of a black pigment and 0.2-3 parts of a color pigment are prepared into resin master batches, and then the resin master batches are mixed with the rest of polyamide resin, 0.3-0.6 part of an antioxidant, 0.5-1 part of a lubricant and 0-20 parts of a filler and are extruded, in the composition capable of being marked by laser, the mass ratio of the up-conversion nanoparticles is 2-5.5%, the mass ratio of the photosensitizer is 0.5-1.5%, the up-conversion nanoparticles can emit light emission at 530-550nm and 630-662nm under the irradiation of 1064nm exciting light, and the emitted light can excite the photosensitizer at the moment, so that the photosensitizer can generate a photothermal effect.
2. The composition of claim 1, wherein the upconverting nanoparticle is NaYF 4: er and Yb with the grain diameter of 20-150 nm; the photosensitizer is selected from: one or more of dihydroporphin, hematoporphyrin, bihematoporphyrin ether and hypocrellin.
3. A composition as claimed in claim 2, wherein the up-conversion nanoparticles NaYF 4: the preparation method of Er and Yb comprises the following steps:
(1) dissolving a rare earth raw material in methanol, adding a high-temperature solvent, evaporating the methanol solvent to dryness, reacting at the temperature of 150 ℃ and 170 ℃ for 30-40min in a nitrogen atmosphere, and cooling to room temperature;
(2) adding the product obtained in the previous step into a methanol solution dissolved with NaOH and NH4F, stirring, evaporating the methanol solvent to dryness, heating to 300-320 ℃ in a nitrogen atmosphere, carrying out heat preservation reaction, and cooling to room temperature;
(3) precipitating with ethanol, centrifuging, and washing to obtain an upconversion precursor;
(4) the precursor is formed into superfine powder through a jet microwave combustion synthesis method to obtain up-conversion nano particles; wherein, the rare earth raw material in the step (1) is selected from: YCl3, YbCl3 and ErCl3, wherein the concentration of YCl3 is 0.9-2.7 mol%, the concentration of YbCl3 is 0.1-1.5 mol%, and the concentration of ErCl3 is 0.1-0.9 mol%.
4. A process for the preparation of a laser colour markable composition according to any of the claims 1 to 3 comprising the steps of:
(1) melting and mixing 5-10% of the expected dosage of polyamide resin with the up-conversion nanoparticles, the photosensitizer, the black pigment and the color pigment to prepare resin master batches, putting the rest polyamide resin and the prepared resin master batches into a high-speed mixer to be uniformly mixed, adding the antioxidant and the lubricant, and continuously mixing until the mixture is uniform;
(2) feeding the uniformly mixed materials into a double-screw extruder, extruding, and adding a filler into the middle part of the extruder;
(3) cooling by an ultra-cold roller;
(4) laser marking was performed on the composition prepared in the above step.
5. The method according to claim 4, wherein the laser marking in step (4) is selected from the group consisting of: the fiber laser marking machine has the laser wavelength of 1064nm, the laser energy of 3-10W, the marking frequency of 20-100KHz and the marking speed of 600-1000 mm/s.
6. Use of a laser colour markable composition according to any one of claims 1 to 3 for the preparation of high precision devices, being integrated circuit chips, computer accessories, electronic communication products or aerospace devices.
CN201811241399.7A 2018-10-24 2018-10-24 Composition capable of being subjected to laser color marking and used for fiber laser Active CN109337356B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811241399.7A CN109337356B (en) 2018-10-24 2018-10-24 Composition capable of being subjected to laser color marking and used for fiber laser

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811241399.7A CN109337356B (en) 2018-10-24 2018-10-24 Composition capable of being subjected to laser color marking and used for fiber laser

Publications (2)

Publication Number Publication Date
CN109337356A CN109337356A (en) 2019-02-15
CN109337356B true CN109337356B (en) 2020-10-20

Family

ID=65311732

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811241399.7A Active CN109337356B (en) 2018-10-24 2018-10-24 Composition capable of being subjected to laser color marking and used for fiber laser

Country Status (1)

Country Link
CN (1) CN109337356B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110343525B (en) * 2019-06-25 2020-11-06 浙江大学 Method for directly exciting triplet state of organic molecule by rare earth ions
CN113084349A (en) * 2021-03-26 2021-07-09 维沃移动通信有限公司 Laser engraving method for plate, plate and electronic device

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103223171A (en) * 2013-04-03 2013-07-31 华南理工大学 Porphyrin and uptransition rare earth nanocomposite, preparation method and application thereof
CN104498037A (en) * 2014-11-28 2015-04-08 赵兵 PAMAM (polyamide-amine)-modified water-soluble upconversion nanoparticles and preparation method thereof
CN104784692A (en) * 2015-05-13 2015-07-22 哈尔滨工业大学 Method for preparing core-shell structure drug carrier with near-infrared light remote response and application thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11228813A (en) * 1998-02-09 1999-08-24 Mitsubishi Eng Plast Corp Polyamide resin composition for laser marking

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103223171A (en) * 2013-04-03 2013-07-31 华南理工大学 Porphyrin and uptransition rare earth nanocomposite, preparation method and application thereof
CN104498037A (en) * 2014-11-28 2015-04-08 赵兵 PAMAM (polyamide-amine)-modified water-soluble upconversion nanoparticles and preparation method thereof
CN104784692A (en) * 2015-05-13 2015-07-22 哈尔滨工业大学 Method for preparing core-shell structure drug carrier with near-infrared light remote response and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
NaYF4:Gd,Yb,Er/PEI上转换纳米颗粒的合成及其在PDT和MRI中的应用;陈小兰 等;《玉林师范学院学报》;20161231;第37卷(第5期);第62-68页 *
Polymer-coated NaYF4:Yb3+,Er3+ upconversion nanoparticles for charge-dependent cellular imaging;Jiefu Jin et al;《ACS NANO》;20110909;第5卷(第10期);第7838-7847页 *

Also Published As

Publication number Publication date
CN109337356A (en) 2019-02-15

Similar Documents

Publication Publication Date Title
Zhou et al. Hydrogen peroxide‐treated carbon dot phosphor with a bathochromic‐shifted, aggregation‐enhanced emission for light‐emitting devices and visible light communication
CN109337356B (en) Composition capable of being subjected to laser color marking and used for fiber laser
CN1011497B (en) Laser marking of pigmented systems
CN1276030C (en) Water-based colorant preparations
CN108504356B (en) Manganese-doped inorganic halogen perovskite quantum dot and preparation method and application thereof
Ji et al. Light of carbon: Recent advancements of carbon dots for LEDs
Hou et al. Facile synthesis of carbon dots in an immiscible system with excitation-independent emission and thermally activated delayed fluorescence
CN108795428B (en) Anti-counterfeiting material and preparation method and application thereof
JPH03106944A (en) Method of effecting laser marking having a special effect on plastic product in any form
JPH024584A (en) Laser marking method of colored material
CN104031477A (en) Panchromatic fluorescent anti-counterfeiting ink based on conjugated polymer nano-particles
CN1238432C (en) Anthrapyridone compound, water-based magenta ink composition, and method of ink-jet recording
CN107513212A (en) A kind of polyolefin laser marking master batch and preparation method thereof
CN109233809B (en) Preparation of composite bifunctional perovskite material combining thermoluminescence and photoluminescence performance
CN112342017A (en) Ultra-long-life room temperature phosphorescent material and preparation method and application thereof
CN109354855B (en) Hard plastic capable of being marked by laser color
JPWO2003106588A1 (en) Spherical phosphorescent phosphor powder and method for producing the same
CN113956869B (en) Manufacturing method of dielectric microsphere patterned array up-conversion luminescence flexible film applied to anti-counterfeiting mark
CN108728089B (en) Manganese-doped inorganic halogen perovskite quantum dot and preparation method thereof
Fu et al. Recent advances in solid-state fluorescent of red carbon dots: A comprehensive review
US7829258B2 (en) Laser coloration of coated substrates
Li et al. Preparation and performance study of dye-based carbon quantum dots
CN110511526B (en) Compound capable of achieving low-temperature laser etching of multiple colors and preparation method thereof
CN1189180A (en) Ink for ink jet printing and method of printing using the same
KR100618083B1 (en) Invisible-Light Absorption Material and Ink and Manufacturing Method of the same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right

Effective date of registration: 20191106

Address after: 311899 building 17, Xueyuan Road, Jiyang street, Zhuji City, Shaoxing City, Zhejiang Province

Applicant after: Zhejiang youkeli New Material Co., Ltd

Address before: Room 4022, 1155 Park East Road, Qingpu District, Shanghai, 201799

Applicant before: Yang Dingjifu

TA01 Transfer of patent application right
GR01 Patent grant
GR01 Patent grant