CN109486128B - Plastic paper capable of being marked with laser color - Google Patents
Plastic paper capable of being marked with laser color Download PDFInfo
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- CN109486128B CN109486128B CN201811241440.0A CN201811241440A CN109486128B CN 109486128 B CN109486128 B CN 109486128B CN 201811241440 A CN201811241440 A CN 201811241440A CN 109486128 B CN109486128 B CN 109486128B
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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
- 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
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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
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses plastic paper capable of being marked by laser colors, which is prepared from a plastic material, sodium allylsulfonate, an initiator, a black pigment, a color pigment, an antioxidant, a flame retardant, a lubricant and optionally added or not added fillers, wherein the types and the mass ratios of the plastic material and the flame retardant, the types of the color pigment and the mass ratio of the color pigment to the black pigment have influence on the heat resistance degree of the plastic paper and the quality of the laser marks. The applicant selects the plastic material, the color pigment and the additive specifically to enable the components to be matched with each other, so that the phenomenon of thermal shrinkage caused by local heat absorption of the plastic paper is avoided in the laser marking process, and the mark to be displayed can be displayed clearly.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to packaging plastic paper capable of being marked by laser colors.
Background
In daily life, some foods, medicines, cosmetics and the like have poor stability and are easy to generate reactions such as oxidation, decomposition, color change and the like when being exposed to light, for example, some chemotherapeutic drugs can generate complex reactions such as ring cleavage, rearrangement, hydrolysis, polymerization, oxidation, isomerization and the like after being dissolved, and the reaction process can be catalyzed under the condition of light. As another example, photosensitizers are used in the treatment of disease, drugs absorb visible light and break down during instillation. Therefore, all the objects which are unstable to light need to be protected from light. In general, people put articles to be stored in dark places or in tinfoil bags for storage, and even if the articles are stored in dark places, a small amount of light can penetrate through the articles, so that the quality of the stored articles is damaged. Based on the background, the inventor provides a plastic packaging paper capable of being used in the dark place, the plastic packaging paper can be used for external packaging of articles, and can also be used for shading in the use process of the articles, for example, chemotherapy drugs cannot be used immediately after being dissolved, or a dropping bottle needs to be shaded when photosensitizer-containing drugs are dropped, and the plastic packaging paper prepared by the invention can be used in the dark place in the situations. Because the packaging plastic paper is added with the black pigment to present black, a plurality of articles are difficult to distinguish after being respectively packaged. In order to be able to clearly distinguish the packaged articles, the inventors chose to mark the packaging plastic paper with a laser. Compared with traditional marking technologies such as ink printing and chemical corrosion, the laser marking technology has superiority in multiple aspects, and the laser marking has the advantages of non-contact property, environmental protection, long durability, rapidness, high efficiency, high applicability and the like.
For laser marking on plastics, there are currently three main forms: firstly, processing a dark mark on a light-colored plastic part; secondly, processing a light-color mark on a dark-color plastic part; and thirdly, directly processing a color mark on the plastic part. The different colors marked are mainly controlled by the type of reaction occurring in the plastic material, the adjustment of laser equipment parameters and the type of laser marking additive added. In addition, the definition and contrast of the color of the mark are in certain relation with the material of the plastic part.
The color of the plastic substrate used for avoiding light is black, and if the color of the mark is white, part of light can be transmitted, which is not beneficial to avoiding light. The inventors of the present application therefore sought to colour mark on black based plastics. For color marking, the development stage is still in progress, and the practical production application is less.
Patent document CN101003225A discloses a color marking method, which comprises applying a laser beam on a surface layer material of an object to be marked to form an oxide film, obtaining a color effect by thin film interference, marking a primary color on the surface layer material three times or more, applying a laser beam according to different primary color effects for each marking, and mixing the primary colors to form a true color effect. The method not only needs multiple laser marking, but also has complicated steps, the color effect of the marking is realized by overlapping the effect after multiple laser irradiation, the process parameters are more in mass production, and the color effect is likely to be uneven and difficult to repeat.
Patent document CN105172403A discloses a method for color marking, which comprises forming a precursor solution layer on the surface of a substrate; partitioning the precursor solution layer according to the color of a preset marking image; sintering and annealing the precursor solution layers in different partitions by adopting laser to form thin film layers with different thicknesses, wherein the thicknesses of the thin film layers and the thicknesses of the precursor solution layers meet a preset relation; the thin film layers with different thicknesses are displayed in different colors and form the preset mark image. The method has the advantages of high realization difficulty, high resource consumption and high cost, and is difficult to be put into large-scale production.
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, and the principle is that the temperature-sensitive substance generates reactions such as thermal decomposition, oxidation and the like at a certain temperature through the heat generated in the laser marking process, so as to destroy the original substance structure to generate a new substance, generate a new color, and realize color laser marking. However, the selection of the temperature sensitive substance is very strict and the application range is limited. Therefore, there is no good method for simple and efficient color laser marking.
In addition, laser marking on plastic paper, one of the most important problems is: the laser irradiation portion locally generates heat, and generally, plastic paper is thin, which easily causes local thermal shrinkage, and causes defects such as wrinkle aggregation, etc., so that the entire mark is irregular, and the resolution is seriously lowered. Patent document CN105121173A discloses an information writing film having chemical resistance and abrasion resistance and suitable for high-contrast white laser marking. Although the problem of local shrinkage of the laser marking of the film is improved, the process is complicated, the information writing film and the read-assisting layer need to be prepared, and the color developing material used as a color developing agent for laser writing is kneaded with a transparent plastic material which has high chemical resistance and structural strength in a molded state, without forming the writing film layer directly. Such complicated and tedious preparation process inevitably leads to over high production cost and low acceptance of consumers after being put into the market.
In order to overcome the defects of the prior art, simplify the preparation steps, reduce the production cost and simultaneously achieve the purpose of carrying out color laser marking on the plastic paper, in the application, the applicant selects the plastic material, the color pigment and the additive specifically to ensure that all the components are matched with each other, so that the phenomenon of thermal shrinkage caused by local heat absorption of the plastic paper is avoided in the laser marking process, and the mark to be presented can be clearly displayed.
Disclosure of Invention
The invention aims to provide plastic paper capable of being marked by laser colors and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
a plastic paper capable of being marked by laser color is prepared from a plastic material, sodium allylsulfonate, an initiator, a black pigment, a color pigment, an antioxidant, a flame retardant, a lubricant and optionally added or not added fillers, wherein the plastic material, the black pigment, the color pigment and the additives are selected so that a thermal shrinkage phenomenon caused by local heat absorption of the plastic paper can not occur in a laser marking process, and a mark to be shown can be clearly displayed, and the plastic material is a combination of polybutylene terephthalate resin, polystyrene resin and polyvinylidene chloride.
Preferably, the plastic paper capable of being color-marked by laser comprises the following raw materials in parts by weight: 30-50 parts of polybutylene terephthalate resin, 25-40 parts of polystyrene resin, 10-20 parts of polyvinylidene chloride, 0.1-0.6 part of sodium allylsulfonate, 0.05-0.2 part of initiator, 0.1-1 part of black pigment, 0.1-3 parts of color pigment, 0.2-0.6 part of antioxidant, 0.1-0.4 part of lubricant, 0.2-1 part of flame retardant and 0-40 parts of filler.
In the preparation process, firstly, 3 to 5 parts of polyethylene terephthalate, 2.5 to 4 parts of polystyrene resin, 1 to 2 parts of polyvinylidene chloride, 0.1 to 1 part of black pigment and 0.1 to 3 parts of color pigment are prepared into resin master batch, and then the resin master batch is mixed with the rest of polyethylene terephthalate, polystyrene resin, polyvinylidene chloride and 0.1 to 0.6 part of all sodium allylsulfonate, 0.05 to 0.2 part of initiator, 0.2 to 0.6 part of antioxidant, 0.1 to 0.4 part of lubricant, 0.2 to 1 part of flame retardant and 0 to 40 parts of filler for extrusion or blow molding.
The intrinsic viscosity of the polybutylene terephthalate resin is 0.68 to 1.35 ml/g.
The initiator is selected from: one or more of benzoyl peroxide, lauroyl peroxide and cyclohexanone peroxide.
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.
More preferably, the colour pigments are selected from: one or the combination of more than two of acetyl arylamine, pyrazolone, 2-hydroxy-3-naphthoic acid and 2-hydroxy-3-naphthoyl arylamine.
The filler is one or the combination of more than two of glass fiber, glass beads, calcium carbonate, talcum powder, barium sulfate, kaolin and clay.
Preferably, the filler is selected from glass fibers.
The antioxidant is selected from pentaerythritol ester and phosphite ester, and the mass part ratio of the pentaerythritol ester to the phosphite ester is 1: 1-1.5.
The lubricant is selected from pentaerythritol stearate.
The flame retardant is selected from: one or the combination of more than two of tributyl phosphate, tetrabromobisphenol A and tetrachlorobisphenol A.
Preferably, the flame retardant is selected from: tetrabromobisphenol A or tetrachlorobisphenol A in combination with tributyl phosphate.
More preferably, the flame retardant is selected from tetrabromobisphenol a and tributyl phosphate.
The color laser mark of the invention can be any shape of pattern, character, two-dimensional code, bar code, etc.
In the invention, the thickness and the hardness degree of the plastic paper can be controlled by reasonably adjusting the mass ratio of the plastic materials, so that the plastic paper suitable for laser marking is obtained. Preferably, the mass part ratio of the polybutylene terephthalate resin to the polystyrene resin to the polyvinylidene chloride resin is 1-2:1: 0.3-0.6; the thickness of the plastic paper is 0.5-3 mm.
More preferably, the mass part ratio of the polybutylene terephthalate resin to the polystyrene resin to the polyvinylidene chloride resin is 1-1.6:1: 0.5; the thickness of the plastic paper is 0.8-1.2 mm.
In the present invention, the kind of the flame retardant and the mass ratio to the plastic material are related to the heat resistance of the plastic paper during the laser marking process. Preferably, the mass ratio of the plastic material to the flame retardant is 80-130: 1.
More preferably, the mass ratio of the plastic material to the flame retardant is 80-90: 1.
In the present invention, the kind of the color pigment and the mass ratio of the color pigment to the black pigment are related to the resolution of the finally formed color mark. Preferably, the mass ratio of the color pigment to the black pigment is 1: 1-3.
More preferably, the mass ratio of the color pigment to the black pigment is 1:1 to 1.6.
A preparation method for preparing plastic paper capable of being marked by laser comprises the following steps:
(1) firstly, taking 10-15% of the predicted dosage of polybutylene terephthalate resin, polystyrene resin and polyvinylidene chloride, melting and mixing the polybutylene terephthalate resin, the polystyrene resin and the polyvinylidene chloride with a black pigment and a color pigment to prepare resin master batches, then putting the rest polybutylene terephthalate resin, the polystyrene resin and the polyvinylidene chloride, sodium allylsulfonate, an initiator and the resin master batches into a high-speed mixer to be uniformly mixed, adding an antioxidant, a lubricant and a flame retardant, 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) and carrying out laser marking on the plastic paper prepared in the 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: c02Laser marking machine, semiconductor laser marking machine, fiber laser marking machine or Nd-YAG laser.
More preferably, the laser is selected from C02The laser marking machine has pulse repetition frequency of 30-50KHz, pulse width of 0.5-1.5us, marking speed of 20-30mm/s and marking current of 8-12A.
In a preferred embodiment of the invention, the laser is selected from C02The laser marking machine has pulse repetition frequency of 30-35KHz, pulse width of 0.5-1us, marking speed of 20-25mm/s and marking current of 8-10A.
Use of a laser-markable plastic paper for the packaging of articles which contain structures of poor light stability and which need to be stored protected from light.
In the invention, the plastic paper with moderate thickness and hardness is prepared by reasonably adjusting the mass ratio of the plastic materials, so that the plastic paper can be used for laser marking; meanwhile, the addition amount of the flame retardant in the prepared material is controlled, and the plastic paper is controlled not to shrink due to local heating in the laser marking process; in addition, the inventor specifically selects the type of the color pigment and the mass ratio of the color pigment to the black pigment, and improves the definition and the resolution of the color laser mark. The plastic paper prepared by the invention can form permanent colorful marks on the surface thereof through laser marking, and meanwhile, the plastic paper can be used for packaging articles because the plastic paper takes black as a basic color, the articles need to be stored in a dark place because of containing a structure with poor light stability, and the colorful marks on the plastic paper are used for identifying the packaged articles.
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.
Preference test for Plastic materials
Example 1 preparation of plastic paper 1
Firstly, taking 5 parts of polybutylene terephthalate resin (with the viscosity of 1ml/g), 2.5 parts of polystyrene resin, 1 part of polyvinylidene chloride, 1 part of black pigment furnace carbon black and 3 parts of color pigment 2-hydroxy-3-naphthoyl aromatic amine, melting and fully mixing to prepare resin master batch; then 45 parts of polybutylene terephthalate resin, 22.5 parts of polystyrene resin, 9 parts of polyvinylidene chloride, 0.5 part of sodium allylsulfonate, 0.1 part of benzoyl peroxide as an initiator and the resin master batch prepared in the steps are put into a high-speed mixer to be mixed uniformly, and then 0.2 part of antioxidant pentaerythritol ester, 0.2 part of phosphite ester, 0.3 part of pentaerythritol stearate, 0.7 part of tetrabromobisphenol A as a flame retardant and 0.3 part of tributyl phosphate are put into the high-speed mixer to be mixed continuously until the mixture is uniform. And transferring the materials into a double-screw extruder, wherein the processing temperature of the extruder is 250 ℃, the rotating speed of a main machine is 500 r/min, and extruding. Then cooling by an ultra-cold roller to obtain the plastic paper. Using C02The laser marking machine carries out laser marking, the repetition frequency of laser pulse is 35KHz, the pulse width is 0.5us, the marking speed is 20mm/s, and the marking current is 10A.
Example 2 preparation of plastic paper 2
48 parts of polybutylene terephthalate resin (viscosity is 1.35ml/g), 30 parts of polystyrene resin and 15 parts of polyvinylidene chloride, wherein 10 percent of the total amount of the three plastic materials are melted and fully mixed with 1 part of black pigment furnace carbon black and 3 parts of color pigment 2-hydroxy-3-naphthoyl aromatic amine to prepare resin master batch; the remaining components and the order of addition were the same as in example 1. And transferring the materials into a double-screw extruder, wherein the processing temperature of the extruder is 250 ℃, the rotating speed of a main machine is 500 r/min, and extruding. Then cooling by an ultra-cold roller to obtain the plastic paper. Using C02The laser marking machine carries out laser marking, the repetition frequency of laser pulse is 35KHz, the pulse width is 0.5us, the marking speed is 20mm/s, and the marking current is 10A.
Example 3 preparation of plastic paper 3
The total weight of 35 parts (viscosity is 0.68ml/g) of polybutylene terephthalate resin, 35 parts of polystyrene resin and 17 parts of polyvinylidene chloride, wherein 10 percent of the total weight of the three plastic materials is melted and fully mixed with 1 part of black pigment furnace carbon black and 3 parts of color pigment 2-hydroxy-3-naphthoyl aromatic amine to prepare resin master batch; the remaining components and the order of addition were the same as in example 1. And transferring the materials into a double-screw extruder, wherein the processing temperature of the extruder is 250 ℃, the rotating speed of a main machine is 500 r/min, and extruding. Then cooling by an ultra-cold roller to obtain the plastic paper. Using C02The laser marking machine carries out laser marking, the repetition frequency of laser pulse is 35KHz, the pulse width is 0.5us, the marking speed is 20mm/s, and the marking current is 10A.
Example 4 preparation of Plastic paper 4
30 parts of polybutylene terephthalate resin (with the viscosity of 0.43ml/g), 40 parts of polystyrene resin and 15 parts of polyvinylidene chloride, wherein 10 percent of the total amount of the three plastic materials is melted and fully mixed with 1 part of black pigment furnace carbon black and 3 parts of color pigment 2-hydroxy-3-naphthoyl aromatic amine to prepare resin master batch; the remaining components and the order of addition were the same as in example 1. And transferring the materials into a double-screw extruder, wherein the processing temperature of the extruder is 250 ℃, the rotating speed of a main machine is 500 r/min, and extruding. Then cooling by an ultra-cold roller to obtain the plastic paper. Using C02The laser marking machine carries out laser marking, the repetition frequency of laser pulse is 30KHz, the pulse width is 0.5us, the marking speed is 20mm/s, and the marking current is 8A.
Example 5 preparation of Plastic paper 5
30 parts of polybutylene terephthalate resin (viscosity is 1.80ml/g), 25 parts of polystyrene resin and 20 parts of polyvinylidene chloride, wherein 10 percent of the total amount of the three plastic materials are melted and fully mixed with 1 part of black pigment furnace carbon black and 3 parts of color pigment 2-hydroxy-3-naphthoyl aromatic amine to prepare the resinA fat masterbatch; the remaining components and the order of addition were the same as in example 1. And transferring the materials into a double-screw extruder, wherein the processing temperature of the extruder is 250 ℃, the rotating speed of a main machine is 500 r/min, and extruding. Then cooling by an ultra-cold roller to obtain the plastic paper. Using C02The laser marking machine carries out laser marking, the repetition frequency of laser pulse is 30KHz, the pulse width is 0.5us, the marking speed is 20mm/s, and the marking current is 8A.
Comparative example 1 preparation of plastic paper comparative example 1
40 parts of polystyrene resin and 30 parts of polyvinylidene chloride, wherein 10 percent of the total amount of the two plastic materials are melted and fully mixed with 1 part of black pigment furnace carbon black and 3 parts of color pigment 2-hydroxy-3-naphthoyl aromatic amine to prepare resin master batch; the remaining components and the order of addition were the same as in example 1. And transferring the materials into a double-screw extruder, wherein the processing temperature of the extruder is 250 ℃, the rotating speed of a main machine is 500 r/min, and extruding. Then cooling by an ultra-cold roller to obtain the plastic paper. Using C02The laser marking machine carries out laser marking, the repetition frequency of laser pulse is 30KHz, the pulse width is 0.5us, the marking speed is 20mm/s, and the marking current is 8A.
Effect examples effect of plastic material on laser marking
The marking effects of the plastic papers prepared in examples 1 to 5 and comparative example 1, which were laser-marked under the conditions as described above, are shown in the following table:
TABLE 1 Effect of different Plastic materials on laser marking
According to the test results, when the plastic materials are only polystyrene resin and polyvinylidene chloride, the formed plastic is too soft, so that the part where the laser passes through is burnt through, and the laser marking cannot be carried out; when the plastic material is polybutylene terephthalate resin, polystyrene resin and polyvinylidene chloride, the problem of laser puncturing of the plastic can not occur. As can be seen from the comparison, in examples 4 and 5, the laser intensity was lower in the laser marking than in examples 1 to 3, but the heat-affected portion shriveled after the laser marking. From the above results, it can be seen that the laser marking effect is most excellent when the mass ratio of the polybutylene terephthalate resin, the polystyrene resin and the polyvinylidene chloride is 1-2:1:0.4-0.5 and the viscosity of the polybutylene terephthalate resin is 0.68-1.35 ml/g.
Preference test for flame retardants
Example 6 preparation of Plastic paper 6
In this example, the flame retardant was tetrabromobisphenol A1.5 parts and tributyl phosphate 1.5 parts, and the remaining raw materials and the preparation method were the same as in example 1. Using C02The laser marking machine carries out laser marking, the repetition frequency of laser pulse is 35KHz, the pulse width is 0.5us, the marking speed is 20mm/s, and the marking current is 10A.
Example 7 preparation of plastic paper 7
In the embodiment, the flame retardant is 0.7 part of tributyl phosphate, and the rest of the preparation raw materials and the preparation method are the same as those in the embodiment 1. Using C02The laser marking machine carries out laser marking, the repetition frequency of laser pulse is 35KHz, the pulse width is 0.5us, the marking speed is 20mm/s, and the marking current is 10A.
Example 8 preparation of Plastic paper 8
In this example, the flame retardant was 0.2 part of tetrabromobisphenol a and 0.1 part of tributyl phosphate, and the remaining raw materials and the preparation method were the same as those in example 1. Using C02The laser marking machine carries out laser marking, the repetition frequency of laser pulse is 35KHz, the pulse width is 0.5us, the marking speed is 20mm/s, and the marking current is 10A.
Example 9 preparation of Plastic paper 9
In this example, 1 part of ammonium polyphosphate was used as a flame retardant, and the other preparation raw materials and preparation methods were the same as those in example 1. Using C02The laser marking machine carries out laser marking, the repetition frequency of laser pulse is 35KHz, the pulse width is 0.5us, the marking speed is 20mm/s, and the marking current is 10A.
Effect examples Effect of flame retardants on laser marking
After the plastic papers prepared in examples 1 and 6 to 9 were laser-marked under the conditions as described above, the marking effects are shown in the following table:
TABLE 2 Effect of flame retardants on laser marking
According to the test results, the type of the flame retardant and the mass ratio of the flame retardant to the plastic material influence the quality of laser marking, and when the flame retardant is the combination of tetrabromobisphenol A and tributyl phosphate, the laser marking effect is better than that of tributyl phosphate used alone and better than that of ammonium polyphosphate; in addition, the laser marking effect can be influenced by too much or too little adding amount of the flame retardant, and in the test, the effect is best when the mass ratio of the plastic material to the flame retardant is 85-120: 1.
Preferred test for color pigments
Example 10 preparation of plastic paper 10
In this example, 1 part of black pigment furnace carbon black and 1.6 parts of color pigment 2-hydroxy-3-naphthoyl aromatic amine were used, and the remaining raw materials and the preparation method were the same as those in example 1. The marking was carried out by using a C02 laser marking machine, the laser pulse repetition rate was 35KHz, the pulse width was 0.5us, the marking speed was 20mm/s, and the marking current was 10A.
Example 11 preparation of Plastic paper 11
In this example, 1 part of black pigment furnace carbon black and 1 part of color pigment 2-hydroxy-3-naphthoyl aromatic amine were prepared, and the remaining raw materials and preparation method were the same as those in example 1. The marking was carried out by using a C02 laser marking machine, the laser pulse repetition rate was 35KHz, the pulse width was 0.5us, the marking speed was 20mm/s, and the marking current was 10A.
Example 12 preparation of Plastic paper 12
In this example, 1 part of black pigment furnace carbon black and 0.5 part of color pigment 2-hydroxy-3-naphthoyl aromatic amine were used, and the remaining raw materials and the preparation method were the same as those in example 1. The marking was carried out by using a C02 laser marking machine, the laser pulse repetition rate was 35KHz, the pulse width was 0.5us, the marking speed was 20mm/s, and the marking current was 10A.
Example 13 preparation of Plastic paper 13
In this example, 1 part of black pigment furnace carbon black and 2 parts of colored pigment lithopone were used, and the remaining raw materials and the preparation method were the same as those in example 1. The marking was carried out by using a C02 laser marking machine, the laser pulse repetition rate was 35KHz, the pulse width was 0.5us, the marking speed was 20mm/s, and the marking current was 10A.
Effect examples Effect of color pigments on laser marking
After the plastic papers prepared in examples 1 and 10 to 13 were laser-marked under the conditions as described above, the marking effects are shown in the following table:
TABLE 3 Effect of color pigments on laser marking
| Mass ratio of black pigment to color pigment | Marking effect | Resolution ratio | |
| Example 1 | 1:3 | The pattern has clear color and regular edge | ++++ |
| Example 10 | 1:1.6 | The pattern has clear and bright color and regular edges | +++++ |
| Example 11 | 1:1 | The pattern has clear color and regular edge | ++++ |
| Example 12 | 1:0.5 | The pattern is substantially invisible | + |
| Example 13 | 1:2 | Clear pattern color and disordered boundary | ++ |
According to the results, the selection of the types of the color pigments and the mass ratio of the color pigments to the black pigments have great influence on the resolution of the mark, and when the color pigments are selected from organic dye 2-hydroxy-3-naphthoyl aromatic amine, the sensitivity to the heated edge part in the laser marking process is better than lithopone; when the amount of the color pigment added is too small, the cluster is substantially invisible; in this test, the pattern resolution was best when the mass ratio of black pigment to color pigment was 1: 1-3.
The above embodiments are merely illustrative of the present disclosure and do not represent a limitation of the present disclosure. Other variations of the specific structure of the invention will occur to those skilled in the art.
Claims (8)
1. A plastic paper capable of being color-marked by laser is prepared from a plastic material, a black pigment, a color pigment and an additive, wherein the additive is one or two of sodium allylsulfonate, an initiator, an antioxidant, a flame retardant, a lubricant and a filler, the plastic material, the black pigment, the color pigment and the additive are selected so that a thermal shrinkage phenomenon caused by local heat absorption of the plastic paper can not occur in a laser marking process, and a mark to be presented can be clearly displayed, and the plastic material is a combination of polybutylene terephthalate resin, polystyrene resin and polyvinylidene chloride, wherein the plastic paper comprises the following raw materials in parts by mass: 30-50 parts of polybutylene terephthalate resin, 25-40 parts of polystyrene resin, 10-20 parts of polyvinylidene chloride, 0.1-0.6 part of sodium allylsulfonate, 0.05-0.2 part of initiator, 0.1-1 part of black pigment, 0.1-3 parts of color pigment, 0.2-0.6 part of antioxidant, 0.1-0.4 part of lubricant, 0.2-1 part of flame retardant and 0-40 parts of filler; the intrinsic viscosity of the polybutylene terephthalate resin is 0.68-1.35 ml/g; the mass part ratio of the polybutylene terephthalate resin to the polystyrene resin to the polyvinylidene chloride is 1-2:1: 0.3-0.6; the mass ratio of the color pigment to the black pigment is 1:1-3 and the mass ratio of the plastic material to the flame retardant is 80-130: 1.
2. The plastic paper as claimed in claim 1, wherein the plastic paper is prepared by first preparing 3-5 parts of polyethylene terephthalate, 2.5-4 parts of polystyrene resin, 1-2 parts of polyvinylidene chloride, 0.1-1 part of black pigment, and 0.1-3 parts of color pigment into a resin master batch, and then mixing the resin master batch with the rest of polyethylene terephthalate, polystyrene resin, polyvinylidene chloride, and 0.1-0.6 part of total sodium allylsulfonate, 0.05-0.2 part of initiator, 0.2-0.6 part of antioxidant, 0.1-0.4 part of lubricant, 0.2-1 part of flame retardant, and 0-40 parts of filler, extruding or blow molding.
3. Plastic paper according to claim 1 or 2, characterized in that the colour pigments are selected from: 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.
4. Plastic paper according to claim 1 or 2, characterized in that the flame retardant is selected from: one or the combination of more than two of tributyl phosphate, tetrabromobisphenol A and tetrachlorobisphenol A.
5. A method of producing a laser colour markable plastic paper according to any of the claims 1 to 4 comprising the steps of:
(1) firstly, taking a small amount of polybutylene terephthalate resin, polystyrene resin, polyvinylidene chloride, black pigment and color pigment for melt mixing to prepare resin master batches, then putting the rest polybutylene terephthalate resin, polystyrene resin, polyvinylidene chloride, sodium allylsulfonate, initiator and resin master batches into a high-speed mixer for uniform mixing, then adding an antioxidant, a lubricant and a flame retardant, and continuously mixing until the mixture is uniform;
(2) feeding the uniformly mixed materials into a double-screw extruder for extrusion, adding a filler into the middle part of the extruder, wherein the processing temperature of the extruder is 210-250 ℃, and the rotating speed of a main machine is 300-600 revolutions per minute;
(3) cooling by an ultra-cold roller;
(4) and carrying out laser marking on the plastic paper prepared in the step.
6. The method according to claim 5, wherein the laser for laser marking in the step (4) is selected from the group consisting of: CO 22Laser marking machine, semiconductor laser marking machine, fiber laser marking machine or Nd-YAG laser.
7. The method of claim 6, wherein the laser is selected from the group consisting of CO2The laser marking machine has pulse repetition frequency of 30-50KHz, pulse width of 0.5-1.5us, marking speed of 20-30mm/s and marking current of 8-12A.
8. Use of a laser colour markable plastic paper according to any of the claims 1 to 4 for the packaging of articles containing structures with poor light stability which need to be stored protected from light.
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| CN201811241440.0A CN109486128B (en) | 2018-10-24 | 2018-10-24 | Plastic paper capable of being marked with laser color |
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| CN101125517A (en) * | 2007-09-24 | 2008-02-20 | 方培基 | Self-service printing material and its preparation method and application |
| CN102666117A (en) * | 2009-12-18 | 2012-09-12 | 爱克发-格法特公司 | Laser markable security film |
| CN104448531A (en) * | 2014-12-29 | 2015-03-25 | 金发科技股份有限公司 | Laser etching master batch for light color identification, preparation method thereof and application |
| CN106589450A (en) * | 2016-11-25 | 2017-04-26 | 四川大学 | Application of barium titanate with specific crystal form serving as additive in preparation of laser markable polymeric material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101125517A (en) * | 2007-09-24 | 2008-02-20 | 方培基 | Self-service printing material and its preparation method and application |
| CN102666117A (en) * | 2009-12-18 | 2012-09-12 | 爱克发-格法特公司 | Laser markable security film |
| CN104448531A (en) * | 2014-12-29 | 2015-03-25 | 金发科技股份有限公司 | Laser etching master batch for light color identification, preparation method thereof and application |
| CN106589450A (en) * | 2016-11-25 | 2017-04-26 | 四川大学 | Application of barium titanate with specific crystal form serving as additive in preparation of laser markable polymeric material |
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