CN109796678B - Temperature-sensitive substance-containing polymer composition capable of being marked by laser color and preparation method thereof - Google Patents
Temperature-sensitive substance-containing polymer composition capable of being marked by laser color and preparation method thereof Download PDFInfo
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- CN109796678B CN109796678B CN201910066087.5A CN201910066087A CN109796678B CN 109796678 B CN109796678 B CN 109796678B CN 201910066087 A CN201910066087 A CN 201910066087A CN 109796678 B CN109796678 B CN 109796678B
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Abstract
The invention provides a temperature-sensitive substance-containing polymer composition capable of being color-marked by laser and a preparation method thereof, belonging to the field of high polymer materials. The polymer composition components include: the polymer is 100 parts by weight, and the content of the laser absorbent is 0.05-5 parts by weight; the content of the temperature-sensitive substance is 0.1-10 parts by weight; the method comprises the following steps: and melting and blending the components of the high molecular polymer, the laser marking powder and the temperature sensing substance according to the component ratio. The invention adds the temperature-sensitive substance, and utilizes the heat generated in the laser marking process to ensure that the temperature-sensitive substance generates reactions such as thermal decomposition, oxidation and the like at a certain temperature. These reactions destroy the original material structure or produce a new material, while producing a new color.
Description
Technical Field
The invention relates to a temperature-sensitive substance-containing polymer composition capable of being subjected to laser color marking and a preparation method thereof, belongs to the field of high polymer materials, and particularly relates to a polymer composition capable of being subjected to laser color marking and a preparation method thereof.
Background
With the development of the times, the laser marking technology has become an effective marking processing method increasingly, and is applied to various industries more and more widely. The superiority of the application of the laser marking technology is increasingly and clearly shown in people, various characters, symbols, patterns and the like can be marked, the size of the characters can be from millimeter to micron, and the laser marking technology has special significance for the anti-counterfeiting of products.
The application of laser marking technology in domestic and foreign industries is being gradually emphasized by people, and various novel marking systems come out endlessly, and replace the traditional marking method with the unique advantages. The technology has been taken as the process standard of industrial processing in some developed countries internationally, China also pays great attention to the technology, and the technology has been classified as 'eight-five torch plan' by the national academy of sciences for research and popularization. At present, the method draws more and more attention of manufacturers in China, and can replace the traditional marking process to inject new vitality into product production. Therefore, the laser marking has huge development potential and wide market prospect.
The problem of color selectivity of laser marked characters and patterns is also gradually paid attention to by users, and becomes one of the most important technical indexes in the market competition of various manufacturers for producing laser marking machines. At present, color marking on plastic substrates is difficult, and how to obtain color marks and apply the color marks to beautify and decorate is a challenge in future work. Therefore, the laser color marking technology is an innovative technology and is bound to be widely applied in the future market. The patent CN 106566068A adopts laser marking powder, temperature-sensitive substances and polymers to blend to prepare a composition capable of laser color marking, but specific laser marking powder needs to be added to the composition to achieve laser marking color. This application uses the low price base member material as laser absorbent, need not to add extra laser marking powder, only needs to form laser marking after it blends with colorant, polymer, and is simple convenient, low cost.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a polymer composition containing a temperature-sensitive substance and capable of being marked by laser color and a preparation method thereof. The composition can be used for forming a color mark on the surface of a substrate by using a laser, so that the mark and the background have higher contrast.
The technical scheme of the invention is as follows:
a laser-markable polymer composition containing a temperature-sensitive substance, which comprises a radiation-and temperature-sensitive substance capable of causing a color change, a laser absorber, and a high-molecular polymer.
The composition for color laser marking includes a substance that undergoes a color change at a certain temperature, the color change being unidirectional, irreversible, and the primary color cannot be restored after cooling.
The content of the laser absorber is 0.05-5 parts by weight, preferably 0.5-2 parts by weight, based on 100 parts by weight of the high molecular polymer; the content of the temperature sensitive substance is 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight.
The finished product is marked by laser to contain various colors such as white, black, green, yellow, blue, red and the like.
The temperature-sensitive substances include two main types of organic substances and inorganic substances, and the irreversible temperature-sensitive substances are commonly used for phosphate, sulfate, nitrate, oxide, sulfide, azo pigment, aryl methane pigment, methyl violet, phenol compound, acid clay and the like of lead, nickel, chromium, zinc, cobalt, iron, cadmium, strontium, magnesium, barium, molybdenum, manganese and the like.
Further, the temperature-sensitive substance is cadmium carbonate, cadmium sulfide, ferric sulfate, copper oxide, iron carbonate, fuchsin, pigment blue 61, pigment violet 3, methyl violet, crystal violet, basic sophorae yellow, pigment yellow (93, 95), pigment red (144, 166, 214, 242, 262, BR), pigment brown (23, 41), permanent orange RN, permanent purplish red KRR, naphthol AS-D, permanent yellow GG, fast yellow G, lisolor fast yellow 3GD, pigment red BR, permanent yellow 3R, fast yellow R, permanent red BLC, or phthalocyanine pigment.
The high molecular polymer is one or more of polyethylene, polypropylene, high-density polyethylene, polyisobutylene, polystyrene, polyvinyl chloride, polymethyl methacrylate, polycarbonate, polyamide, polyester, polyphenyl ether, polyurethane, nylon 66 and ABS copolymer.
The temperature-sensitive substance has a color change in the range of 100 ℃ to 550 ℃. The color change principle is that the reaction such as thermal decomposition, oxidation and the like is generated at a certain temperature. These reactions destroy the original material structure or produce a new material, while producing a new color.
The laser used to laser mark the polymer composition of the present invention may be CO2Laser (wavelength 10600nm), Nd: YAG laser (wavelength 1064nm and 532nm), pulsed UV laser (excimer laser), and the like.
The laser absorbent has the main functions of absorbing laser energy, converting the laser beam into heat energy, and generating heating action, carbonization action, evaporation action and chemical reaction on plastics. Comprises one or more than two of carbon black, melanin, black iron oxide, titanium black, zinc powder, starch and boron nitride.
The polymer composition is added with an auxiliary agent according to actual requirements, and the auxiliary agent is a lubricant or an antioxidant.
A preparation method of a polymer composition containing a temperature-sensitive substance and capable of being marked by laser colors is specifically characterized in that the polymer composition is prepared by melting and blending a high molecular polymer, a laser absorber and the temperature-sensitive substance according to the component proportion.
In the preparation of the polymer composition of the present invention, the melt blending temperature of the materials is the blending temperature used in the processing of the conventional polymer materials, and can be determined according to the melt temperature of the polymer. The blending equipment for mixing the materials in the preparation method of the present invention can adopt various mixing equipment used in the prior art, such as a stirrer, a kneader and the like.
The melt blending equipment used in the preparation method is general blending equipment in the plastic processing industry, and can be a double-screw extruder, a single-screw extruder, an open mill or an internal mixer and the like.
A laser marking method of a polymer composition containing temperature-sensitive substances and capable of laser color marking comprises the following specific processes: mixing the high molecular polymer, the laser absorbent and the temperature-sensitive substance uniformly in a high-speed mixer; melting and extruding the mixture in a double-screw extruder, and cooling and pelletizing; drying the obtained granules at 90 ℃ for 12h, performing injection molding at 180-260 ℃, preparing standard sample strips according to requirements, and performing laser marking.
The mark can be characterized by visually judging whether the lines of the character mark are smooth and clear or not and whether the surface of a large area is flat or not.
The invention has the beneficial effects that: the preparation method provided by the invention is simple and reliable in process, and can be applied to polymer products needing to be marked in almost all industrial departments. For example, it is necessary to note a production date, a valid date, a bar code, a company trademark, a serial number, and the like on the article.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1:
for polypropylene resins: 100 parts by mass of polypropylene resin, 0.05 part by mass of black iron oxide serving as a laser absorber and 0.1 part by mass of temperature-sensitive pigment blue (61) are placed in a stirrer to be uniformly mixed, then the mixture is added into a double-screw extruder to be subjected to melt blending, and extrusion granulation is carried out, wherein the extrusion temperature is 160-220 ℃, and the screw rotation speed is 300 rpm. And drying the extruded material particles in a 90 ℃ oven for 12 hours, then injecting the dried material particles into a standard sample strip at 160-220 ℃ and carrying out a laser marking test.
Example 2:
for polyethylene resins: 100 parts by mass of polyethylene resin, 0.3 part by mass of laser absorber melanin and 1 part by mass of temperature-sensitive material pigment red (144) are placed in a stirrer to be uniformly mixed, then the mixture is added into a double-screw extruder to be subjected to melt blending, and extrusion granulation is carried out, wherein the extrusion temperature is 160-220 ℃, and the screw rotation speed is 300 rpm. And drying the extruded material particles in a 90 ℃ oven for 12 hours, then injecting the dried material particles into a standard sample strip at 160-220 ℃ and carrying out a laser marking test.
Example 3:
for ABS resins: 100 parts by mass of ABS resin, 2 parts by mass of laser absorbent starch and 4 parts by mass of temperature-sensitive material crystal violet are placed in a stirrer to be uniformly mixed, then the mixture is added into a double-screw extruder to be subjected to melt blending, and extrusion granulation is carried out, wherein the extrusion temperature is 160-220 ℃, and the screw rotation speed is 300 rpm. And drying the extruded material particles in a 90 ℃ oven for 12 hours, then injecting the dried material particles into a standard sample strip at 160-220 ℃ and carrying out a laser marking test.
Example 4:
for polystyrene resins: 100 parts by mass of polystyrene resin, 5 parts by mass of laser absorbent boron nitride and 10 parts by mass of temperature-sensitive material permanent yellow 3R are placed in a stirrer to be uniformly mixed, then the mixture is added into a double-screw extruder to be subjected to melt blending, and extrusion granulation is carried out, wherein the extrusion temperature is 160-220 ℃, and the screw rotation speed is 300 rpm. And drying the extruded material particles in a 90 ℃ oven for 12 hours, then injecting the dried material particles into a standard sample strip at 160-220 ℃ and carrying out a laser marking test.
Example 5:
for polycarbonate resins: 100 parts by weight of polycarbonate resin, 3 parts by weight of laser absorbent melanin and 8 parts by weight of temperature-sensitive substance phthalocyanine green 3G are placed in a stirrer to be uniformly mixed, then the mixture is added into a double-screw extruder to be subjected to melt blending, and extrusion granulation is carried out, wherein the extrusion temperature is 160-220 ℃, and the screw rotation speed is 300 rpm. And drying the extruded material particles in a 90 ℃ oven for 12 hours, then injecting the dried material particles into a standard sample strip at 160-220 ℃ and carrying out a laser marking test.
Example 6:
for high density polyethylene resins: 100 parts by weight of high-density polyethylene resin, 0.1 part by weight of laser absorbent boron nitride and 2 parts by weight of temperature-sensitive material permanent orange RN are placed in a stirrer to be uniformly mixed, then the mixture is added into a double-screw extruder to be subjected to melt blending, and extrusion granulation is carried out, wherein the extrusion temperature is 160-220 ℃, and the screw rotation speed is 300 rpm. And drying the extruded material particles in a 90 ℃ oven for 12 hours, then injecting the dried material particles into a standard sample strip at 160-220 ℃ and carrying out a laser marking test.
Example 7:
for polypropylene resins: 100 parts by mass of polypropylene resin, 1 part by mass of laser absorber melanin and 5 parts by mass of temperature-sensitive material pigment brown (23) are placed in a stirrer to be uniformly mixed, then the mixture is added into a double-screw extruder to be subjected to melt blending, and extrusion granulation is carried out, wherein the extrusion temperature is 160-220 ℃, and the screw rotation speed is 300 rpm. And drying the extruded material particles in a 90 ℃ oven for 12 hours, then injecting the dried material particles into a standard sample strip at 160-220 ℃ and carrying out a laser marking test.
Comparative examples 1 to 2:
the conditions were the same as in the previous examples except that the temperature sensitive substance was not heated. The specific formula is shown in table 1, wherein the content of each component is calculated by weight portion. The laser marking effect is shown in table 1.
Comparative example 3:
for polypropylene resins: 100 parts by mass of polypropylene resin and 0.1 part by mass of temperature-sensitive substance pigment blue (61) are placed in a stirrer to be uniformly mixed, then the mixture is added into a double-screw extruder to be subjected to melt blending, and extrusion granulation is carried out, wherein the extrusion temperature is 160-220 ℃, and the screw rotation speed is 300 rpm. And drying the extruded material particles in a 90 ℃ oven for 12 hours, then injecting the dried material particles into a standard sample strip at 160-220 ℃ and carrying out a laser marking test. The laser marking effect is shown in table 1.
TABLE 1
The comparative examples 1 and 2 are not added with temperature-sensitive substances, and after marking, the marking color is white, so that a color mark cannot be formed; in comparative example 3, no laser absorber was added and laser marking was not possible. In examples 1 to 7, the addition of the temperature sensitive substance and the laser absorber together gave excellent color laser marking effects.
Claims (6)
1. A polymer composition containing a temperature-sensitive substance capable of laser color marking, which is characterized by consisting of a temperature-sensitive substance which can cause color change and is sensitive to radiation and temperature, a laser absorber and a high molecular polymer;
the content of the laser absorber is 0.05-5 parts by weight based on 100 parts by weight of the high molecular polymer; the content of the temperature-sensitive substance is 0.1-10 parts by weight;
the laser absorbent is starch or boron nitride;
when the laser absorbent is starch, the temperature-sensitive substances are crystal violet, fuchsine, pigment violet 3, methyl violet, alkaline pagodatree yellow, pigment yellow 93, sun-proof yellow G and permanent yellow GG;
when the laser absorbent is boron nitride, the temperature-sensitive substances are permanent orange RN or permanent yellow 3R, pigment red 144, pigment red 166, pigment red 214, pigment red 242, color brown 23, color brown 41, naphthol AS-D and phthalocyanine pigments;
the high molecular polymer is one or more of polyethylene, polypropylene, polyisobutylene, polystyrene, polyvinyl chloride, polymethyl methacrylate, polycarbonate, polyamide, polyester, polyphenyl ether, polyurethane and ABS copolymer.
2. The laser-markable polymer composition containing a temperature-sensitive substance according to claim 1, wherein the laser absorber is contained in an amount of 0.5 to 2 parts by weight; the content of the temperature-sensitive substance is 1 to 5 parts by weight.
3. The laser color markable polymer composition containing a temperature sensitive substance according to claim 1 wherein an auxiliary agent is added to the polymer composition according to actual requirements, the auxiliary agent being a lubricant or an antioxidant.
4. The laser color markable polymer composition containing a temperature sensitive substance according to claim 2 wherein an auxiliary agent is added to the polymer composition according to actual requirements, the auxiliary agent being a lubricant or an antioxidant.
5. The method for preparing the polymer composition containing the temperature-sensitive substance and capable of being color-marked by the laser as claimed in claim 1, wherein the temperature-sensitive substance is prepared by melt blending a high molecular polymer, a laser absorber and the temperature-sensitive substance according to the component proportions.
6. The laser marking method of the thermo-sensitive substance laser color markable polymer composition according to claim 1, characterized in that the specific process is as follows: mixing the high molecular polymer, the laser absorbent and the temperature-sensitive substance uniformly in a high-speed mixer; melting and extruding the mixture in a double-screw extruder, and cooling and pelletizing; drying the obtained granules at 90 ℃ for 12h, performing injection molding at 180-260 ℃, preparing standard sample strips according to requirements, and performing laser marking.
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| CN110483891A (en) * | 2019-08-23 | 2019-11-22 | 江苏金发科技新材料有限公司 | A kind of preparation method of plastic surface dimpled grain reason |
| CN110527238A (en) * | 2019-08-23 | 2019-12-03 | 上海金发科技发展有限公司 | A kind of preparation method with bubble effect dermatoglyph |
| CN110498947A (en) * | 2019-08-23 | 2019-11-26 | 上海金发科技发展有限公司 | A method of increasing surface of plastic product frictional force |
| CN110511526B (en) * | 2019-08-23 | 2021-05-28 | 江苏金发科技新材料有限公司 | Compound capable of achieving low-temperature laser etching of multiple colors and preparation method thereof |
| CN110551360B (en) * | 2019-08-23 | 2021-06-01 | 江苏金发科技新材料有限公司 | Composition for visually inspecting welding strength and preparation method thereof |
| CN110387104A (en) * | 2019-08-23 | 2019-10-29 | 上海金发科技发展有限公司 | A kind of preparation method with frosted finish effect dermatoglyph |
| CN112375347B (en) * | 2020-11-12 | 2023-04-18 | 江苏金发科技新材料有限公司 | Black PBT composition capable of laser marking blue fonts and preparation thereof |
| CN117186463A (en) * | 2023-11-08 | 2023-12-08 | 苏州大学 | Sulfur-based material-based laser high-sensitivity film, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TW314534B (en) * | 1993-09-01 | 1997-09-01 | Hoechst Ag | |
| CN101497287A (en) * | 2004-01-16 | 2009-08-05 | 大科能树脂有限公司 | Multi-color marking-carrying molding and laser marking method |
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| AU2004272303A1 (en) * | 2003-09-17 | 2005-03-24 | Luiva Mb Holdings Pty Ltd | Laser markable polymeric compositions |
| CN106566068A (en) * | 2016-10-19 | 2017-04-19 | 玫瑰塑胶(昆山)有限公司 | Composition capable of laser color marking and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW314534B (en) * | 1993-09-01 | 1997-09-01 | Hoechst Ag | |
| CN101497287A (en) * | 2004-01-16 | 2009-08-05 | 大科能树脂有限公司 | Multi-color marking-carrying molding and laser marking method |
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