CN112719608A - Compound capable of laser engraving red marks and preparation method thereof - Google Patents
Compound capable of laser engraving red marks and preparation method thereof Download PDFInfo
- Publication number
- CN112719608A CN112719608A CN202011495041.4A CN202011495041A CN112719608A CN 112719608 A CN112719608 A CN 112719608A CN 202011495041 A CN202011495041 A CN 202011495041A CN 112719608 A CN112719608 A CN 112719608A
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- Prior art keywords
- laser
- red
- compound
- laser engraving
- compound capable
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- 238000010147 laser engraving Methods 0.000 title claims abstract description 20
- 150000001875 compounds Chemical class 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 6
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 claims description 22
- 239000003550 marker Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 229920006112 polar polymer Polymers 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 3
- XXLJGBGJDROPKW-UHFFFAOYSA-N antimony;oxotin Chemical compound [Sb].[Sn]=O XXLJGBGJDROPKW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000004033 plastic Substances 0.000 abstract description 16
- 239000000049 pigment Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012545 processing Methods 0.000 description 5
- 238000010329 laser etching Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229920005669 high impact polystyrene Polymers 0.000 description 3
- 239000004797 high-impact polystyrene Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000005284 excitation Effects 0.000 description 2
- 238000010330 laser marking Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007649 pad printing Methods 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- SKRWFPLZQAAQSU-UHFFFAOYSA-N stibanylidynetin;hydrate Chemical compound O.[Sn].[Sb] SKRWFPLZQAAQSU-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- B23K26/70—Auxiliary operations or equipment
- B23K26/702—Auxiliary equipment
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2258—Oxides; Hydroxides of metals of tungsten
Abstract
The invention relates to a compound capable of laser-engraving red marks and a preparation method thereof. The invention can form red marks on the surface of the plastic product by laser engraving without adding any toner or pigment, has bright and clear color and high cost performance, and has good market application prospect.
Description
Technical Field
The invention belongs to the technical field of plastic surface processing, and particularly relates to a compound capable of laser engraving red marks and a preparation method thereof.
Background
With the continuous improvement of living standard and environmental awareness, people pay more and more attention to the quality of plastic products, so that the pollution of the plastic products to the environment is required to be reduced, and the appearance quality of the plastic products is also paid more and more attention. In order to improve the popularity of products and promote brand promotion, many brand manufacturers need to mark information such as production date, logo, company name, serial number and the like with clear and beautiful appearance on the appearance surface of plastic products. The traditional surface treatment process of plastic products comprises silk screen printing, pad printing, hot stamping, water transfer printing, oil spraying, electroplating and the like, although the processing modes have a long history in the current plastic processing and manufacturing, in some products with long contact, the mark is easy to wear, meanwhile, certain pollution is caused to the environment, and the cost is relatively high. Therefore, the laser carving mode is adopted for the surface processing of the plastic products, and the laser carving mode is characterized by non-contact processing, no pollution, high operation precision, high marking speed and capability of marking on the surface with an irregular shape.
The traditional plastic marks generally only can realize the laser engraving of black marks with white ground color or the laser engraving of white marks with black ground color, and some researches can realize the laser engraving of color marks at present, for example, CN110387104A provides a color frosted effect which is realized by adding flatting agents and organic toner to the surface of a plastic product under the laser pulse; CN106566068A provides a method for generating color on the surface of a plastic product under laser pulse by adding a temperature-sensitive substance, a pearlescent pigment and a laser-sensitive pigment, which all need to add extra toner or pigment to laser engrave the plastic product with color effect.
Disclosure of Invention
The invention aims to solve the technical problem of providing a compound capable of laser engraving red marks and a preparation method thereof, wherein the compound can form the red marks on the surfaces of plastic products through laser engraving without adding any toner or pigment, and has bright and clear color, high cost performance and good market application prospect.
The invention provides a compound capable of being radium-carved with red marks, which comprises the following components in parts by weight:
100 parts of polar polymer;
0.1-3 parts of phenolphthalein;
0.1-3 parts of marking agent.
The polar polymer is ABS or ASA. The polymer needs to have certain polarity, and the nonpolar PP or HIPS polymer cannot realize the radium carving red effect.
The marking agent is at least one of porous carbon black, tungsten oxide, indium tin oxide and tin antimony oxide.
The weight parts of the phenolphthalein and the marking agent are the proportion of the mass of the polar polymer.
The invention also provides a preparation method of the compound capable of laser engraving red marks, which comprises the following steps:
premixing the raw materials according to the proportion, putting the raw materials into a double-screw extruder for melt extrusion granulation to obtain a compound capable of laser engraving red marks; wherein the extrusion temperature is 180-220 ℃, and the rotation speed is 300-500 r/min.
The premixing rotating speed is 100-200 r/min, and the premixing time is 3-5 min.
The invention also provides application of the compound capable of laser engraving red marks in laser engraving.
According to the invention, phenolphthalein is introduced into the composite, a certain interaction is generated between the polar polymer and the phenolphthalein, the phenolphthalein is converted to a quinoid structure under the excitation of laser energy, and simultaneously, the quinoid structure is fixed along with the cooling of the resin, so that a red color is displayed.
Advantageous effects
The invention can form red marks on the surface of the plastic product by laser engraving without adding any toner or pigment, has bright and clear color and high cost performance, and has good market application prospect.
Drawings
Fig. 1 is a laser etching identification picture of example 1.
Fig. 2 is a laser engraving identification picture of comparative example 1.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
(1) The raw materials used
A. Polymer (b):
ABS: ABS HI-121H, Korean LG;
ASA: ASA LI912, korean LG;
PP: PP K8003, solitary petrochemicals;
HIPS: HIPS-622, shanghai seiki;
B.
phenolphthalein, Sigma-Aldrich;
C. marking agent:
porous carbon BLACK, DENKA BLACK, japan electrochemical industries co;
tungsten oxide, indium tin oxide, antimony tin oxide, kelling & Walker;
weighing the raw materials according to the weight parts shown in table 1, putting the raw materials into a mixer with the rotation speed of about 100 revolutions per minute for dry mixing for 3-5 minutes, then melting and extruding the mixed raw materials in a double-screw extruder with the length-diameter ratio of 40:1, the temperature interval of 160 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃ and the rotation speed of 450 revolutions per minute for granulation to obtain plastic particles, carrying out injection molding on the particles at about 200 ℃ to obtain a product, and carrying out laser marking by adopting a laser marking machine of a main-family EP-12 model under the conditions of 20A current, 1000mm/s marking speed and 17KH/Z frequency to obtain the laser carving marks with the effects shown in table 1.
TABLE 1 comparative examples, formulations of examples and laser engraving effect
As can be seen from comparative example 1 and examples 1 to 9, in the case of laser etching without adding phenolphthalein, ABS or ASA does not form a mark with a special color effect, but only forms a whitish layer on the surface; under the condition of adding phenolphthalein, marks with red effects can be formed on the surfaces of the ABS and ASA base materials under the excitation of laser, and the color is bright and beautiful. As can be seen from comparative example 2 and examples 1 to 3, when the phenolphthalein addition ratio was > 3, the color changed to dark brown after laser etching. As can be seen from comparative examples 3 to 4 and examples 2 and 4 to 5, when the marking agent is not added, the substrate cannot be laser-etched, and when the adding ratio of the marking agent is more than 3, the color of the substrate after laser etching is scorched and blackened, and the substrate is carbonized. As can be seen from comparative examples 6-9, no sign of red effect appeared after laser engraving for PP and HIPS substrates regardless of whether phenolphthalein was added or not.
Claims (6)
1. A compound capable of being laser-engraved with a red mark, which is characterized in that: the composition comprises the following components in parts by weight:
100 parts of polar polymer;
0.1-3 parts of phenolphthalein;
0.1-3 parts of marking agent.
2. The compound of claim 1, wherein: the polar polymer is ABS or ASA.
3. The compound of claim 1, wherein: the marking agent is at least one of porous carbon black, tungsten oxide, indium tin oxide and tin antimony oxide.
4. A method of preparing the laser engravable red marking compound of claim 1, comprising:
premixing the raw materials according to the proportion, putting the raw materials into a double-screw extruder for melt extrusion granulation to obtain a compound capable of laser engraving red marks; wherein the extrusion temperature is 180-220 ℃, and the rotation speed is 300-500 r/min.
5. The method of claim 4, wherein: the premixing rotating speed is 100-200 r/min, and the premixing time is 3-5 min.
6. Use of the laser engravable red marking compound of claim 1 in laser engraving.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011495041.4A CN112719608B (en) | 2020-12-17 | 2020-12-17 | Compound capable of carrying out laser carving to obtain red marks and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011495041.4A CN112719608B (en) | 2020-12-17 | 2020-12-17 | Compound capable of carrying out laser carving to obtain red marks and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112719608A true CN112719608A (en) | 2021-04-30 |
| CN112719608B CN112719608B (en) | 2023-11-24 |
Family
ID=75603919
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011495041.4A Active CN112719608B (en) | 2020-12-17 | 2020-12-17 | Compound capable of carrying out laser carving to obtain red marks and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112719608B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB212034A (en) * | 1923-01-17 | 1924-03-06 | Walter Albert Patrick | Improved manufacture of catalytic agents |
| US6460417B1 (en) * | 2001-08-24 | 2002-10-08 | General Electric Company | Formability testing of small-size coatings and materials |
| DE102006003608A1 (en) * | 2006-01-25 | 2007-09-06 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Process to recover high-purity silicon material from laser etching in polycrystalline form |
| WO2008042537A2 (en) * | 2006-10-04 | 2008-04-10 | General Electric Company | Optical article having a thermally responsive material as an anti-theft feature and a system and method for inhibiting theft of same |
| CN102168391A (en) * | 2011-02-17 | 2011-08-31 | 无锡侨颂特种纸有限公司 | Method for manufacturing chemical anti-counterfeiting paper |
| CN102227415A (en) * | 2008-09-29 | 2011-10-26 | 沙伯基础创新塑料知识产权有限公司 | Catalytic method for producing phenolphthalein compounds |
| CN105330898A (en) * | 2015-12-08 | 2016-02-17 | 四川大学 | Laser marker additive and preparation method and application thereof |
| CN206421122U (en) * | 2017-01-10 | 2017-08-18 | 昆山龙腾光电有限公司 | Board unit and liquid crystal display device |
| CN109651587A (en) * | 2018-12-07 | 2019-04-19 | 南京工程学院 | It is a kind of to derive material resources mutagens color high molecular material and preparation method thereof containing phenolphthalein with fast self-recovery property |
| CN109810409A (en) * | 2019-01-24 | 2019-05-28 | 江南大学 | It is a kind of can laser red-label polymer composition and be blended forming method |
-
2020
- 2020-12-17 CN CN202011495041.4A patent/CN112719608B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB212034A (en) * | 1923-01-17 | 1924-03-06 | Walter Albert Patrick | Improved manufacture of catalytic agents |
| US6460417B1 (en) * | 2001-08-24 | 2002-10-08 | General Electric Company | Formability testing of small-size coatings and materials |
| DE102006003608A1 (en) * | 2006-01-25 | 2007-09-06 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Process to recover high-purity silicon material from laser etching in polycrystalline form |
| WO2008042537A2 (en) * | 2006-10-04 | 2008-04-10 | General Electric Company | Optical article having a thermally responsive material as an anti-theft feature and a system and method for inhibiting theft of same |
| CN102227415A (en) * | 2008-09-29 | 2011-10-26 | 沙伯基础创新塑料知识产权有限公司 | Catalytic method for producing phenolphthalein compounds |
| CN102168391A (en) * | 2011-02-17 | 2011-08-31 | 无锡侨颂特种纸有限公司 | Method for manufacturing chemical anti-counterfeiting paper |
| CN105330898A (en) * | 2015-12-08 | 2016-02-17 | 四川大学 | Laser marker additive and preparation method and application thereof |
| CN206421122U (en) * | 2017-01-10 | 2017-08-18 | 昆山龙腾光电有限公司 | Board unit and liquid crystal display device |
| CN109651587A (en) * | 2018-12-07 | 2019-04-19 | 南京工程学院 | It is a kind of to derive material resources mutagens color high molecular material and preparation method thereof containing phenolphthalein with fast self-recovery property |
| CN109810409A (en) * | 2019-01-24 | 2019-05-28 | 江南大学 | It is a kind of can laser red-label polymer composition and be blended forming method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112719608B (en) | 2023-11-24 |
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