CN112266545A - Anti-yellowing laser etching identification composition - Google Patents
Anti-yellowing laser etching identification composition Download PDFInfo
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- CN112266545A CN112266545A CN202011124361.9A CN202011124361A CN112266545A CN 112266545 A CN112266545 A CN 112266545A CN 202011124361 A CN202011124361 A CN 202011124361A CN 112266545 A CN112266545 A CN 112266545A
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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
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
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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
- 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
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2272—Ferric oxide (Fe2O3)
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- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
Abstract
The invention relates to a yellowing-resistant laser carving identification composition which comprises a polymer, a filling type toughening agent and a laser marking agent. According to the yellowing-resistant laser carving mark composition, the white laser mark prepared by using the material has better durability, and the yellowing resistance of the white laser mark is greatly improved.
Description
Technical Field
The invention belongs to the field of plastic laser etching, and particularly relates to a yellowing-resistant laser etching identification composition.
Background
Laser engraving, as a process for processing patterns on the surface of plastic products, is gradually widely used due to the advantages of high marking speed, clear marked patterns and characters, non-contact processing, no material consumption, no environmental pollution, easy automation and the like. The plastic laser engraving can generally realize black-to-white, white-to-black, color-to-black and the like, and has no special requirements on plastic substrates. However, when the laser marking patterns are carried out on the surfaces of ABS and HIPS products, particularly when black is printed to be white, the white patterns formed after laser etching are easily changed from white to yellow after being irradiated for a period of time, and the pattern marks on the surfaces of plastic products are yellowed, so that the appearance of the products is seriously influenced, and the application of the products is limited.
CN105131564A discloses a method for manufacturing a body-building equipment encapsulating layer LOGO, an encapsulating material and laser engraving equipment, wherein weather resistance is improved by containing weather resistant agent in the components, but white marks are the colors displayed by plastic foaming, the problem that the weather resistant agent cannot improve the light yellowing of the white marks due to the particularity of the white marks is solved, and related reports for improving the white laser engraving marks are also rarely reported at present.
Disclosure of Invention
The invention aims to solve the technical problem of providing a yellowing-resistant laser engraving identification composition, and overcomes the technical defect of light yellowing of white laser patterns of ABS and HIPS in the prior art.
The invention relates to a laser etching identification composition, which comprises the following raw material components in parts by weight:
100 parts of a polymer, namely the polypropylene resin,
15-40 parts of a filling type toughening agent,
and 0.1-3 parts of laser marking agent.
The polymer is styrene-acrylonitrile copolymer or polystyrene.
The filling type toughening agent is a filling filled styrene-butadiene-acrylonitrile copolymer or a filling filled styrene-butadiene copolymer.
The filler is one or more of calcium carbonate, silicon micropowder, calcium hydroxide, magnesium hydroxide, antimony oxide, silicon oxide and iron oxide.
The filling type toughening agent has a sea-island structure, wherein an island region is a filler, and a sea region is a styrene-butadiene-acrylonitrile copolymer or a styrene-butadiene copolymer.
The filling type toughening agent contains 5-10 wt% of filler.
The filling toughening agent is prepared from styrene, butadiene and acrylonitrile or a copolymer formed by styrene and butadiene by a nano particle in-situ emulsion polymerization-grafting method or a nano particle in-situ suspension polymerization-grafting method or a nano particle in-situ continuous bulk method.
The laser marking agent is one or more of carbon black, antimony oxide, zinc antimonide, aluminum antimonide and nickel antimonide.
The invention relates to a laser etching mark based on the composition.
The invention discloses a method for preparing a laser etching mark, which comprises the following steps:
the preparation method comprises the steps of putting 100 parts by weight of polymer, 15-40 parts by weight of filling type toughening agent and 0.1-3 parts by weight of laser marking agent into a mixer with the rotating speed of about 100 revolutions per minute for dry mixing for 3-5 minutes, then carrying out melt extrusion granulation on the mixed raw materials in a double-screw extruder with the rotating speed of 300-500 revolutions per minute at the temperature of 180-220 ℃ to obtain plastic particles, carrying out injection molding on the particles at the temperature of about 200 ℃ to obtain a product, and then carrying out laser marking by adopting a laser marking machine of a main laser EP-12 model under the conditions of 20A current, 1000mm/s marking speed and 17KH/Z frequency to obtain white laser carved patterns.
The invention relates to application of a laser etching mark.
In the invention, when white laser marking is carried out on the surface of the black base material, the laser marking agent is vaporized, the polymer is migrated to the surface to be foamed to form a white mark under the vaporization effect, and the filling type toughening agent is difficult to migrate to the surface to be foamed. Therefore, the formed white mark is mainly styrene-acrylonitrile copolymer or polystyrene and does not contain double bonds, and the color durability of the white mark is greatly improved.
Advantageous effects
(1) According to the invention, the white pattern can be carved out from the black plastic material through laser, the white pattern is resistant to illumination and yellowing and is not easy to change color, and the color durability of the mark is improved;
(2) the invention does not need to add weather resisting agent, the cost performance is high;
(3) according to the yellowing-resistant laser carving mark composition, the white laser mark prepared by using the material has better durability, and the yellowing resistance of the white laser mark is greatly improved.
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) And (3) performance testing:
the standard sample with the white mark was subjected to xenon lamp aging test according to GB/T16422.2-2014, method A cycle 2, and the white mark b value was measured to characterize the yellowing result, as shown in the table.
(2) Raw materials
A. Polymer (b):
a-1: styrene-acrylonitrile copolymer, SAN-2437, medium petroleum chemicals;
a-2: polystyrene, GPPS 123P, shanghai seideae;
B. a toughening agent:
b-1: styrene-butadiene-acrylonitrile copolymer, HR181 POWER, korea brocade lake;
b-2: styrene-butadiene copolymer, HIPS-POWER, a continuous bulk synthesis process product, shanghai seiki;
b-3: calcium carbonate filled styrene-butadiene-acrylonitrile copolymer, the weight percentage of the filler used in the examples is 6%; comparative example 3 the filler weight percentage content is 3%; comparative example 4a 15% filler weight percentage was used;
b-4: iron oxide filled styrene-butadiene-acrylonitrile copolymer, the weight percentage content of the filler is 8%;
b-5: a silica-filled styrene-butadiene copolymer having a filler content of 10% by weight;
b-6: antimony oxide filled styrene-butadiene copolymer, the filler weight percentage content is 5%;
b-3, B-4, B-5 and B-6 are nano composite copolymers formed by adopting styrene, butadiene and acrylonitrile or styrene and butadiene, and the filling toughening agent can be prepared by adopting a nano particle in-situ emulsion polymerization-grafting method or a nano particle in-situ suspension polymerization-grafting method or a nano particle in-situ continuous bulk method, the preparation method and the molecular structure are conventional technical schemes in the field, and the final performance effect is not influenced by the preparation method;
C. laser marking agent:
c-1: carbon BLACK, DENKA BLACK, japan electrical chemical industries co;
c-2: antimony oxide, modified antimony oxide ATO, Keeling & Walker;
c-3: nickel antimonide, modified antimony oxide ATO, Keeling & Walker;
examples 1 to 10
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 then 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 radium/Z frequency to obtain white carved patterns.
Comparative examples 1 to 4
The raw materials were weighed according to the weight parts shown in table 2, and the specific preparation process was the same as in the above examples.
Table 1 shows the aging properties of the raw materials and the materials obtained in the examples.
Table 2 shows the raw material components used in the comparative examples and the aging properties of the finally obtained materials:
as can be seen from the results of the xenon lamp aging tests of examples 1-10 and comparative examples 1-3, the filled tougheners used in the present invention can effectively improve the yellowing resistance of white laser marks. The material of the non-filling type toughening agent is adopted, and after laser etching, the xenon lamp aging result b value of a white mark after 200 hours is more than 20, and the xenon lamp is seriously yellowed; by adopting the filling type toughening agent, the xenon lamp aging result b value of the white mark after 200h is under 10, the excellent yellowing resistance is shown, the white mark is more durable, and the service life is longer.
Example 2 used a filled toughener with a filler weight content of 6%; comparative example 3 used a filled toughener with a filler weight content of 3%; comparative example 4 used a filled toughener with a filler weight content of 15%. In the comparative example 3, as the filler is less, the b value of the white mark is increased from 6 to 22 after 200h of xenon lamp aging, and severe yellowing occurs; comparative example 4 has a large amount of filler, and the mark is scorched and cannot exhibit a black and white marking effect due to carbonization during laser marking.
Claims (10)
1. The laser etching identification composition comprises the following raw materials in parts by weight:
100 parts of a polymer, namely the polypropylene resin,
15-40 parts of a filling type toughening agent,
and 0.1-3 parts of laser marking agent.
2. The composition of claim 1, wherein the polymer is a styrene-acrylonitrile copolymer or polystyrene.
3. The composition of claim 1, wherein the filled toughener is a filler filled styrene-butadiene-acrylonitrile copolymer or a filler filled styrene-butadiene copolymer.
4. The composition of claim 3, wherein the filler is one or more of calcium carbonate, silicon micropowder, calcium hydroxide, magnesium hydroxide, antimony oxide, silicon oxide and iron oxide.
5. The composition of claim 1, wherein the filled toughener has a sea-island structure, wherein the island regions are filler and the sea regions are styrene-butadiene-acrylonitrile copolymer and/or styrene-butadiene copolymer.
6. The composition of claim 1, wherein the filled toughener has a filler weight percentage of 5% to 10%.
7. The composition of claim 1, wherein the laser marking agent is one or more of carbon black, antimony oxide, zinc antimonide, aluminum antimonide and nickel antimonide.
8. A laser engraved marking based on the composition of claim 1.
9. A preparation method of a laser etching mark comprises the following steps:
according to the weight parts, 100 parts of polymer, 15-40 parts of filling type toughening agent and 0.1-3 parts of laser marking agent are uniformly premixed, and then are melted, extruded and granulated, molded and marked by laser.
10. Use of the laser engraved mark of claim 8.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011124361.9A CN112266545B (en) | 2020-10-20 | 2020-10-20 | Composition of yellowing-resistant laser engraving mark |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011124361.9A CN112266545B (en) | 2020-10-20 | 2020-10-20 | Composition of yellowing-resistant laser engraving mark |
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| CN112266545A true CN112266545A (en) | 2021-01-26 |
| CN112266545B CN112266545B (en) | 2023-10-13 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109401160A (en) * | 2018-11-30 | 2019-03-01 | 广东威林工程塑料股份有限公司 | Wide-angle curved transparent is without scratch AS alloy laser engraving material and preparation method thereof |
| CN110408165A (en) * | 2019-08-09 | 2019-11-05 | 四川大学 | A kind of discoloration auxiliary agent and preparation method thereof for manufacturing white or light-colored label |
| CN110511526A (en) * | 2019-08-23 | 2019-11-29 | 江苏金发科技新材料有限公司 | It is a kind of can low temperature laser carving multiple color compound and preparation method thereof |
-
2020
- 2020-10-20 CN CN202011124361.9A patent/CN112266545B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109401160A (en) * | 2018-11-30 | 2019-03-01 | 广东威林工程塑料股份有限公司 | Wide-angle curved transparent is without scratch AS alloy laser engraving material and preparation method thereof |
| CN110408165A (en) * | 2019-08-09 | 2019-11-05 | 四川大学 | A kind of discoloration auxiliary agent and preparation method thereof for manufacturing white or light-colored label |
| CN110511526A (en) * | 2019-08-23 | 2019-11-29 | 江苏金发科技新材料有限公司 | It is a kind of can low temperature laser carving multiple color compound and preparation method thereof |
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| CN112266545B (en) | 2023-10-13 |
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