CN112961484A

CN112961484A - Laser etching agent, laser etching polycarbonate, and preparation method and application thereof

Info

Publication number: CN112961484A
Application number: CN202110524891.0A
Authority: CN
Inventors: 罗伟; 张丛见; 任月璋
Original assignee: Suzhou Omay Optical Materials Co ltd
Current assignee: Suzhou Omay Optical Materials Co ltd
Priority date: 2021-05-14
Filing date: 2021-05-14
Publication date: 2021-06-15
Anticipated expiration: 2041-05-14
Also published as: CN112961484B

Abstract

The invention discloses a laser etching agent, laser etching polycarbonate, and a preparation method and application thereof. The laser etching agent consists of antimony-doped tin oxide and a laser marking plastic auxiliary agent, wherein the mass ratio of the antimony-doped tin oxide to the laser marking plastic auxiliary agent is (0.5-10) to (0.5-10), and the laser marking plastic auxiliary agent is Iriotec^®8825 and Iriotec^®8820. Laser made of the laser etching agent of the inventionWhen the etched polycarbonate is used for etching identification cards, the etched polycarbonate has clearer images and high resolution, is widely suitable for etching various safety cards such as identity cards and various credit cards, is environment-friendly and has the characteristic of permanent fastness.

Description

Laser etching agent, laser etching polycarbonate, and preparation method and application thereof

Technical Field

The invention relates to the technical field of laser etching, in particular to a laser etching agent, laser etching polycarbonate and a preparation method and application thereof.

Background

The laser etching technology is one of the largest application fields of laser processing, and the laser etching is an etching method which utilizes high-energy-density laser to locally irradiate a workpiece to enable a surface layer material to be vaporized or to generate a chemical reaction of color change, so that permanent etching is left. Various characters, symbols, patterns and the like can be printed by laser etching, the size of the characters can be from millimeter to micron, and the laser etching has special significance for the anti-counterfeiting of products.

The etching of products during laser etching has become an important process in the production process. The traditional etching methods such as thermal printing, stamping, carving and the like almost copy letters, symbols and decorations to the surface of a finished product. However, with the increasing demands on the apparent quality of the etching on the plastic, the etching speed, the adaptability, the ease of use and the cost control, there is a strong need for a better marking method, which is the case with the laser marking method.

Laser ink is the most common application of laser marking technology, and is currently used in a large number in the food packaging industry, but the method does not fully take advantage of laser etching, and etching should be generated on the surface or even inside the marked object (such as plastic) in order to make etching permanent and not worn. However, the development of laser-markable plastics is a challenge for many companies, since most plastics, such as polyolefins, cannot be etched or marked with a laser. If general plastics of any color can be etched by laser, the application of the laser etching technology of the plastics has a completely new prospect.

At present, with the development of society, security cards with identification functions, such as passports, identity cards, drivers licenses and the like, are widely used. In order to facilitate identity authentication, the existing security card is printed with image-text identity information of the owner of the card, so that the existing security card has certain anti-counterfeiting capability which is a basic requirement on modern security cards in order to prevent the identity information on the security card from being maliciously tampered.

In the prior art, when the security card is produced, portrait and character identity information of a user need to be etched on a PC (polycarbonate) substrate of an information surface of the security card in a laser etching mode; the substrate after laser etching is irreversibly chemically changed, so that personal information of a user can be effectively prevented from being tampered, and the method is simple in process and suitable for on-site decentralized certificate making. However, after laser etching, the black and white portrait of the user is generated in the identification card, so that the identification card image produced by the method is generated by laser etching components, and the definition and the resolution cannot meet the expected requirements when the current state relates to a face image.

CN106566068A discloses a composition capable of laser color marking and a preparation method thereof. The composition comprises the following components: 100 parts by weight of a polymer; the content of the laser marking powder is 0.05-2 parts by weight; the content of the temperature-sensitive substance is 0.1-10 parts by weight. The preparation method comprises the following steps: and melting and blending the components of the polymer, the laser marking powder and the temperature-sensitive substance according to the component ratio. The invention adds temperature-sensitive material, uses the heat generated in the laser marking process to make the temperature-sensitive material generate reactions such as thermal decomposition, oxidation and the like at a certain temperature, the reactions destroy the original material structure or generate a new material and generate a new color at the same time, the color change is unidirectional and irreversible, and the primary color can not be recovered after cooling, thereby forming stable permanent marks on the product.

CN110229507A discloses a laser-markable halogen-free flame-retardant polyamide composition and a preparation method thereof, comprising 47.4-78.8wt% of polyamide, 10-20wt% of halogen-free flame retardant, 10-30wt% of mineral filler, 1-3wt% of self-made laser additive, 0.1-0.3wt% of dispersant and 0.1-0.4wt% of antioxidant; the self-made laser additive is prepared by melting and blending a mixture of titanium dioxide, mica powder, nano tin antimony oxide and copper chromite according to the mass ratio of 10-10.4:2.5-7.2:1.4-1.5:1 through a screw extruder, and the obtained polyamide composition simultaneously meets the requirements of infrared laser and ultraviolet laser on clear dark marks and keeps better mechanical and electrical properties.

However, when the prepared laser-markable composition is used for card etching, a human face image generated by laser etching is not clear, and the effective resolution cannot be achieved.

CN109504053B discloses a polycarbonate laser etching film for smart cards and a preparation method thereof, wherein the film is prepared by an extrusion process according to the following formula, 100 parts of polycarbonate resin, 1-1.5 parts of chain extender, 1-3 parts of modified carbon nano tube, 1-2 parts of light stabilizer and 1-2 parts of antioxidant. The raw materials are uniformly mixed according to the proportion, the mixture is dried and then put into an extruder, and the melt is cooled and shaped through a filter, a melt pump, a die and a three-roller calender to prepare the polycarbonate laser etching film. The invention realizes the laser anti-counterfeiting function of the polycarbonate film by adopting the copolymerized polycarbonate as the main raw material and adding the modified carbon nano tube, and modifies the polycarbonate by adopting the chain extender, so that the polycarbonate has holographic anti-counterfeiting function. Also, the resolution of the polycarbonate laser etching film for the smart card provided by the invention needs to be further improved.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a laser etching agent, laser etching polycarbonate, a preparation method and application thereof.

One of the objectives of the present invention is to provide a laser etching agent, and to achieve the objective, the present invention adopts the following technical scheme:

the laser etching agent consists of antimony-doped tin oxide and a laser marking plastic additive, wherein the mass ratio of the antimony-doped tin oxide to the laser marking plastic additive is (0.5-10) to (0.5-10), and the laser marking plastic additive is Iriotec^®8825 and Iriotec^®8820.

The laser etching agent adopts antimony doped tin oxide and Iriotec^®8825 and Iriotec^®8820 and laser-marking plastic adjuvant used together to form laser-etched imageMore clear and high resolution.

Specifically, the mass ratio of the antimony-doped tin oxide to the laser marking plastic additive is (0.5-10): (0.5-10). If the mass ratio of the antimony-doped tin oxide to the laser marking plastic additive is too small, the color of a laser etched image is too light, and obvious moderate gradual change ash does not exist; if the mass ratio of the antimony-doped tin oxide to the laser marking plastic additive is too large, the color of a laser etching image is too dark, and moderate gradual change of gray is excessive.

Iriotec is a plastic auxiliary agent for labeling high polymer material parts or products by laser. Laser marking is to mark parts or products made of high molecular materials by laser. Different from ink jet marking, the marking is carried out on the surface of a high polymer material part or a product through a laser marking machine, so that the effects of water resistance, erasure prevention and lasting preservation can be achieved, and for a user, the laser marking process does not need auxiliary materials or solvents. Through adding the Iriotec laser marking plastic auxiliary agent who mixes in macromolecular material, just can realize laser marking on the part or the goods that processing such as moulding plastics, extrude for the material is sensitive to laser, absorbs the energy of laser and converts into the heat, impels plastics surface carbonization or foaming, thereby leaves permanent seal of a government organization in old china.

Preferably, the Iriotec of the present invention^®8825 and said Iriotec^®8820 the mass ratio of (0.5-5) to (0.5-5). If Iriotec^®8825 and Iriotec^®8820, the mass ratio is too small, so that the laser etched image is not clear and has insufficient blackness; if Iriotec^®8825 and Iriotec^®8820, too large a mass ratio would make the laser etched image too dark, increasing the cost.

The invention also aims to provide a laser etching polycarbonate resin, which adopts the laser etching agent of the first aim as a raw material and comprises the following components in percentage by mass:

80-98.5% of polycarbonate

1-20% of laser etching agent

0.5 to 2 percent of antioxidant.

The invention can produce specific pictures and texts and colors under the irradiation of laser beams by mixing and plasticizing the laser etching agent and the polycarbonate resin powder to process the base material resin with the etching function, and the polycarbonate film or sheet processed by the resin can be used for etching various etching products.

Specifically, the laser etching polycarbonate resin comprises the following components in percentage by mass:

the mass percentage of the polycarbonate is 80 to 98.5%, for example, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 98.5%.

The laser etchant is 1 to 20% by mass, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, or the like.

The antioxidant is 0.3 to 2% by mass, for example, 0.3%, 0.4%, 0.5%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, or 2%.

In the present invention, the particle size of the polycarbonate is less than 1 μm, and is, for example, 10 nm, 20 nm, 30 nm, 40 nm, 50nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800nm, 900 nm or 950 nm.

In the present invention, the particle size of the laser etchant is less than 0.2 μm, for example, 10 nm, 20 nm, 30 nm, 40 nm, 50nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 110 nm, 120 nm, 130 nm, 140 nm, 150nm, 160 nm, 170 nm, 180 nm, 190 nm, etc.

In the invention, the laser etching agent comprises, by mass, 1-20% of antimony-doped tin oxide and 0.5-5% of Iriotec^®8825 and 0.5-5% Iriotec^®8820.

The antioxidant is any one or a mixture of at least two of tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), n-octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2, 6-di-tert-butyl-4-methylphenol, and 2, 2' -methylenebis (4-methyl-6-tert-butylphenol) pentaerythritol-tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], and is preferably tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) pentaerythritol ester.

A third object of the present invention is to provide a method for preparing a laser-etched polycarbonate resin, the method comprising the steps of:

1) respectively grinding polycarbonate and a laser etching agent;

2) and premixing the ground polycarbonate, the laser etching agent and the antioxidant according to the proportion, and performing extrusion granulation to obtain the laser etching polycarbonate resin.

In the step 1), the laser etching agent is ground by adopting wet slurry, and the nano-scale particle size is obtained by grinding.

The fourth purpose of the present invention is to provide an application of the laser-etched polycarbonate resin of the second purpose, wherein the laser-etched polycarbonate resin is used for laser etching of security cards, such as identity cards and various credit cards, and has the characteristics of environmental protection and fastness after being engraved.

Compared with the prior art, the invention has the beneficial effects that:

when the laser etching polycarbonate resin prepared by the laser etching agent is used for card etching, an image after etching is clearer, the resolution is high, the resolution is 2000-2800, the black-white-gray transition is excellent, the etching has no bubble phenomenon, the dot matrix is uniformly distributed, and no burr is generated after the dot matrix circle is amplified.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments.

Unless otherwise specified, various starting materials of the present invention are commercially available or prepared according to conventional methods in the art.

Example 1

The laser-etched polycarbonate resin of the embodiment comprises the following components in percentage by mass:

polycarbonate Panlite L-1250Y 98.2%

Laser etching agent 1.5%

0.3 percent of tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid) pentaerythritol ester;

wherein the laser etching agent consists of 0.5 percent of antimony doped tin oxide and 0.5 percent of Iriotec^®8825 and 0.5% Iriotec^®8820, the particle size of polycarbonate is 800nm, and the particle size of laser etching agent is 150 nm.

The preparation method of the laser etching polycarbonate resin comprises the following steps:

1) respectively grinding polycarbonate and a laser etching agent;

Example 2

polycarbonate Panlite L-1250Y 90%

Laser etching agent 9%

1% of tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid) pentaerythritol ester;

wherein the laser etching agent consists of 1 percent of antimony doped tin oxide and 4 percent of Iriotec^®8825 and 4% Iriotec^®8820, the particle size of polycarbonate is 800nm, and the particle size of laser etching agent is 150 nm.

The laser-etched polycarbonate resin of this example was the same as that of example 1.

Example 3

polycarbonate Panlite L-1250Y 83%

15 percent of laser etching agent

2% of n-octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate;

wherein the laser etching agent consists of 5 percent of antimony doped tin oxide and 5 percent of Iriotec^®8825 and 5% Iriotec^®8820, the particle size of polycarbonate is 800nm, and the particle size of laser etching agent is 150 nm.

Example 4

This example differs from example 1 in that the laser etchant is used in an amount of 0.6%, and is composed of 0.2% antimony doped tin oxide, 0.2% Iriotec^®8825 and 0.2% Iriotec^®8820, the amount of the laser etchant used was increased on average to other components, all other components being the same as in example 1.

Example 5

This example differs from example 1 in that the laser etchant was used in an amount of 30%, and was doped with 10% antimony-doped tin oxide, 10% Iriotec^®8825 and 10% Iriotec^®8820, the amount of added laser etchant is on average subtracted from the other components, all other components being the same as in example 1.

Example 6

This example is different from example 1 in that the particle size of the polycarbonate is 30 μm, and the other examples are the same as example 1.

Example 7

This example is different from example 1 in that the particle size of the laser etchant is 1.5 μm, and the others are the same as example 1.

Example 8

This example is different from example 1 in that the particle size of polycarbonate is 30 μm, the particle size of laser etchant is 1.5 μm, and the others are the same as example 1.

Comparative example 1

The laser-etched polycarbonate resin of the comparative example comprises the following components in percentage by mass:

polycarbonate Panlite L-1250Y 99.7%

wherein the particle size of the polycarbonate is 30 μm.

The preparation method of the laser etching polycarbonate resin of the comparative example comprises the following steps: and pre-mixing the ground polycarbonate and the antioxidant according to the proportion, and performing extrusion granulation to obtain the laser etching polycarbonate resin.

Comparative example 2

polycarbonate Panlite L-1250Y 99.2%

0.5 percent of antimony doped tin oxide

wherein the particle size of the polycarbonate is 30 mu m, and the particle size of the antimony doped tin oxide is 150 nm.

The preparation method of the laser etching polycarbonate resin of the comparative example comprises the following steps: and pre-mixing the ground polycarbonate, antimony-doped tin oxide and an antioxidant according to a ratio, and performing extrusion granulation to obtain the laser etching polycarbonate resin.

Comparative example 3

polycarbonate Panlite L-1250Y 98.7%

0.5 percent of antimony doped tin oxide

Iriotec^®8825 0.5%

wherein the particle size of the polycarbonate is 30 μm, and the laser etching agent is antimony doped tin oxide and Iriotec^®8825, the grain size of the laser etching agent is 150 nm.

The preparation method of the laser etching polycarbonate resin of the comparative example comprises the following steps:

1) mixing antimony doped tin oxide and Iriotec according to the proportion^®8825 mixing to prepare laser etching agent;

2) and pre-mixing the ground polycarbonate with a laser etching agent and an antioxidant according to a ratio, and performing extrusion granulation to obtain the laser etching polycarbonate resin.

Comparative example 4

polycarbonate Panlite L-1250Y 98.7%

0.5 percent of antimony doped tin oxide

Iriotec^®8820 0.5%

wherein the particle size of the polycarbonate is 30 μm, and the laser etching agent is antimony doped tin oxide and Iriotec^®8820, the grain size of the laser etching agent is 150 nm.

1) mixing antimony doped tin oxide and Iriotec according to the proportion^®8820 mixing to prepare laser etching agent;

Comparative example 5

polycarbonate Panlite L-1250Y 98.7%

Iriotec^®8825 0.5%

Iriotec^®8820 0.5%

wherein the particle size of the polycarbonate is 30 μm, and the laser etching agent is Iriotec^®8825 and Iriotec^®8820, the grain size of the laser etching agent is 150 nm.

1) mixing Iriotec according to a certain proportion^®8825 and Iriotec^®8820 mixing to prepare laser etching agent;

Comparative example 6

This comparative example differs from example 1 in that antimony doped tin oxide was replaced with tin oxide not doped with antimony, and the rest was the same as example 1.

Comparative example 7

This comparative example differs from example 1 in that Iriotec is added^®The substitution was made with LaserAT-8632P, and the others were the same as those in example 1.

Comparative example 8

The comparison example is different from the example 1 in that the mass ratio of the antimony doped tin oxide to the laser marking plastic additive is that the laser etching agent consists of 0.05 percent of antimony doped tin oxide and 0.5 percent of Iriotec^®8825 and 0.5% Iriotec^®8820, the rest is the same as in example 1.

Comparative example 9

The comparative example is different from example 1 in that the mass ratio of the antimony doped tin oxide to the laser marking plastic additive is 1.5% of antimony doped tin oxide and 0.5% of Iriotec^®8825 and 0.5% Iriotec^®8820, the rest is the same as in example 1.

Comparative example 10

This comparative example differs from example 1 in that Iriotec^®8825 and Iriotec^®8820 Iriotec 0.05 wt%^®8825 and 0.95% Iriotec^®8820, the rest is the same as in example 1.

Comparative example 11

This comparative example differs from example 1 in that Iriotec^®8825 and Iriotec^®8820 Iriotec 0.95 wt%^®8825 and 0.05% Iriotec^®8820, the rest is the same as in example 1.

The laser-etched polycarbonate resins prepared in examples 1 to 8 and comparative examples 1 to 11 were used for laser etching, and the properties after engraving were tested, and the experimental results are shown in table 1.

Wherein the resolution test is performed according to the ISO 12233 standard.

TABLE 1

As can be seen from Table 1, when the laser etching polycarbonate resin prepared by the laser etching agent is used for etching identification cards, images after etching are clearer, the resolution is high, the resolution is 2000-2800, the transition of black and white and gray is excellent, the etching has no bubble phenomenon, the dot matrix is uniformly distributed, and no burr is generated after the dot matrix circle is enlarged.

Example 4 too little laser etchant was used, the resolution decreased, and the black-white-gray transition was normal.

Example 5 too much laser etchant was used, the resolution decreased, and the dot circles had burrs after enlargement.

If the particle size of the polycarbonate is too large in example 6 and the particle size of the laser etching agent is too large in example 7, the particle size of the polycarbonate and the particle size of the laser etching agent are both large in example 8, so that the resolution is low and burrs are formed after enlarging the dot matrix circle.

Comparative example 1 contains no laser etchant, and results in low resolution, poor black-white-gray transition, bubbling etching, uneven dot pattern distribution, rough edges after enlarging dot matrix circle, and poor etching effect.

Comparative example 2 laser etchant with antimony doped tin oxide only, comparative example 3 with addition of Iriotec only^®8825 comparisonExample 4 addition of an Iriotec^®8820, comparative example 5, which does not contain antimony doped tin oxide, all resulted in lower resolution and burr after enlargement of the dot matrix circle.

Comparative example 6 replacing antimony doped tin oxide with antimony undoped tin oxide would obscure the laser etched image.

Comparative example 7 replacing Iriotec with LaserAT-8632P causes the laser etched image to be unclear.

Comparative example 8 the mass ratio of antimony doped tin oxide to laser marking plastic adjuvant is too low, which makes the laser etched image too light in color without obvious moderate gradual change ash.

Comparative example 9 mass ratio of antimony doped tin oxide to laser marking plastic additive is too large, which may result in too dark color of laser etched image and excessive moderate gradual gray.

Comparative example 10Iriotec^®8825 and Iriotec^®8820, too small a mass ratio can result in an unclear laser-etched image and insufficient blackness.

Comparative example 11Iriotec^®8825 and Iriotec^®8820, too large a mass ratio would make the laser etched image too dark, increasing the cost.

The present invention is illustrated by the above-mentioned examples, but the present invention is not limited to the above-mentioned detailed process equipment and process flow, i.e. it is not meant to imply that the present invention must rely on the above-mentioned detailed process equipment and process flow to be practiced. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.

In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims

1. The laser etching agent is characterized by comprising antimony-doped tin oxide and a laser marking plastic auxiliary agent, wherein the mass ratio of the antimony-doped tin oxide to the laser marking plastic auxiliary agent is (0.5-10) to (0.5-10), and the laser marking plastic auxiliary agent is Iriotec^®8825 and Iriotec^®8820 to (b);

the Iriotec^®8825 and said Iriotec^®8820 the mass ratio of (0.5-5) to (0.5-5).

2. A laser-etched polycarbonate resin comprising the laser etchant according to claim 1, wherein the laser etchant comprises the following components in percentage by mass:

80-98.5% of polycarbonate

1-20% of laser etching agent

0.3 to 2 percent of antioxidant.

3. The laser-etched polycarbonate resin according to claim 2, wherein the polycarbonate has a particle size of less than 1 μm.

4. The laser-etched polycarbonate resin according to claim 2 or 3, wherein the particle size of the laser etchant is less than 0.2 μm.

5. The laser-etched polycarbonate resin according to claim 2, wherein the laser etchant comprises 0.5-10% of antimony-doped tin oxide and 0.5-5% of Iriot by mass percentage of 1-20%c^®8825 and 0.5-5% Iriotec^®8820.

6. The laser-etched polycarbonate resin according to claim 2, wherein the antioxidant is any one of pentaerythritol tetrakis (β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate), n-octadecyl-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, 2, 6-di-t-butyl-4-methylphenol, 2' -methylenebis (4-methyl-6-t-butylphenol) pentaerythritol-tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], or a mixture of at least two thereof.

7. A method for preparing a laser-etched polycarbonate resin according to any one of claims 2 to 6, comprising the steps of:

1) respectively grinding polycarbonate and a laser etching agent;

8. The preparation method of claim 7, wherein in the step 1), the laser etching agent is ground by wet slurry to obtain nano-scale particle size.

9. Use of a laser etched polycarbonate resin according to any of claims 2 to 6 for laser etching of security cards.