CN116178851A - Styrene compound, product, preparation method and application thereof - Google Patents

Abstract

The invention relates to a styrene compound, a product, a preparation method and application thereof. The styrene compound comprises a styrene polymer, a butadiene toughening agent and a black-and-white laser marking agent. The invention takes the styrene polymer as the base material, and adds a specific amount of black-and-white laser marking agent, so that white marks can be laser-carved in the base material, and the surface layer of the base material has excellent scratch resistance.

Description

A kind of styrene compound, product and its preparation method and application

technical field

The invention belongs to the technical field of plastic laser engraving, and in particular relates to a styrene compound, a product, a preparation method and an application thereof.

Background technique

Laser engraving processing technology is widely used in the texture modification of various graphics and marks on the surface of plastic products due to its economical and environmental protection, automation and flexible design. Plastic laser engraving can generally be used in black and white, white and black, and black and color. Among them, laser engraving black and white can be used to carve letters, LOGO and patterns on black electrical shells, and is widely used in black home appliances and OA industries. popular. However, the plastic radium engraving black and white is produced by laser-excited surface foaming to present a white mark. The foamed white mark has very poor scratch resistance and is easily scratched to form scratches, which seriously affects the appearance.

At present, a patent has provided a polypropylene composite material, which uses polypropylene as the base material, uses barium sulfate and toughening compatibilizers to improve scratch resistance, and adds radium engraving additives to realize radium engraving, but its improved It is the scratch resistance of the polypropylene composite material. The logo on the surface of the material still has the defect of poor scratch resistance after laser engraving.

Therefore, it is of great research significance and application value to develop a laser engraving material that can engrave scratch-resistant white marks with laser.

Contents of the invention

The object of the present invention is to overcome the defects or shortcomings of the white markings of radium engraving materials in the prior art that are not resistant to scratches, and provide a styrene compound. The invention uses styrene polymer as the base material and adds a specific amount of black and white laser marking agent to carve white marks inside the base material with radium, and its surface layer has excellent scratch resistance.

Another object of the present invention is to provide a preparation method of the above-mentioned styrene compound.

Another object of the present invention is to provide the application of the above-mentioned styrene compound in laser engraving.

Another object of the present invention is to provide a laser engraved product with a white logo.

In order to realize the above-mentioned purpose of the invention, the present invention adopts following technical scheme:

A styrene composite, comprising the following components in parts by weight:

100 parts of styrene polymer,

0-3 parts of butadiene toughening agent,

0.01-0.05 parts of black and white laser marking agent.

The present invention uses styrene polymer as the base material, and adds a specific amount of black and white laser marking agent. When the obtained styrene composite is marked by laser, the black and white laser marking agent absorbs the laser energy Bubbles are generated inside the base material, which can not only obtain white marks inside the base material, but also avoid the problem of scratch resistance due to foaming on the surface layer. It has excellent scratch resistance and can be widely used in black household appliances, etc. that require laser engraving. Products identified in white.

The selection of substrate, the selection and dosage of black and white laser marking agent have a great influence on the position of bubbles and the effect of laser engraving. If other commonly used laser engraving materials are used as the substrate, such as polymethyl methacrylate or polycarbonate, it is easy to be heated into carbon under laser excitation, and dark marks will appear after laser engraving, which cannot achieve black and white printing. If the amount of black and white laser marking agent is too small, laser engraving cannot be done well; if the amount of black and white laser marking agent is too large, when laser engraving, the laser will form a large number of bubbles inside and on the surface of the composite , which also causes the surface of the white logo to be scratch-resistant. However, if other laser marking agents are used, such as pearlescent pigments, although the laser marking has certain scratch resistance, the color of the laser marking is black and yellow, and it is difficult to obtain a white laser marking. It is generally used for dark laser marking.

Preferably, the styrene polymer is one or more of styrene-acrylonitrile copolymer or polystyrene.

The melt index of styrenic polymers has a large effect on processability and a slight effect on scratch resistance.

Preferably, according to ISO1133-2011, the melt index of the styrene polymer under the condition of 200° C. and 5 kg is 1-10 g/10 min; more preferably 2.5-8 g/10 min.

Preferably, the butadiene toughening agent is one or more of styrene-butadiene-acrylonitrile copolymer or styrene-butadiene copolymer.

Preferably, according to the infrared quantitative analysis method, the butadiene toughening agent has a BD structure (butadiene structure) component content of 60wt.%-80wt.%, more preferably 60wt.%-75wt.%.

Preferably, the weight portion of the butadiene toughening agent is 0.01-3 parts, more preferably 0.01-1 part.

Adding an appropriate amount of butadiene toughening agent can improve the mechanical properties of styrene composites without affecting the laser engraving effect. If the amount of butadiene toughening agent added is too large, it is impossible to guarantee that only bubbles will be generated inside the substrate during laser engraving, which will affect the scratch resistance performance.

Preferably, the black and white laser marking agent is carbon black.

The preparation method of the above-mentioned styrene compound comprises the following steps: uniformly mixing the styrene polymer, the butadiene toughening agent and the black and white laser marking agent to obtain a mixture, and then melting and extruding the mixture, granulating, That is, the styrene complex is obtained.

Preferably, the styrene polymer, butadiene toughening agent and black-and-white laser marking agent are mixed uniformly in a high-speed mixer to obtain a compound, and then the compound is added to a twin-screw extruder for melt extrusion, Granulating to obtain the styrene compound.

More preferably, a high mixer is used for stirring and mixing, the stirring speed is 60-100 rpm, and the stirring time is 3-5 minutes.

Preferably, a twin-screw extruder is used for melt extrusion and granulation; the extrusion temperature of the twin-screw extruder is 160-220°C, the aspect ratio is 40-65:1, and the screw speed is 300-450 rpm min.

The application of the above-mentioned styrene compound in laser engraving is also within the protection scope of the present invention.

A laser engraved product with a white mark, which is obtained by injecting the styrene compound and then performing laser engraving to obtain a white mark.

Preferably, the article is black goods.

Compared with the prior art, the present invention has the following beneficial effects:

The invention uses styrene polymer as the base material and adds a specific amount of black and white laser marking agent to carve white marks inside the base material with radium, and its surface layer has excellent scratch resistance.

Detailed ways

The present invention is further set forth below in conjunction with embodiment. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. The experimental method that does not indicate specific conditions in the following example embodiment, usually according to the conventional conditions in this field or according to the conditions suggested by the manufacturer; used raw materials, reagents, etc., if no special instructions, are available from commercial channels such as conventional markets Raw materials and reagents obtained. Any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention fall within the scope of the present invention.

The partial reagents that each embodiment of the present invention and comparative examples select are described as follows:

A. Polymer

Styrene-acrylonitrile copolymer 1# (SAN 1#): SAN-2437, PetroChina Jihua, according to ISO1133-2011, the melt index is 2.5g/10min at 200°C and 5kg;

Styrene-acrylonitrile copolymer 2# (SAN 2#): SAN 310NTR, Kumho, South Korea, according to ISO1133-2011, the melt index at 200°C and 5kg is 3.0g/10min;

Styrene-acrylonitrile copolymer 3# (SAN 3#): SAN NX3400, Ningbo Taihua, according to ISO1133-2011, the melt index at 200°C, 5kg is 1.0g/10min;

Polystyrene 1# (GPPS1#): GPPS123P, Shanghai Secco, according to ISO1133-2011, the melt index at 200°C and 5kg is 8.0g/10min;

Polystyrene 2# (GPPS2#): GPPS861N, Delta Chemical, in accordance with ISO1133-2011, the melt index at 200°C and 5kg is 6.6g/10min;

PMMA (polymethyl methacrylate): PMMA CM-207, Chimei, Taiwan, according to ISO1133-2011, the melt index at 230°C, 3.8kg is 8.5ml/10min;

B. Butadiene Toughener

Styrene-butadiene-acrylonitrile copolymer 1# (B1-1#): ABS POW HR181, Kumho, South Korea, BD structural component content 60%;

Styrene-butadiene-acrylonitrile copolymer 2# (B1-2#): ABS high rubber powder 60P, Taiwan Guoqiao, BD structural component content 68%;

Styrene-butadiene copolymer 1# (B2-1#): TUFPRENE 125, Asahi Kasei, BD component content 75%;

Styrene-butadiene copolymer 1# (B2-2#): TUFPRENE 126, Asahi Kasei, BD component content 74%;

C. Laser marking agent:

Carbon black, black and white laser marking agent, DENKA BLACK, Japan Denki Chemical Industry Co., Ltd.;

Pearlescent pigment, dark laser marking agent, IRIODIN 183, Merck.

Compounds in Examples 1-13 of the present invention and Comparative Examples 1-5 were prepared through the following process:

Weigh each raw material and put it into a mixer with a rotation speed of about 100 rpm for 3-5 minutes, then mix the mixed raw materials at an aspect ratio of 40:1 and a temperature range of 160°C, 190°C, 190°C, 200°C, 210°C, 210°C, 210°C, 220°C, 220°C, 220°C, 220°C, twin-screw extruder with a speed of 450 rpm for melt extrusion and granulation to obtain plastic particles, which are compounds.

The plastic particles are injection molded into a color plate (thickness 2mm) at about 200°C, and then use the Han’s Laser EP-12 laser marking machine to carry out laser engraving under the conditions of a current of 20A, a marking speed of 1000mm/s, and a frequency of 17kHz. , get the laser engraving mark.

Test the color, pencil hardness, and surface scratch resistance of the swatch before laser engraving, and test the pencil hardness and scratch resistance of the surface of the mark on the color mark of the swatch mark after laser marking; laser engraving The test position before the laser engraving is consistent with the test position after laser engraving.

(1) Color: Under visible light, observe the color with the naked eye.

(2) Pencil hardness: measured according to the standard of GB/T6739-2006.

(3) Scratch resistance: Measured according to the scratch resistance standard of Volkswagen Baige cross scratch PV3952-2019 plastic inner cavity components, the load is 10N, and the scraping speed is 1000mm/min. Test the L value and gloss of the same position before and after the scratch resistance test. The L value is measured by a colorimeter according to the standard GB/T11186-1989; the gloss is measured by a gloss meter (60°) according to the standard GB/T 8807-1988 . If the L value increases more, or the gloss drops more, it means that its scratch resistance performance is relatively poor.

Examples 1-13

This example provides a series of styrene compounds, the formulations of which are shown in Table 1.

The formula (part) of table 1 embodiment 1～13

Comparative example 1-5

This comparative example provides a series of compounds, the formulations of which are shown in Table 2.

The formula (part) of comparative example 1～5 of table 2

The properties of the styrene composites (or composites) provided in the examples and comparative examples were tested according to the aforementioned performance testing method, and the results are shown in Table 3.

The performance test result of the composition that table 3 embodiment 1～13 and comparative example 1～5 provide

From the above test results, it can be seen that the styrene composites provided in Examples 1-13 can be used to obtain white markings through black and white laser engraving. The pencil hardness test is carried out on the same position, and the pencil hardness before and after laser engraving is basically the same without any change. Comparing the changes in L and gloss before and after laser engraving, it can be seen that the scratch resistance of the white marking is almost the same as that before laser engraving. It can be seen that the styrene composites provided in Examples 1-13 only foam inside the matrix during laser engraving, and the bubbles exist inside and do not migrate to the surface. High hardness, good scratch resistance. In Comparative Example 1, when the butadiene toughening agent was added in an excessive amount, air bubbles were generated on the surface and inside of the substrate during laser engraving, and the obtained white mark had poor scratch resistance. The black and white laser marking agent added in Comparative Example 2 is too little to be laser engraved. Too much black and white laser marking agent was added in Comparative Example 3. During laser engraving, the laser will form a large number of bubbles inside and on the surface of the compound, resulting in the surface of the white mark obtained by laser engraving is not resistant to scratches. The PMMA used in Comparative Example 4 was used as the base material. During laser engraving, the composite was severely carbonized, the surface was uneven, and the mark was black and yellow. It was impossible to form a white mark, and the pencil hardness and scratch resistance tests could not be performed. In Comparative Example 5, the pearlescent pigment laser marking agent was used. During laser engraving, the compound was also severely carbonized, the surface was uneven, the mark was black and yellow, and white marks could not be formed. Pencil hardness and scratch resistance tests could not be performed.

Those skilled in the art will appreciate that the embodiments herein are to help readers understand the principles of the present invention, and it should be understood that the protection scope of the present invention is not limited to such specific statements and embodiments. Those skilled in the art can make various other specific modifications and combinations based on the technical revelations disclosed in the present invention without departing from the essence of the present invention, and these modifications and combinations are still within the protection scope of the present invention.

Claims (10)

1. a styrene compound, is characterized in that, comprises the component of following parts by weight: 100 parts of styrene polymer, 0-3 parts of butadiene toughening agent, Black and white laser marking agent 0.01～0.05 parts. 2. The styrene composite according to claim 1, wherein the styrene polymer is one or more of styrene-acrylonitrile copolymer or polystyrene. 3. according to the described styrene compound of claim 1, it is characterized in that, described butadiene toughening agent is a kind of in styrene-butadiene-acrylonitrile copolymer or styrene-butadiene copolymer or several. 4 . The styrene composite according to claim 1 , wherein the butadiene toughening agent has a BD structural component content of 60wt.% to 80wt.% according to the infrared quantitative analysis method. 5. The styrene composite according to claim 1, characterized in that, the butadiene toughening agent is in parts by weight of 0.01-1 part. 6. The styrene composite according to claim 1, wherein the black and white laser marking agent is carbon black. 7. The method for preparing the styrene composite according to any one of claims 1 to 6, characterized in that it comprises the steps of: uniformly mixing the styrene polymer, the butadiene toughening agent and the black-and-white laser marking agent to obtain The mixture is then melt-extruded and granulated to obtain the styrene compound. 8. according to the described preparation method of claim 7, it is characterized in that, comprises the steps: styrene polymer, butadiene toughening agent and black and white laser marking agent are mixed uniformly in high mixer to obtain compound, then Put the mixture into a twin-screw extruder to melt and extrude, and granulate to obtain the styrene compound. 9. The application of the styrene compound according to any one of claims 1 to 6 in laser engraving. 10. A laser engraved product with a white mark, characterized in that the product is obtained by injecting the styrene compound according to any one of claims 1 to 6 and then performing laser engraving to obtain a white mark.