CN115678160B - Composition with laser marking function - Google Patents
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- CN115678160B CN115678160B CN202211280744.4A CN202211280744A CN115678160B CN 115678160 B CN115678160 B CN 115678160B CN 202211280744 A CN202211280744 A CN 202211280744A CN 115678160 B CN115678160 B CN 115678160B
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Abstract
The invention provides a composition with a laser marking function, which comprises the following components in parts by mass: 100 parts of polypropylene and a color reagent, namely dodecyl cage-shaped silsesquioxane ((C) 6 H 5 SiO 1.5 ) 12 ) 2-3 parts of inducer decabromodiphenyl ethane 1-3 parts of heat conductive agent 1-3 parts; the heat conducting agent is a titanium dioxide surface modified boron nitride nano-sheet, wherein the sum G2 of the mass G1 of the dodecyl cage-shaped silsesquioxane, the mass G2 of the decabromodiphenylethane and the heat conducting agent meets the condition that G1:G2=1:1.5-2. The composition may further comprise at least one of a compatibilizer, an antioxidant, a toughening agent, and a coupling agent; the composition provided by the invention has high blackness and high definition of the laser mark, and ensures that the appearance mark of the final laser marked product is not easily damaged. The composition has good application prospect in various containers, especially medical container shells.
Description
Technical Field
The invention relates to the field of plastics, in particular to a composition with a laser marking function.
Background
In general, a laser marking method is used in which a target is irradiated with a laser beam to record (so-called laser printing) various packaging containers for accommodating foods, beverages, medicines, quasi-medicines, cosmetics, and the like, packaging materials for various packaging materials such as films and papers, and the like.
The laser marking technology is based on the principle that high-energy laser beam irradiates the surface of material or workpiece to vaporize or color the surface, so as to display the preset pattern or text on the surface of material or workpiece. The laser marking technology has certain requirements on the material itself or the addition of auxiliary agents, namely, the surface of the material is required to be melted, gasified or carbonized at the high-energy laser beam irradiation part, the surrounding part is not changed, or the auxiliary agents added into the material have a color development effect, the part irradiated by the laser beam is developed, and the other surrounding part is not developed. For the material which can be marked by laser, the molecules of the material are required to have certain thermal stability, and under the action of a laser beam, the illumination part is carbonized to display the graphic characters; while other materials need to be correspondingly modified, the basic materials which can be used for modification require certain stability and auxiliary compatibility of molecules; since the laser marking method is so-called non-contact type, there are advantages such as: high-precision recording can be performed; high-speed recording can be performed; recording can be performed on various surface shapes of the object. Further, the laser marking method has an advantage that it is a recording that can be hardly erased as compared with a recording by a hot stamping method or an inkjet method.
Disclosure of Invention
The invention provides a composition with a laser marking function, which comprises the following components in parts by mass: 100 parts of polypropylene and a color reagent, namely dodecyl cage-shaped silsesquioxane ((C) 6 H 5 SiO 1.5 ) 12 ) 2-3 parts of inducer decabromodiphenyl ethane 1-3 parts of heat conductive agent 1-3 parts; the heat conducting agent is a titanium dioxide surface modified boron nitride nano-sheet, wherein the sum G2 of the mass G1 of the dodecyl cage-shaped silsesquioxane, the mass G2 of the decabromodiphenylethane and the heat conducting agent meets the condition that G1:G2=1:1.5-2. The composition may further comprise at least one of a compatibilizer, an antioxidant, a toughening agent, and a coupling agent; the composition provided by the invention has high blackness and high definition of the laser mark, and ensures that the appearance mark of the final laser marked product is not easily damaged. The composition has wide application prospect in various pipe bodies, container shells, especially biomedical materials, consumables and other related fields.
The specific scheme comprises the following steps:
a composition with a laser marking function, comprising, in parts by mass: 100 parts of polypropylene and a color reagent, namely dodecyl cage-shaped silsesquioxane ((C) 6 H 5 SiO 1.5 ) 12 ) 2-3 parts of inducer decabromodiphenyl ethane 1-3 parts of heat conductive agent 1-3 parts; the heat conducting agent is a titanium dioxide surface modified boron nitride nano-sheet, wherein the sum G2 of the mass G1 of the dodecyl cage-shaped silsesquioxane, the mass G2 of the decabromodiphenylethane and the heat conducting agent meets the condition that G1:G2=1:1.5-2.
Further, the composition also comprises 10-12 parts of a compatilizer, wherein the compatilizer is at least one selected from maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, glycidyl ester grafted polyethylene, glycidyl ester grafted polypropylene, maleic anhydride grafted polypropylene, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-vinyl alcohol copolymer and ethylene-vinyl acetate copolymer.
Further, the composition also comprises at least one of an antioxidant, a toughening agent and a coupling agent.
Further, the antioxidant is 0.2 to 0.8 part by mass, and the antioxidant is at least one selected from beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester, triethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 4' -thiobis (6-tert-butyl-3-methylphenol), tris (2, 4-di-tert-butylphenyl) phosphite and tetra (2, 4-di-tert-butylphenol) -4, 4-biphenyldiphosphite.
Further, the toughening agent is 0.5 to 3.0 parts by mass, and the toughening agent is at least one selected from the group consisting of polyoctene-maleic anhydride grafts, ethylene-ethyl acrylate copolymers, polycaprolactone and polybutyl adipate terephthalate.
Further, the coupling agent is 0.2-1 part by mass, and the coupling agent is at least one selected from silane coupling agent KH550, gamma-aminopropyl triethoxysilane and phenylaminomethyl trimethoxysilane.
Further, the composition may further comprise a color toner, wherein the color refers to a single common color of red, blue, orange, yellow, cyan, green, purple, or various mixed colors of the above colors.
Further, the titanium dioxide surface modified boron nitride nano-sheet is prepared by the following method, 2.5g of tetraisopropyl titanate is taken and dissolved in 200ml of mixed solvent of ethanol and dimethylformamide in a volume ratio of 1:1, 10g of boron nitride nano-sheet is added, the mixture is placed in a hydrothermal reaction kettle, an inner tank body of the reaction kettle is a polytetrafluoroethylene sealed tank, the inner tank body is sealed, the hydrothermal reaction is carried out for 4-6 hours at 120 ℃, the sediment is obtained after filtration, ethanol and deionized water are respectively used for washing, and drying is carried out, so that the titanium dioxide surface modified boron nitride nano-sheet is obtained.
Further, the particle size of the boron nitride nano-sheet is 300-500nm.
The beneficial technical effects of the invention
1) Dodecyl cage silsesquioxane ((C) 6 H 5 SiO 1.5 ) 12 ) Colorless in visible light, can be added into polypropylene plastics with any color, and has higher blackness value and high identification degree after the material is carbonized in the heating process;
2) The decabromodiphenylethane can absorb laser and promote the carbonization of the dodecaphenyl cage-shaped silsesquioxane, so that the blackness of laser marking is improved, meanwhile, titanium dioxide in the titanium dioxide surface-modified boron nitride nanosheets can absorb laser and generate heat, and the boron nitride nanosheets serve as good conductors of heat, so that the rapid carbonization of laser irradiation parts is promoted, and black marks with high contrast and definition are generated on the surfaces.
Detailed Description
The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples within the scope of the present invention.
A composition with a laser marking function, comprising, in parts by mass: 100 parts of polypropylene and a color reagent, namely dodecyl cage-shaped silsesquioxane ((C) 6 H 5 SiO 1.5 ) 12 ) 2-3 parts of inducer decabromodiphenyl ethane 1-3 parts of heat conductive agent 1-3 parts; the heat conducting agent is a titanium dioxide surface modified boron nitride nano-sheet, wherein the sum G2 of the mass G1 of the dodecyl cage-shaped silsesquioxane, the mass G2 of the decabromodiphenylethane and the heat conducting agent meets the condition that G1:G2=1:1.5-2.
Further, the content of the compatibilizer is not particularly limited, preferably 10 to 12 parts, and the type of the compatibilizer is not particularly limited, and may be at least one selected from maleic anhydride-grafted polyethylene, maleic anhydride-grafted polypropylene, glycidyl ester-grafted polyethylene, glycidyl ester-grafted polypropylene, maleic anhydride-grafted polypropylene, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-vinyl alcohol copolymer, and ethylene-vinyl acetate copolymer.
Further, the composition also comprises at least one of an antioxidant, a toughening agent and a coupling agent.
Further, the content of the antioxidant is not particularly limited, and preferably 0.2 to 0.8 parts by mass, and the antioxidant is not particularly limited, and may be at least one selected from the group consisting of n-stearyl β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, triethylene glycol bis [ β - (3-t-butyl-4-hydroxy-5-methylphenyl) propionate, 4' -thiobis (6-t-butyl-3-methylphenol), tris (2, 4-di-t-butylphenyl) phosphite, and tetrakis (2, 4-di-t-butylphenol) -4, 4-biphenyldiphosphite.
Further, the content of the toughening agent is not particularly limited, preferably 0.5 to 3.0 parts by mass, and the type of the toughening agent is not particularly limited, and may be at least one selected from the group consisting of polyocten-maleic anhydride graft, ethylene-ethyl acrylate copolymer, polycaprolactone, and polybutyl adipate terephthalate.
The content of the coupling agent is not particularly limited, and preferably 0.2 to 1 part by mass, and the type of the coupling agent is not particularly limited, and may be at least one selected from the group consisting of silane coupling agents KH550, γ -aminopropyl triethoxysilane, and anilinomethyl trimethoxysilane.
Further, the composition may further comprise a color toner, wherein the color refers to a single common color of red, blue, orange, yellow, cyan, green, purple, or various mixed colors of the above colors.
Further, the titanium dioxide surface modified boron nitride nano-sheet is prepared by the following method, 2.5g of tetraisopropyl titanate is taken and dissolved in 200ml of mixed solvent of ethanol and dimethylformamide in a volume ratio of 1:1, 10g of boron nitride nano-sheet is added, the mixture is placed in a hydrothermal reaction kettle, an inner tank body of the reaction kettle is a polytetrafluoroethylene sealed tank, the inner tank body is sealed, the hydrothermal reaction is carried out for 4-6 hours at 120 ℃, the sediment is obtained after filtration, ethanol and deionized water are respectively used for washing, and drying is carried out, so that the titanium dioxide surface modified boron nitride nano-sheet is obtained. The particle size of the boron nitride nano-sheet is 300-500nm.
The following specific examples only tested the visualization properties of the three components of the composition of the invention, the component developer dodecylcage silsesquioxane, the inducer decabromodiphenylethane, and the thermally conductive titanium dioxide surface modified boron nitride nanoplatelets for laser marking, while no further testing was performed for mechanical properties.
The titanium dioxide surface-modified boron nitride nanosheets of the embodiment are prepared by the following method, 2.5g of tetraisopropyl titanate is dissolved in 200ml of mixed solvent of ethanol and dimethylformamide in a volume ratio of 1:1, 10g of boron nitride nanosheets with the particle size of 400nm are added, the mixture is placed in a hydrothermal reaction kettle, an inner tank body of the reaction kettle is polytetrafluoroethylene, the inner tank body is sealed, hydrothermal reaction is carried out for 6 hours at 120 ℃, the mixture is filtered to obtain precipitate, ethanol and deionized water are respectively used for washing 3 times, and the mixture is heated to 350 ℃ and dried for 1 hour, so that the titanium dioxide surface-modified boron nitride nanosheets are obtained.
The mass parts of the color-developing agent, namely the dodecylbenzene cage-shaped silsesquioxane, the inducer, namely the decabromodiphenylethane and the heat-conducting agent, namely the titanium dioxide surface-modified boron nitride nano-sheets are shown in the table 1, and the contents of other components are the same and are not shown in the table 1, based on 100 parts by mass of polypropylene in the examples and the comparative examples;
TABLE 1
Data and results
The compositions of examples and comparative examples were injection molded into high gloss plaques and then laser marked to make test specimens. The laser wavelength is 1064nm, the speed is 1000mm/s, the laser energy is 8W, the laser frequency is 80kHz, the definition and the blackness of the laser printing marks are respectively evaluated by adopting a 15-time magnifying glass, and the laser printing marks are classified into 10 grades according to the definition of the laser marks: from very clear to unclear, which corresponds to a number of levels of 10 to 1, respectively. And then the darkness of the black color is detected by using a spectrophotometer.
As shown in table 2 below.
TABLE 2
As can be seen from table 2, when G2/G1 is between 1.5 and 2, a very clear contrast can be obtained, the edges are clear, the contrast is high, and a blackness value is better, and when G2/G1 is lower than 1.5, the blackness value is reduced, and as G2 is reduced, the contrast is reduced; however, when G2/G1 is higher than 2, there is little change in the blackness value, but the contrast ratio is significantly lowered.
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description is not to be considered as limiting the invention.
Claims (8)
1. A composition having a laser marking function, characterized in that the composition comprises, in parts by mass: 100 parts of polypropylene and a color reagent, namely dodecyl cage-shaped silsesquioxane ((C) 6 H 5 SiO 1.5 ) 12 ) 2-3 parts of inducer decabromodiphenyl ethane 1-3 parts of heat conductive agent 1-3 parts; the heat conducting agent is a titanium dioxide surface modified boron nitride nano-sheet, wherein the sum G2 of the mass G1 of the dodecyl benzene clathrate silsesquioxane, the mass G2 of the decabromodiphenylethane and the heat conducting agent meets the condition that G1:G2=1:1.5-2; the titanium dioxide surface modified boron nitride nanosheets are prepared by the following method, 2.5g of tetraisopropyl titanate is taken and dissolved in 200ml of mixed solvent of ethanol and dimethylformamide in a volume ratio of 1:1, 10g of boron nitride nanosheets are added, the mixture is placed in a hydrothermal reaction kettle, an inner tank body of the reaction kettle is a polytetrafluoroethylene sealed tank, the inner tank body is sealed, the hydrothermal reaction is carried out for 4-6 hours at 120 ℃, the sediment is obtained by filtering, and ethanol and dimethylformamide are respectively used for precipitatingWashing with deionized water, and drying to obtain the titanium dioxide surface-modified boron nitride nanosheets.
2. The composition of claim 1, further comprising a compatibilizer, the compatibilizer being 10-12 parts, the compatibilizer being selected from at least one of maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, glycidyl ester grafted polyethylene, glycidyl ester grafted polypropylene, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer.
3. The composition of claim 2, further comprising at least one of an antioxidant, a toughening agent, and a coupling agent.
4. The composition according to claim 3, wherein the antioxidant is 0.2 to 0.8 parts by mass, and the antioxidant is at least one selected from the group consisting of n-stearyl β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, triethylene glycol bis [ β - (3-t-butyl-4-hydroxy-5-methylphenyl) propionate, 4' -thiobis (6-t-butyl-3-methylphenol), tris (2, 4-di-t-butylphenyl) phosphite, and tetrakis (2, 4-di-t-butylphenol) -4, 4-biphenyldiphosphite.
5. The composition according to claim 3, wherein the toughening agent is 0.5 to 3.0 parts by mass, and the toughening agent is at least one selected from the group consisting of polyoctene-maleic anhydride graft, ethylene-ethyl acrylate copolymer, polycaprolactone, and polybutyl adipate terephthalate.
6. The composition according to claim 3, wherein the coupling agent is 0.2 to 1 part by mass, and the coupling agent is at least one selected from the group consisting of silane coupling agent KH550 and phenylaminomethyltrimethoxysilane.
7. The composition of claim 1, further comprising a colored colorant other than black.
8. The composition of claim 7, wherein the boron nitride nanoplatelets have a particle size of 300-500nm.
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