CN112051632A - High-brightness black glass bead type license plate grade reflective film and preparation method thereof - Google Patents
High-brightness black glass bead type license plate grade reflective film and preparation method thereof Download PDFInfo
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- CN112051632A CN112051632A CN202011063939.4A CN202011063939A CN112051632A CN 112051632 A CN112051632 A CN 112051632A CN 202011063939 A CN202011063939 A CN 202011063939A CN 112051632 A CN112051632 A CN 112051632A
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Abstract
The invention discloses a high-brightness black glass bead type license plate-level reflective film which sequentially comprises a transparent composite surface layer, a black bead-embedding layer, a focusing layer, an aluminum-plated layer, a back adhesive layer and a release layer from bottom to top, wherein the black bead-embedding layer comprises a black color layer and glass beads, the glass beads are embedded into the black color layer, the transparent composite surface layer comprises a first surface layer and a second surface layer, the thickness of the second surface layer is 20-30% of the particle size of the glass beads, the sum of the thicknesses of the black color layer and the second surface layer is 60-80% of the particle size of the glass beads, the glass beads are sunk into the second surface layer, and the bottoms of the glass beads are in contact with the first surface layer. The glass beads are sunk into the second surface layer and are in contact with the first surface layer, so that the black color layer does not influence light to be transmitted to the glass beads, the defect that the black color layer is remained between the glass beads and the surface layer in the prior art is overcome, and the reflective brightness performance of the reflective glass bead is enhanced.
Description
Technical Field
The invention relates to the field of reflective films, in particular to a high-brightness black glass bead type license plate grade reflective film and a preparation method thereof.
Background
Nowadays, the preference of each country for the appearance, color and material of the license plate is different, the black license plate is deeply loved by people all the time, the black color is darker and is easy to attract attention, and therefore, the black reflective film is more and more applied in the field of license plates. However, the black color layer of the existing black license plate film is on the surface layer, and light is difficult to spread to the microbeads, so that the reflection brightness of the black license plate film is low, and the diversified application of the black license plate is limited.
Disclosure of Invention
Aiming at the defect of low reflective brightness of a black license plate film in the prior art, the invention provides a novel high-brightness black glass bead type license plate grade reflective film and a preparation method thereof.
In order to solve the technical problems, the invention is realized by the following technical scheme:
the utility model provides a high brightness black glass bead type license plate level reflective membrane, from up including transparent composite surface layer, black plant pearl layer, focus layer, aluminized layer, gum layer, from the type layer down in proper order, it is from one of type paper, from type PET or CPP to follow the type layer, the gum layer is thermoplasticity acrylic acid pressure-sensitive adhesive, focus layer is one of polyester resin, polyurethane resin, acrylic resin, the black is planted the pearl layer and is included black colour layer, glass microballon, the glass microballon embedding black colour layer, transparent composite surface layer includes first surface layer, second surface layer, the thickness of first surface layer is 35 ~ 50 mu m, the thickness of second surface layer is 20 ~ 30% of glass microballon particle diameter, the thickness sum of black colour layer with the second surface layer is 60 ~ 80% of glass microballon particle diameter, the second surface layer is the thermoplasticity type, the glass beads are sunk into the second surface layer, and the bottoms of the glass beads are in contact with the first surface layer.
The transparent composite surface layer is a colorless transparent resin film, the focusing layer can enable light to have a better retro-reflection effect when the light penetrates through the black bead-implanted layer, so that higher light reflection brightness is obtained, the aluminum-plated layer can further improve the light reflection effect of the transparent composite surface layer, the back adhesive layer is used for bonding with a carrier, and the release layer has the effect of protecting the back adhesive layer.
The second surface layer is a thermoplastic surface layer, and the glass beads are sunk into the second surface layer and are in contact with the first surface layer, so that the black color layer does not influence light to be transmitted to the glass beads, and the reflective brightness of the reflective glass is enhanced. The invention overcomes the defect that a black color layer is remained between the glass beads and the surface layer in the prior art, thereby obviously enhancing the reflective brightness performance of the invention.
Preferably, the preparation method of the high-brightness black glass bead type license plate grade reflective film comprises the following steps:
q1: taking PET without corona treatment as a coating base material, wherein the temperature resistance value of the PET is 180-220 ℃, the heat shrinkage rate of the PET is less than 1.5%, and the thickness of the PET is 50-100 mu m;
q2: mixing resin A, trimer isocyanate A and methylcellulose, wherein the weight ratio of the resin A to the trimer isocyanate A to the methylcellulose is 100: 0.5-15: 3-8, fully stirring for 20-30 min at the rotation speed of 800-1000 rpm, coating the mixture on PET after stirring, placing the mixture in an oven at the temperature of 75-155 ℃, and drying for 5-8 min to obtain the first surface layer;
q3: mixing resin B, vinyl chloride-vinyl acetate copolymer and trimer isocyanate B, wherein the weight ratio of the resin B to the vinyl chloride-vinyl acetate copolymer to the trimer isocyanate B is 100: 10-15: 0.5-1.5, fully stirring for 20-30 min, wherein the stirring speed is 800-1000 rpm, coating the mixture on the first surface layer after stirring, placing the mixture in an oven at 75-155 ℃, and drying for 5-8 min to obtain a second surface layer;
q4: mixing black ink and a solvent, wherein the black ink comprises grinding resin, a dispersing agent and carbon black, and the weight ratio of the grinding resin, the dispersing agent, the carbon black and the solvent is 100: 5-10: 30-40: 40-50, fully stirring for 3-5 min, and filtering by using 200-mesh gauze after stirring to obtain black pigment;
q5: mixing resin C with the black pigment, fully stirring for 6-8 min, and then adding isocyanate and an organic tin catalyst, wherein the weight ratio of the resin C to the black pigment to the isocyanate to the organic tin catalyst is 100: 4-8: 0.5-15: 0.01-0.015, continuously stirring for 20-30 min, wherein the stirring speed is 800-1000 rpm, coating the mixture on the second surface layer after stirring, placing the mixture in an oven at 90-130 ℃, and drying for 2-3 min to obtain an incompletely dried black color layer;
q6: uniformly and compactly arranging glass beads on the black color layer by adopting a bead planting device, and then placing the black color layer in a drying oven at 110-150 ℃ for drying for 3-4 min to obtain a black bead planting layer;
q7: coating the resin D on the black bead-planting layer, and then placing the black bead-planting layer in an oven at 100-155 ℃ for drying for 8-10 min to obtain a focusing layer;
q8: adopting vacuum aluminizing equipment, setting the vacuum degree to be 133Pa, setting the coiling speed to be 100-150 m/min, setting the aluminum conveying speed to be 0.15-0.35 m/min, and forming an aluminized layer on the surface of the focusing layer after the vacuum aluminizing is finished;
q9: coating the thermoplastic acrylic pressure-sensitive adhesive on a release layer, placing the release layer in an oven at 90-120 ℃, and drying for 3-5 min to obtain a back adhesive layer;
q10: and (2) setting the compounding pressure to be 0.4-0.6 MPa by adopting a compounding device, compounding the back glue layer and the aluminum coating, peeling off the PET and the first surface layer, and rolling to obtain the high-brightness black glass bead type license plate grade reflective film.
In the step Q1, the PET with better temperature resistance is selected to ensure that the PET is not easy to deform and shrink in the coating process.
In the step Q2, the resin A, the tripolymer isocyanate A and the methyl cellulose are mixed and coated, and the mixture is dried at the temperature of 75-155 ℃ to prepare the first surface layer with smooth surface and no obvious bubbles. The resin A, the tripolymer isocyanate A and the methylcellulose are mixed, and the three can be fully crosslinked and cured in the high-temperature drying process, so that the first surface layer has better tensile strength, breaking strength performance and solvent resistance, and the strippability between the first surface layer and PET is better.
In the step Q3, the three resins of the resin B, the vinyl chloride-vinyl acetate copolymer and the tripolymer isocyanate B are mixed and fully stirred until the three resins are completely dissolved, so that the condition of generating gel in the subsequent reaction process can be avoided. The resin B, the vinyl chloride-vinyl acetate copolymer and the tripolymer isocyanate B are selected and mixed, so that the prepared second surface layer can be softened at high temperature, and when the glass beads are settled and enter the second surface layer after bead planting, the glass beads are continuously settled until contacting with the first surface layer due to the self gravity of the glass beads and the softening action of the second surface layer. In addition, the second surface layer prepared from the components has better adhesion fastness with the first surface layer.
In step Q4, the black ink and the solvent are mixed and stirred and filtered, thereby sufficiently dispersing the black ink.
In the step Q5, the black pigment and the resin C are mixed and stirred, and then the isocyanate and the organic tin catalyst are added, so that the black pigment can be completely dispersed in the resin C, the compatibility is better, and the uniformity of the coating color is ensured. And drying at 90-130 ℃ to enable the black color layer to reach a surface dry state, thereby being beneficial to the implantation and sedimentation of the subsequent glass beads. By adopting the formula of the resin C, the isocyanate and the organic tin catalyst, not only can the crosslinking reaction be accelerated, but also the adhesive property of the glass beads and the black color layer can be increased, and the tensile strength performance of the invention is improved.
In the step Q6, the glass beads are implanted into the black color layer and sufficiently dried to completely volatilize the solvent in the black color layer, thereby obtaining a uniform and dense black bead-implanted layer.
In the step Q7, the resin D is dried in an oven at 100-155 ℃ so that each component of the resin D is subjected to sufficient crosslinking curing reaction.
In the step Q8, vacuum aluminum plating is performed in a vacuum environment of 133Pa, so that an aluminum plating layer uniformly covering the focusing layer can be prepared after the aluminum wire is vaporized.
And in the step Q9, drying at 90-120 ℃ to fully cure the thermoplastic acrylic pressure-sensitive adhesive.
In the step Q10, the back adhesive layer and the aluminum-plated layer are sufficiently pressed under the composite pressure environment of 0.4-0.6 Mpa, so that air is discharged conveniently, and bubbles are not easy to generate.
Preferably, the high-brightness black glass bead type license plate grade reflective film has the particle size of 45-80 μm and the refractive index of 2.1-2.3.
The invention has better retro-reflection effect by selecting the glass beads with high refractive index, and the light has higher reflection brightness after passing through the glass beads and being reflected by the aluminum coating.
Preferably, in the above method for preparing a high-brightness black glass bead type license plate-grade reflective film, in step Q2, the resin a includes one or more of thermoplastic polyester resin, polyurethane resin, and acrylic resin.
The resin A has better stripping property to the first surface layer finally prepared.
Preferably, in step Q3, the resin B includes one or more of a thermoplastic polyester resin, a polyurethane resin, and an acrylic resin, the thermoplastic polyester resin has a glass transition temperature of 30 to 50 ℃, a molecular weight of 15000 to 25000Mw, and a hydroxyl value of 6mgKOHg to 10mgKOHg, the polyurethane resin has a shore hardness of 75 to 80, a melting temperature of 120 to 130 ℃, the acrylic resin has a molecular weight of 5000 to 6000Mw, a glass transition temperature of 65 to 70 ℃, the vinyl acetate resin is a ternary vinyl chloride-vinyl acetate resin, and the vinyl acetate resin has a vinyl acetate content of 10 to 15% and a hydroxyl value of 50mgKOH/g to 60 mgKOH/g.
The resin B is adopted to ensure that the finally prepared second surface layer has better adhesion fastness with the first surface layer.
Preferably, in step Q4, the method for preparing the high-brightness black glass bead type license plate-level reflective film includes that the solid content of the black ink is 30-40% and the color content is 15-20%, the grinding resin includes one or more of a ternary vinyl chloride-acetate resin, an acrylic resin, a polyester resin and a vinyl resin, the hydroxyl value of the grinding resin is 70 mgKOH/g-80 mgKOH/g, the dispersing agent is an anionic carboxylate dispersing agent, the carbon black is a common pigment channel method carbon black, the black color value My of the carbon black is 200-300, the oil absorption is 250g/100 g-350 g/100g, and the primary particle size is 20 nm-30 nm.
The selected carbon black with high chroma and small particle size can increase the color concentration of the black ink color and ensure that the black ink has better dispersion performance in the resin C, and the selected anionic ammonium carboxylate dispersant can avoid the phenomena of flocculation, precipitation and aggregation of the black ink, thereby ensuring that the compatibility and the glossiness of the black ink are better.
Preferably, in the above method for preparing a high-brightness black glass bead type license plate-grade reflective film, in step Q5, the resin C is one of polyester resin, polyurethane resin, and acrylic resin.
The resin C has better compatibility, so that the color of the finally prepared black color layer is more uniform.
Preferably, in the license plate-grade reflective film with high brightness and black glass beads, in step Q7, the resin D is one of polyester resin, polyurethane resin and acrylic resin.
The focusing layer is made of one of polyester resin, polyurethane resin and acrylic resin, so that the strength and the elongation of the focusing layer are better, and the focusing layer is not easy to deform and crack in the processing deformation process.
Preferably, in the step Q4, the solvent is one of a lipid solvent, a benzene solvent, and a ketone solvent.
One of lipid solvent, benzene solvent and ketone solvent is used as the solvent of the invention, so that the invention has better volatilization trapezoidal temperature, the black ink has better compatibility, and the dispersion uniformity of the black ink in the resin C is also improved.
Drawings
FIG. 1 is a schematic structural view of a high-brightness black glass bead type license plate grade reflective film according to the present invention.
Detailed Description
The invention will be described in further detail below with reference to the accompanying figure 1 and the detailed description, but they are not intended to limit the invention:
example 1
The utility model provides a high brightness black glass bead type license plate level reflective membrane, from up including transparent composite surface course 1, black plant pearl layer 2, focusing layer 3, aluminized layer 4, gum layer 5, from type layer 6 down in proper order, from type layer 6 for from type paper, from type PET or CPP in one kind, gum layer 5 is thermoplasticity acrylic acid pressure-sensitive adhesive, focusing layer 3 is one kind among polyester resin, polyurethane resin, acrylic resin, black plant pearl layer 2 includes black colour layer 21, glass microballon 22 imbeds black colour layer 21, transparent composite surface course 1 includes first surface course 11, second surface course 12, the thickness of first surface course 11 is 35 mu m, the thickness of second surface course 12 is 20% of the glass microballon 22 particle diameter, the thickness sum of black colour layer 21 with second surface course 12 is 60% of glass microballon 22 particle diameter, the second face layer 12 is a thermoplastic face layer, the glass beads 22 sink into the second face layer 12, and the bottoms of the glass beads 22 are in contact with the first face layer 11.
Preferably, the method comprises the following steps:
q1: taking PET without corona treatment as a coating base material, wherein the temperature resistance value of the PET is 180 ℃, the heat shrinkage rate is less than 1.5%, and the thickness is 50 μm;
q2: mixing resin A, trimer isocyanate A and methylcellulose, wherein the weight ratio of the resin A to the trimer isocyanate A to the methylcellulose is 100: 0.5: 3, fully stirring for 20min at the rotation speed of 800 revolutions per minute, coating the mixture on PET after stirring, placing the mixture in a 75 ℃ oven, and drying for 5min to obtain the first surface layer 11;
q3: mixing resin B, vinyl chloride-vinyl acetate copolymer and trimer isocyanate B, wherein the weight ratio of the resin B to the vinyl chloride-vinyl acetate copolymer to the trimer isocyanate B is 100: 10: 0.5, fully stirring for 20min at the rotation speed of 800 revolutions per minute, coating the mixture on the first surface layer 11 after stirring, then placing the mixture in a 75 ℃ oven, and drying for 5min to obtain a second surface layer 12;
q4: mixing black ink and a solvent, wherein the black ink comprises grinding resin, a dispersing agent and carbon black, and the weight ratio of the grinding resin, the dispersing agent, the carbon black and the solvent is 100: 5: 30: 40, fully stirring for 3min, and filtering by using 200-mesh gauze after stirring to obtain black pigment;
q5: mixing resin C with the black pigment, fully stirring for 6min, and then adding isocyanate and an organic tin catalyst, wherein the weight ratio of the resin C to the black pigment to the isocyanate to the organic tin catalyst is 100: 4: 0.5: 0.01, continuously stirring for 20min at the rotating speed of 800 rpm, coating the mixture on the second surface layer 12 after stirring, and drying the mixture in a drying oven at the temperature of 90 ℃ for 2min to obtain an incompletely dried black color layer 21;
q6: uniformly and compactly arranging the glass beads 22 on the black color layer 21 by adopting a bead planting device, and then placing the glass beads in a drying oven at 110 ℃ for drying for 3min to obtain a black bead planting layer 2;
q7: coating the resin D on the black bead-planting layer 2, and then placing the resin D in a drying oven at 100 ℃ for drying for 8min to obtain a focusing layer 3;
q8: adopting vacuum aluminizing equipment, setting the vacuum degree to be 133Pa, the coiling speed to be 100m/min and the aluminum conveying speed to be 0.15m/min, and forming an aluminized layer 4 on the surface of the focusing layer 3 after the vacuum aluminizing is finished;
q9: taking a release layer 6, coating the thermoplastic acrylic pressure-sensitive adhesive on the release layer 6, placing in a drying oven at 90 ℃, and drying for 3min to obtain a back adhesive layer 5;
q10: and setting the composite pressure to be 0.4MPa by adopting a composite device, compounding the back glue layer 5 and the aluminum coating layer 4, peeling off the PET and the first surface layer 11, and rolling to obtain the high-brightness black glass bead type license plate grade reflective film.
Preferably, the glass beads 22 have a particle size of 45 μm and a refractive index of 2.1.
Preferably, in the step Q2, the resin a comprises one or more of thermoplastic polyester resin, polyurethane resin and acrylic resin.
Preferably, in step Q3, the resin B comprises one or more of a thermoplastic polyester resin, a polyurethane resin and an acrylic resin, the thermoplastic polyester resin has a glass transition temperature of 30 ℃, a molecular weight of 15000Mw and a hydroxyl value of 6mgKOHg, the polyurethane resin has a shore hardness of 75, a melting temperature of 120 ℃, the acrylic resin has a molecular weight of 5000Mw and a glass transition temperature of 65 ℃, the vinyl chloride-vinyl acetate resin is a ternary vinyl chloride-vinyl acetate resin, and the vinyl chloride-vinyl acetate resin has a vinyl acetate content of 10% and a hydroxyl value of 50 mgKOH/g.
Preferably, in step Q4, the black ink has a solid content of 30% and a color content of 15%, the grinding resin includes one or more of a ternary vinyl chloride-acetate copolymer resin, an acrylic resin, a polyester resin, and a vinyl resin, the hydroxyl value of the grinding resin is 70mgKOH/g, the dispersant is an anionic ammonium carboxylate dispersant, the carbon black is a common pigment channel black, the black color degree My of the carbon black is 200, the oil absorption is 250g/100g, and the primary particle size is 20 nm.
Preferably, in step Q5, the resin C is one of polyester resin, polyurethane resin and acrylic resin.
Preferably, in step Q7, the resin D is one of a polyester resin, a polyurethane resin, and an acrylic resin.
Preferably, in step Q4, the solvent is one of a lipid solvent, a benzene solvent, and a ketone solvent.
Example 2
The utility model provides a high brightness black glass bead type license plate level reflective membrane, from up including transparent composite surface course 1, black plant pearl layer 2, focusing layer 3, aluminized layer 4, gum layer 5, from type layer 6 down in proper order, from type layer 6 for from type paper, from type PET or CPP in one kind, gum layer 5 is thermoplasticity acrylic acid pressure-sensitive adhesive, focusing layer 3 is one kind among polyester resin, polyurethane resin, acrylic resin, black plant pearl layer 2 includes black colour layer 21, glass microballon 22 imbeds black colour layer 21, transparent composite surface course 1 includes first surface course 11, second surface course 12, the thickness of first surface course 11 is 50 mu m, the thickness of second surface course 12 is 30% of the glass microballon 22 particle diameter, the thickness sum of black colour layer 21 with the second surface course 12 is 80% of glass microballon 22 particle diameter, the second face layer 12 is a thermoplastic face layer, the glass beads 22 sink into the second face layer 12, and the bottoms of the glass beads 22 are in contact with the first face layer 11.
Preferably, the method comprises the following steps:
q1: taking PET without corona treatment as a coating base material, wherein the temperature resistance value of the PET is 220 ℃, the heat shrinkage rate is less than 1.5%, and the thickness is 100 mu m;
q2: mixing resin A, trimer isocyanate A and methylcellulose, wherein the weight ratio of the resin A to the trimer isocyanate A to the methylcellulose is 100: 15: 8, fully stirring for 30min at the rotation speed of 1000 rpm, coating the mixture on PET after stirring, placing the mixture in an oven at the temperature of 155 ℃, and drying for 8min to obtain the first surface layer 11;
q3: mixing resin B, vinyl chloride-vinyl acetate copolymer and trimer isocyanate B, wherein the weight ratio of the resin B to the vinyl chloride-vinyl acetate copolymer to the trimer isocyanate B is 100: 15: 1.5, fully stirring for 30min at the rotation speed of 1000 rpm, coating the mixture on the first surface layer 11 after stirring, then placing the mixture in an oven at 155 ℃, and drying for 8min to obtain a second surface layer 12;
q4: mixing black ink and a solvent, wherein the black ink comprises grinding resin, a dispersing agent and carbon black, and the weight ratio of the grinding resin, the dispersing agent, the carbon black and the solvent is 100: 10: 40: 50, fully stirring for 5min, and filtering by using 200-mesh gauze after stirring to obtain black pigment;
q5: mixing resin C with the black pigment, fully stirring for 8min, and then adding isocyanate and an organic tin catalyst, wherein the weight ratio of the resin C to the black pigment to the isocyanate to the organic tin catalyst is 100: 8: 15: 0.015, continuously stirring for 30min, wherein the stirring speed is 1000 rpm, coating the mixture on the second surface layer 12 after the stirring is finished, and then placing the mixture in a drying oven at the temperature of 130 ℃ for drying for 3min to obtain an incompletely dried black color layer 21;
q6: uniformly and compactly arranging the glass beads 22 on the black color layer 21 by adopting a bead planting device, and then drying in a drying oven at 150 ℃ for 4min to obtain a black bead planting layer 2;
q7: coating the resin D on the black bead-planting layer 2, and then placing the resin D in an oven at 155 ℃ for drying for 10min to obtain a focusing layer 3;
q8: adopting vacuum aluminizing equipment, setting the vacuum degree to be 133Pa, the coiling speed to be 150m/min and the aluminum conveying speed to be 0.35m/min, and forming an aluminized layer 4 on the surface of the focusing layer 3 after the vacuum aluminizing is finished;
q9: taking a release layer 6, coating the thermoplastic acrylic pressure-sensitive adhesive on the release layer 6, then placing the release layer in a drying oven at 120 ℃, and drying for 5min to obtain a back adhesive layer 5;
q10: and setting the compounding pressure to be 0.6MPa by adopting a compounding device, compounding the back glue layer 5 and the aluminum coating layer 4, peeling off the PET and the first surface layer 11, and rolling to obtain the high-brightness black glass bead type license plate grade reflective film.
Preferably, the glass beads 22 have a particle size of 80 μm and a refractive index of 2.3.
Preferably, in the step Q2, the resin a comprises one or more of thermoplastic polyester resin, polyurethane resin and acrylic resin.
Preferably, in step Q3, the resin B includes one or more of a thermoplastic polyester resin, a polyurethane resin, and an acrylic resin, the thermoplastic polyester resin has a glass transition temperature of 50 ℃, a molecular weight of 25000Mw, and a hydroxyl value of 10mgKOHg, the polyurethane resin has a shore hardness of 80, a melting temperature of 130 ℃, the acrylic resin has a molecular weight of 6000Mw, and a glass transition temperature of 70 ℃, the vinyl chloride-vinyl acetate resin is a ternary vinyl chloride-vinyl acetate resin, and the vinyl acetate resin has a vinyl acetate content of 15% and a hydroxyl value of 60 mgKOH/g.
Preferably, in step Q4, the black ink has a solid content of 40% and a color content of 20%, the grinding resin includes one or more of a ternary vinyl chloride-acetate copolymer resin, an acrylic resin, a polyester resin, and a vinyl resin, the hydroxyl value of the grinding resin is 80mgKOH/g, the dispersant is an anionic carboxylate dispersant, the carbon black is a common pigment channel black, and the black color degree My of the carbon black is 300, the oil absorption is 350g/100g, and the primary particle size is 30 nm.
Preferably, in step Q5, the resin C is one of polyester resin, polyurethane resin and acrylic resin.
Preferably, in step Q7, the resin D is one of a polyester resin, a polyurethane resin, and an acrylic resin.
Preferably, in step Q4, the solvent is one of a lipid solvent, a benzene solvent, and a ketone solvent.
Example 3
The utility model provides a high brightness black glass bead type license plate level reflective membrane, from up including transparent composite surface course 1, black plant pearl layer 2, focusing layer 3, aluminized layer 4, gum layer 5, from type layer 6 down in proper order, from type layer 6 for from type paper, from type PET or CPP in one kind, gum layer 5 is thermoplasticity acrylic acid pressure-sensitive adhesive, focusing layer 3 is one kind among polyester resin, polyurethane resin, acrylic resin, black plant pearl layer 2 includes black colour layer 21, glass microballon 22 imbeds black colour layer 21, transparent composite surface course 1 includes first surface course 11, second surface course 12, the thickness of first surface course 11 is 45 mu m, the thickness of second surface course 12 is 25% of the glass microballon 22 particle diameter, the thickness sum of black colour layer 21 with second surface course 12 is 70% of glass microballon 22 particle diameter, the second face layer 12 is a thermoplastic face layer, the glass beads 22 sink into the second face layer 12, and the bottoms of the glass beads 22 are in contact with the first face layer 11.
Preferably, the method comprises the following steps:
q1: taking PET without corona treatment as a coating base material, wherein the temperature resistance value of the PET is 200 ℃, the heat shrinkage rate is less than 1.5%, and the thickness is 80 μm;
q2: mixing resin A, trimer isocyanate A and methylcellulose, wherein the weight ratio of the resin A to the trimer isocyanate A to the methylcellulose is 100: 8: 5.5, fully stirring for 25min at the rotation speed of 900 revolutions per minute, coating the mixture on PET after stirring, placing the mixture in a drying oven at the temperature of 115 ℃, and drying for 7min to obtain the first surface layer 11;
q3: mixing resin B, vinyl chloride-vinyl acetate copolymer and trimer isocyanate B, wherein the weight ratio of the resin B to the vinyl chloride-vinyl acetate copolymer to the trimer isocyanate B is 100: 12.5: 1, fully stirring for 25min at the rotation speed of 900 revolutions per minute, coating the mixture on the first surface layer 11 after stirring, then placing the mixture in an oven at the temperature of 115 ℃, and drying for 7min to obtain a second surface layer 12;
q4: mixing black ink and a solvent, wherein the black ink comprises grinding resin, a dispersing agent and carbon black, and the weight ratio of the grinding resin, the dispersing agent, the carbon black and the solvent is 100: 7.5: 35: 45, fully stirring for 4min, and filtering by using 200-mesh gauze after stirring to obtain black pigment;
q5: mixing resin C with the black pigment, fully stirring for 7min, and then adding isocyanate and an organic tin catalyst, wherein the weight ratio of the resin C to the black pigment to the isocyanate to the organic tin catalyst is 100: 6: 8: 0.012, continuously stirring for 25min at the rotating speed of 900 rpm, coating the mixture on the second surface layer 12 after stirring, and drying the mixture in a drying oven at the temperature of 110 ℃ for 2.5min to obtain a black color layer 21 which is not completely dried;
q6: uniformly and compactly arranging the glass beads 22 on the black color layer 21 by adopting a bead planting device, and then placing the glass beads in a drying oven at 130 ℃ for drying for 3.5min to obtain a black bead planting layer 2;
q7: coating the resin D on the black bead-planting layer 2, and then placing the resin D in a drying oven at 125 ℃ for drying for 9min to obtain a focusing layer 3;
q8: adopting vacuum aluminizing equipment, setting the vacuum degree to be 133Pa, the coiling speed to be 125m/min and the aluminum conveying speed to be 0.25m/min, and forming an aluminized layer 4 on the surface of the focusing layer 3 after the vacuum aluminizing is finished;
q9: taking a release layer 6, coating the thermoplastic acrylic pressure-sensitive adhesive on the release layer 6, then placing the release layer in a drying oven at 105 ℃, and drying for 4min to obtain a back adhesive layer 5;
q10: and setting the composite pressure to be 0.5MPa by adopting a composite device, compounding the back glue layer 5 and the aluminum coating layer 4, peeling off the PET and the first surface layer 11, and rolling to obtain the high-brightness black glass bead type license plate grade reflective film.
Preferably, the glass beads 22 have a particle size of 65 μm and a refractive index of 2.2.
Preferably, in the step Q2, the resin a comprises one or more of thermoplastic polyester resin, polyurethane resin and acrylic resin.
Preferably, in step Q3, the resin B comprises one or more of a thermoplastic polyester resin, a polyurethane resin and an acrylic resin, the thermoplastic polyester resin has a glass transition temperature of 40 ℃, a molecular weight of 20000Mw and a hydroxyl value of 8mgKOHg, the polyurethane resin has a shore hardness of 78, a melting temperature of 125 ℃, the acrylic resin has a molecular weight of 5500Mw and a glass transition temperature of 68 ℃, the vinyl chloride-vinyl acetate resin is a ternary vinyl chloride-vinyl acetate resin, and the vinyl acetate resin has a vinyl acetate content of 12% and a hydroxyl value of 55 mgKOH/g.
Preferably, in step Q4, the black ink has a solid content of 35% and a color content of 17.5%, the grinding resin includes one or more of a ternary vinyl chloride-acetate resin, an acrylic resin, a polyester resin, and a vinyl resin, the hydroxyl value of the grinding resin is 75mgKOH/g, the dispersant is an anionic ammonium carboxylate dispersant, the carbon black is a common pigment channel black, and the black color degree My value of the carbon black is 250, the oil absorption is 300g/100g, and the primary particle size is 25 nm.
Preferably, in step Q5, the resin C is one of polyester resin, polyurethane resin and acrylic resin.
Preferably, in step Q7, the resin D is one of a polyester resin, a polyurethane resin, and an acrylic resin.
Preferably, in step Q4, the solvent is one of a lipid solvent, a benzene solvent, and a ketone solvent.
Example 4
Taking the high-brightness black glass bead type license plate-grade reflective film obtained in each embodiment, taking the existing black 680 type glass bead type license plate-grade reflective film as a comparative example, and testing the chromaticity performance, the retroreflection performance, the breaking strength and the breaking elongation performance, wherein the testing method comprises the following steps:
firstly, testing the chromaticity performance: testing the surface color according to the method specified in GA 666-2018;
evaluation criteria: LAB using a colorimeter represents the colorimetric value of the sample, where the L value represents black and white and the smaller the L value, the darker the color of the sample.
Secondly, testing the retroreflection performance: retroreflection performance tested using U.S. GM932 retroreflection test instrument;
evaluation criteria: 0.2/5 is the main angle of retroreflection performance, the better the brightness at this angle, the higher the value, the better the retroreflection performance of the sample.
Thirdly, testing the breaking strength: placing the sample in an environment with the temperature of 23% +/-1% and the temperature of 50% +/-5% for curing for 12 hours, and then testing the fracture strength performance of the sample by using a universal tensile machine;
evaluation criteria: in order to meet the stamping performance of the automobile license plate, the license plate film needs to meet certain tensile strength performance, and according to the requirements in GA666, the tensile strength of 10% tensile strain of the license plate film is not less than 15N, and the breaking strength is not less than 25N.
Fourthly, testing the breaking elongation: placing the sample in an environment with the temperature of 23 +/-1% and the temperature of 50 +/-5% for curing for 12 hours, and testing the fracture strength performance of the sample by using a universal tensile machine;
evaluation criteria: in order to meet the stamping performance of the automobile license plate, the license plate film needs to meet certain tensile performance, and the fracture tensile stress of the license plate film is not less than 90 percent according to the requirements in GA 666-2018.
The high-brightness black glass bead type license plate grade reflective film and the comparative example performance parameters obtained by the embodiments of the invention are shown in the following table 1:
TABLE 1
| Sample (I) | Color properties | Retroreflection performance | Breaking strength | Elongation at break |
| Example 1 | L＝9.25 | 0.2/5 45 | ≥15/25 | ≥90％ |
| Example 2 | L＝8.30 | 0.2/5 40 | ≥15/25 | ≥90％ |
| Example 3 | L＝9.02 | 0.2/5 43 | ≥15/25 | ≥90％ |
| Comparative example 1 | L＝10.11 | 0.2/5 30 | ≥15/25 | ≥90％ |
In summary, the above-mentioned embodiments are only preferred embodiments of the present invention, and all equivalent changes and modifications made within the scope of the claims of the present invention should be covered by the present invention.
Claims (9)
1. A high-brightness black glass bead type license plate grade reflective film is characterized in that: from up including transparent composite surface layer (1), black pearl layer (2), focusing layer (3), aluminized layer (4), gum layer (5), from type layer (6) down in proper order, be from type layer (6) for from type paper, from one kind in type PET or CPP, gum layer (5) are thermoplasticity acrylic acid pressure-sensitive adhesive, focus layer (3) are one kind among polyester resin, polyurethane resin, the acrylic resin, black pearl layer (2) are planted including black colour layer (21), glass microballon (22) embedding black colour layer (21), transparent composite surface layer (1) includes first surface course (11), second surface course (12), the thickness of first surface course (11) is 35 ~ 50 mu m, the thickness of second surface course (12) does the 20 ~ 30% of glass microballon (22) particle diameter, black colour layer (21) with the thickness sum of second surface course (12) does glass microballon (12) do 22) 60-80% of particle size, second surface course (12) are the thermoplastic profile layer, glass bead (22) sink into second surface course (12), the bottom of glass bead (22) with first surface course (11) contact.
2. The method for preparing the high-brightness black glass bead type license plate grade reflective film according to claim 1, which is characterized in that: the method comprises the following steps:
q1: taking PET without corona treatment as a coating base material, wherein the temperature resistance value of the PET is 180-220 ℃, the heat shrinkage rate of the PET is less than 1.5%, and the thickness of the PET is 50-100 mu m;
q2: mixing resin A, trimer isocyanate A and methylcellulose, wherein the weight ratio of the resin A to the trimer isocyanate A to the methylcellulose is 100: 0.5-15: 3-8, fully stirring for 20-30 min at the rotation speed of 800-1000 rpm, coating the mixture on PET after stirring, placing the mixture in an oven at the temperature of 75-155 ℃, and drying for 5-8 min to obtain the first surface layer (11);
q3: mixing resin B, vinyl chloride-vinyl acetate copolymer and trimer isocyanate B, wherein the weight ratio of the resin B to the vinyl chloride-vinyl acetate copolymer to the trimer isocyanate B is 100: 10-15: 0.5-1.5, fully stirring for 20-30 min at the rotation speed of 800-1000 rpm, coating the mixture on the first surface layer (11) after stirring, placing the mixture in an oven at the temperature of 75-155 ℃, and drying for 5-8 min to obtain a second surface layer (12);
q4: mixing black ink and a solvent, wherein the black ink comprises grinding resin, a dispersing agent and carbon black, and the weight ratio of the grinding resin, the dispersing agent, the carbon black and the solvent is 100: 5-10: 30-40: 40-50, fully stirring for 3-5 min, and filtering by using 200-mesh gauze after stirring to obtain black pigment;
q5: mixing resin C with the black pigment, fully stirring for 6-8 min, and then adding isocyanate and an organic tin catalyst, wherein the weight ratio of the resin C to the black pigment to the isocyanate to the organic tin catalyst is 100: 4-8: 0.5-15: 0.01-0.015, continuously stirring for 20-30 min, wherein the stirring speed is 800-1000 r/min, coating the mixture on the second surface layer (12) after stirring, placing the mixture in a drying oven at 90-130 ℃, and drying for 2-3 min to obtain an incompletely dried black color layer (21);
q6: uniformly and compactly arranging the glass beads (22) on the black color layer (21) by adopting a bead planting device, and then drying the glass beads in a drying oven at the temperature of 110-150 ℃ for 3-4 min to obtain a black bead planting layer (2);
q7: coating the resin D on the black bead-planting layer (2), and then placing the black bead-planting layer in an oven at 100-155 ℃ for drying for 8-10 min to obtain a focusing layer (3);
q8: adopting vacuum aluminizing equipment, setting the vacuum degree to be 133Pa, setting the coiling speed to be 100-150 m/min, setting the aluminum conveying speed to be 0.15-0.35 m/min, and forming an aluminized layer (4) on the surface of the focusing layer (3) after the vacuum aluminizing is finished;
q9: taking a release layer (6), coating the thermoplastic acrylic pressure-sensitive adhesive on the release layer (6), and then placing the release layer in a drying oven at 90-120 ℃ for drying for 3-5 min to obtain a back adhesive layer (5);
q10: and (2) setting the composite pressure to be 0.4-0.6 MPa by adopting a composite device, compounding the back glue layer (5) and the aluminum-plated layer (4), peeling off the PET and the first surface layer (11), and rolling to obtain the high-brightness black glass bead type license plate-level reflective film.
3. The high-brightness black glass bead type license plate-grade reflective film according to claim 1, wherein: the particle size of the glass beads (22) is 45-80 microns, and the refractive index is 2.1-2.3.
4. The method for preparing the high-brightness black glass bead type license plate grade reflective film according to claim 2, which is characterized in that: in step Q2, the resin a includes one or more of thermoplastic polyester resin, polyurethane resin, and acrylic resin.
5. The method for preparing the high-brightness black glass bead type license plate grade reflective film according to claim 2, which is characterized in that: in the step Q3, the resin B comprises one or more of thermoplastic polyester resin, polyurethane resin and acrylic resin, the glass transition temperature of the thermoplastic polyester resin is 30-50 ℃, the molecular weight is 15000-25000 Mw, the hydroxyl value is 6 mgKOHg-10 mgKOHg, the Shore hardness of the polyurethane resin is 75-80, the melting temperature is 120-130 ℃, the molecular weight of the acrylic resin is 5000-6000 Mw, the glass transition temperature is 65-70 ℃, the vinyl chloride-vinyl acetate resin is ternary vinyl chloride-vinyl acetate resin, the vinyl acetate content of the vinyl chloride-vinyl acetate resin is 10-15%, and the hydroxyl value is 50 mgKOH/g-60 mgKOH/g.
6. The method for preparing the high-brightness black glass bead type license plate grade reflective film according to claim 2, which is characterized in that: in the step Q4, the solid content of the black ink is 30-40%, the color content is 15-20%, the grinding resin comprises one or more of ternary vinyl chloride-acetate resin, acrylic resin, polyester resin and vinyl resin, the hydroxyl value of the grinding resin is 70 mgKOH/g-80 mgKOH/g, the dispersing agent is an anionic ammonium carboxylate dispersing agent, the carbon black is common pigment channel method carbon black, the black color My value of the carbon black is 200-300, the oil absorption is 250g/100 g-350 g/100g, and the primary particle size is 20 nm-30 nm.
7. The method for preparing the high-brightness black glass bead type license plate grade reflective film according to claim 2, which is characterized in that: in the step Q5, the resin C is one of polyester resin, polyurethane resin, and acrylic resin.
8. The high-brightness black glass bead type license plate-grade reflective film according to claim 1, wherein: in the step Q7, the resin D is one of polyester resin, polyurethane resin, and acrylic resin.
9. The high-brightness black glass bead type license plate-grade reflective film according to claim 1, wherein: in the step Q4, the solvent is one of a lipid solvent, a benzene solvent, and a ketone solvent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114114491A (en) * | 2021-11-11 | 2022-03-01 | 凯丰集团有限公司 | Preparation method of dyeing-resistant and light-reflecting cut film |
| CN114150511A (en) * | 2021-12-08 | 2022-03-08 | 浙江龙游道明光学有限公司 | Long afterglow washable light-storing cloth |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114114491A (en) * | 2021-11-11 | 2022-03-01 | 凯丰集团有限公司 | Preparation method of dyeing-resistant and light-reflecting cut film |
| CN114114491B (en) * | 2021-11-11 | 2024-02-13 | 凯丰集团有限公司 | Preparation method of dyeing-resistant reflective shredding film |
| CN114150511A (en) * | 2021-12-08 | 2022-03-08 | 浙江龙游道明光学有限公司 | Long afterglow washable light-storing cloth |
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