Durable road marking paint and method of making same

Abstract

The application relates to a durable road marking paint and a preparation method thereof, and belongs to the technical field of paints, and comprises an A component and a B component with a mass ratio of (4-5):(95-96), wherein the A component comprises, in mass fraction, 15-30 parts of polyvinyl chloride, 15-20 parts of styrene-acrylic acid resin, 5-10 parts of acrylonitrile-butadiene-styrene copolymer, 5-10 parts of polyetherimide, 20-30 parts of silane coupling agent and 15-30 parts of polyether modified organosilicon; and the B component comprises 10-15 parts of petroleum resin, 5-10 parts of polytetrafluoroethylene, 5-8 parts of rutile titanium dioxide, 38-42 parts of superfine calcium carbonate powder and 5-10 parts of nano spherical silicon powder and 18-20 parts of reflective glass microbeads. The road marking paint can improve the durability of the paint, improve the overall reflective performance of the material, and prolong the service life of the road marking.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of coatings, and particularly relates to a durable road marking paint and a preparation method thereof. BACKGROUND

[0002] Road marking refers to various lines, arrows, words, patterns and the like drawn on roads by paint, which is used for guiding traffic, regulating traffic order and guaranteeing traffic safety. They are an important part of traffic facilities, which can provide good conditioned reflex for drivers and pedestrians, effectively reduce accidents and improve driving efficiency.

[0003] Road marking paint is paint used for marking road marking, mainly including thermoplastic paint, two-component paint, solvent-based paint and the like. Although road marking and marking paint play an important role in traffic management, there are still some problems:

[0004] 1. Aging, the font and color of the mark and the marking line may become unclear, leading to misleading and ambiguous situations.

[0005] 2. Poor reflective effect, when driving at night or in rainy weather, the reflective effect of the mark and the marking line is poor, the readability and visibility are greatly reduced, and the risk of traffic accidents is increased.

[0006] 3. Poor durability, prone to problems such as blistering, hollowing, cracking, peeling, falling off, discoloration, color change, yellowing and the like. SUMMARY

[0007] The application aims to provide a durable road marking paint and a preparation method thereof, which can improve the durability of road marking and improve the reflective performance of the marking line.

[0008] The application adopts the following technical scheme to achieve the purpose:

[0009] A durable road marking paint comprises A component and B component with a mass ratio of (4-5):(95-96), wherein the A component comprises, in terms of mass fraction, polyvinyl chloride 15-30 parts, styrene-acrylic resin 15-20 parts, acrylonitrile-butadiene-styrene copolymer 5-10 parts, polyetherimide 5-10 parts, silane coupling agent 20-30 parts and polyether modified silicone 15-30 parts; and the B component comprises petroleum resin 10-15 parts, polytetrafluoroethylene 5-10 parts, rutile titanium dioxide 5-8 parts, ultra-fine calcium carbonate powder 38-42 parts, nano spherical silica powder 5-10 parts and reflective glass microbeads 18-20 parts.

[0010] Further, the reflective glass microbeads are surface-coated and pretreated by hyperbranched polyurethane.

[0011] Further, the surface coating pretreatment comprises the following steps:

[0012] S1. After cleaning and drying the reflective glass beads, place them in a low-temperature plasma treatment machine, vacuumize to 400-500 Pa, introduce oxygen, and treat for 3-5 min;

[0013] S2. Dilute the hyperbranched polyurethane resin with a solvent, add aluminum powder, then spray it on the surface of the reflective glass beads treated in step S1, with a spraying thickness of 10-20 μm, solidify, polish, and obtain reflective glass beads coated with hyperbranched polyurethane resin on the surface.

[0014] Further, in step S1, the oxygen flow rate is 50-100 sccm.

[0015] Further, in step S2, the solvent is ethanol or acetone, diluted to a solid content of 60-70%, and the amount of aluminum powder added is 2-3% of the hyperbranched polyurethane resin.

[0016] Further, the particle size of the superfine calcium carbonate powder is 100-200 mesh; the SiO2 content in the nanoscale spherical silica powder is ≥99.6%; and the particle size of the reflective glass beads is 50-60 μm.

[0017] Further, the silane coupling agent is one or any combination of silane coupling agent KH550, silane coupling agent KH560, silane coupling agent KH570, and silane coupling agent KH792.

[0018] A preparation method of a durable road marking paint, comprising the following steps:

[0019] (1) Prepare raw materials: according to mass fraction, prepare 15-30 parts of polyvinyl chloride, 15-20 parts of styrene-acrylic resin, 5-10 parts of acrylonitrile-butadiene-styrene copolymer, 5-10 parts of polyetherimide, 20-30 parts of silane coupling agent, 15-30 parts of polyether-modified silicone, 10-15 parts of petroleum resin, 5-10 parts of polytetrafluoroethylene, 5-8 parts of rutile titanium dioxide, 38-42 parts of superfine calcium carbonate powder, 5-10 parts of nanoscale spherical silica powder, and 18-20 parts of reflective glass beads;

[0020] (2) Prepare component B: perform surface coating pretreatment on the reflective glass beads with hyperbranched polyurethane, then mix the rutile titanium dioxide, superfine calcium carbonate powder, and nanoscale spherical silica powder uniformly; mix the petroleum resin and polytetrafluoroethylene uniformly, melt them, then uniformly add the mixed powder to obtain component B;

[0021] (3) Preparation of A component: polyvinyl chloride, styrene-acrylic resin, acrylonitrile-butadiene-styrene copolymer, polyetherimide, silane coupling agent, polyether modified silicone are mixed uniformly, heated and stirred until the solid components are completely melted, then sheared, cooled and ground to obtain A component;

[0022] (4) A component is mixed with B component at a mass ratio of (4-5):(95-96), and stirred uniformly at 160-180 DEG C to obtain the product.

[0023] The present application has the following advantages:

[0024] The road marking paint of the present application can improve the durability of the paint, and also can improve the overall reflective performance of the material, prolong the service life of the road marking.

[0025] The present application can improve the adhesion and adhesion of the reflective glass microbeads and the primer by coating a layer of hyperbranched polyurethane on the surface of the reflective glass microbeads and adding aluminum powder. The surface of the microbeads can be treated by plasma technology to improve the chemical properties and physical structure of the surface, increase the surface activity, and improve the adhesion of the resin. The reflective property of the reflective glass microbeads can be improved after low-temperature plasma treatment. The surface smoothness and glossiness of the material can be improved by polishing the cured reflective glass microbeads, thereby ensuring the reflective performance. The hyperbranched polyurethane in the present application is obtained by grafting polyurethane prepolymer onto hyperbranched polymer.

[0026] The styrene-acrylic resin in the present application can improve the adhesion, enhance the weather resistance, provide good mechanical properties, and improve the chemical corrosion resistance in the hot melt type paint.

[0027] The polyether modified silicone in the present application can improve the wettability of the paint on the substrate, prevent surface defects such as shrinkage and edge shrinkage, and has good heat resistance.

[0028] The polyetherimide in the present application has excellent heat resistance and chemical corrosion resistance. In addition, the addition of polyetherimide also has good mechanical strength and wear resistance. DETAILED DESCRIPTION

[0029] The present application will be described in detail below with reference to specific embodiments. Obviously, the described embodiments are part of the embodiments of the present application, but not all. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor shall fall within the scope of protection of the present application.

[0030] Example 1

[0031] A durable road marking paint, comprising a mass ratio of 5:95 of component A and component B, wherein, in terms of mass fraction,

[0032] The component A comprises: 23 parts of polyvinyl chloride, 17 parts of styrene-acrylic resin, 7 parts of acrylonitrile-butadiene-styrene copolymer, 8 parts of polyetherimide, 25 parts of silane coupling agent KH560, and 20 parts of polyether modified silicone;

[0033] The component B comprises 15 parts of petroleum resin, 6 parts of polytetrafluoroethylene, 6 parts of rutile titanium dioxide, 40 parts of 100-200 mesh ultra-fine calcium carbonate powder, 8 parts of nano spherical silica powder, and 20 parts of 50-60 mu reflective glass microbeads, wherein the reflective glass microbeads need to be surface coated and pretreated with hyperbranched polyurethane.

[0034] The surface coating and pretreatment of the reflective glass microbeads comprises the following steps:

[0035] S1. After the reflective glass microbeads are washed and dried, they are placed in a low-temperature plasma treatment machine, vacuumed to 400 Pa, and oxygen is introduced at a flow rate of 80 sccm for 4 minutes;

[0036] S2. The hyperbranched polyurethane resin is diluted with ethanol to a solid content of 65%, 2% aluminum powder by mass of the hyperbranched polyurethane resin is added, and then the mixture is sprayed onto the surface of the reflective glass microbeads treated in step S1, with a spraying thickness of 15 mu, solidification, polishing, to obtain reflective glass microbeads coated with hyperbranched polyurethane resin on the surface.

[0037] A method for preparing a durable road marking paint, comprising the following steps:

[0038] (1) Preparing raw materials: preparing raw materials according to the above proportions;

[0039] (2) Preparing component B: the reflective glass microbeads are surface coated and pretreated with hyperbranched polyurethane, and then rutile titanium dioxide, ultra-fine calcium carbonate powder, and nano spherical silica powder are mixed evenly; petroleum resin and polytetrafluoroethylene are mixed evenly, heated and melted, and then evenly added to the mixed powder to obtain component B;

[0040] (3) Preparing component A: polyvinyl chloride, styrene-acrylic resin, acrylonitrile-butadiene-styrene copolymer, polyetherimide, silane coupling agent, and polyether modified silicone are mixed evenly, heated and stirred until the solid components are completely melted, and then sheared, cooled, and ground to obtain component A;

[0041] (4) Mixing component A and component B at a mass ratio of 5:95, stirring evenly at 160°C, to obtain the product.

[0042] Example 2

[0043] A durable road marking paint, comprising a mass ratio of 5:95 of A component and B component, wherein, in terms of mass fraction,

[0044] The A component comprises: 15 parts of polyvinyl chloride, 15 parts of styrene-acrylic resin, 5 parts of acrylonitrile-butadiene-styrene copolymer, 5 parts of polyetherimide, 20 parts of silane coupling agent KH560, and 15 parts of polyether modified silicone;

[0045] The B component comprises 10 parts of petroleum resin, 5 parts of polytetrafluoroethylene, 5 parts of rutile titanium dioxide, 42 parts of 100-200 mesh ultra-fine calcium carbonate powder, 5 parts of nano spherical silica powder, and 18 parts of reflective glass microbeads with a size of 50-60 μm. The reflective glass microbeads need to be surface coated and pretreated with hyperbranched polyurethane.

[0046] The surface coating and pretreatment of the reflective glass microbeads comprises the following steps:

[0047] S1. After the reflective glass microbeads are cleaned and dried, they are placed in a low-temperature plasma treatment machine, vacuumed to 500 Pa, and oxygen is introduced at a flow rate of 100 sccm for 3 min;

[0048] S2. The hyperbranched polyurethane resin is diluted with ethanol to a solid content of 60%, and 2% aluminum powder by mass of the hyperbranched polyurethane resin is added and mixed, and then the mixture is sprayed onto the surface of the reflective glass microbeads treated in step S1 to a thickness of 10 μm, solidified, polished, and the reflective glass microbeads coated with hyperbranched polyurethane resin are obtained.

[0049] A preparation method of a durable road marking paint, comprising the following steps:

[0050] (1) Preparing raw materials: preparing raw materials according to the above proportions;

[0051] (2) Preparing B component: the reflective glass microbeads are surface coated and pretreated with hyperbranched polyurethane, and then rutile titanium dioxide, ultra-fine calcium carbonate powder, and nano spherical silica powder are mixed uniformly; petroleum resin and polytetrafluoroethylene are mixed uniformly, heated and melted, and then uniformly added to the mixed powder to obtain B component;

[0052] (3) Preparing A component: polyvinyl chloride, styrene-acrylic resin, acrylonitrile-butadiene-styrene copolymer, polyetherimide, silane coupling agent, and polyether modified silicone are mixed uniformly, heated and stirred until the solid components are completely melted, and then sheared, cooled, and ground to obtain A component;

[0053] (4) Mixing A component and B component at a mass ratio of 5:95, uniformly stirring at 160℃, and obtaining the product.

[0054] Embodiment 3

[0055] A durable road marking paint, comprising a group A component and a group B component in a mass ratio of 4:96, wherein the group A component comprises, by mass fraction,

[0056] The group A component comprises: 30 parts of polyvinyl chloride, 20 parts of styrene-acrylic resin, 10 parts of acrylonitrile-butadiene-styrene copolymer, 10 parts of polyetherimide, 30 parts of silane coupling agent KH560, and 25 parts of polyether-modified silicone;

[0057] The group B component comprises 12 parts of petroleum resin, 8 parts of polytetrafluoroethylene, 8 parts of rutile titanium dioxide, 38 parts of 100-200 mesh ultra-fine calcium carbonate powder, 10 parts of nanometer spherical silica powder, and 20 parts of 50-60 μm reflective glass microbeads, wherein the reflective glass microbeads need to be pre-treated by surface coating with hyperbranched polyurethane.

[0058] The pre-treatment of the surface coating of the reflective glass microbeads comprises the following steps:

[0059] S1. After the reflective glass microbeads are cleaned and dried, they are placed in a low-temperature plasma treatment machine, vacuumed to 500 Pa, and oxygen is introduced at a flow rate of 100 sccm for 4 min;

[0060] S2. The hyperbranched polyurethane resin is diluted with ethanol to a solid content of 70%, 2% aluminum powder by mass of the hyperbranched polyurethane resin is added, and then the mixture is sprayed onto the surface of the reflective glass microbeads treated in step S1 to a thickness of 20 μm, solidified, polished, and the reflective glass microbeads coated with hyperbranched polyurethane resin are obtained.

[0061] A method for preparing a durable road marking paint, comprising the following steps:

[0062] (1) Preparing raw materials: preparing raw materials according to the above proportions;

[0063] (2) Preparing the group B component: the reflective glass microbeads are pre-treated by surface coating with hyperbranched polyurethane, and then rutile titanium dioxide, ultra-fine calcium carbonate powder, and nanometer spherical silica powder are added and mixed uniformly; petroleum resin and polytetrafluoroethylene are mixed uniformly, heated and melted, and then uniformly added to the mixed powder to obtain the group B component;

[0064] (3) Preparing the group A component: polyvinyl chloride, styrene-acrylic resin, acrylonitrile-butadiene-styrene copolymer, polyetherimide, silane coupling agent, and polyether-modified silicone are mixed uniformly, heated and stirred until the solid components are completely melted, and then sheared, cooled, and ground to obtain the group A component;

[0065] (4) A component and B component are mixed in a mass ratio of 4:96, and the product is obtained by stirring uniformly at 160°C.

[0066] Comparative Example 1

[0067] A durable road marking paint, comprising A component and B component in a mass ratio of 5:95, wherein, in terms of mass fraction,

[0068] The A component comprises: 23 parts of polyvinyl chloride, 17 parts of styrene-acrylic resin, 7 parts of acrylonitrile-butadiene-styrene copolymer, 8 parts of polyetherimide, 25 parts of silane coupling agent KH560, and 20 parts of polyether modified silicone;

[0069] The B component comprises 15 parts of petroleum resin, 6 parts of polytetrafluoroethylene, 6 parts of rutile titanium dioxide, 40 parts of 100-200 mesh ultra-fine calcium carbonate powder, 8 parts of nano spherical silica powder, and 20 parts of 50-60 μm reflective glass microbeads.

[0070] A preparation method of a durable road marking paint, comprising the following steps:

[0071] (1) Preparing raw materials: preparing raw materials according to the above proportions;

[0072] (2) Preparing B component: mixing reflective glass microbeads, rutile titanium dioxide, ultra-fine calcium carbonate powder, and nano spherical silica powder uniformly; mixing petroleum resin and polytetrafluoroethylene uniformly, and then uniformly adding the mixed powder after hot melting to obtain B component;

[0073] (3) Preparing A component: mixing polyvinyl chloride, styrene-acrylic resin, acrylonitrile-butadiene-styrene copolymer, polyetherimide, silane coupling agent, and polyether modified silicone uniformly, and then heating and stirring until the solid components are completely melted, followed by shearing, cooling, and grinding to obtain A component;

[0074] (4) A component and B component are mixed in a mass ratio of 5:95, and the product is obtained by stirring uniformly at 160°C.

[0075] Comparative Example 2

[0076] A durable road marking paint, comprising A component and B component in a mass ratio of 5:95, wherein, in terms of mass fraction,

[0077] The A component comprises: 23 parts of polyvinyl chloride, 17 parts of styrene-acrylic resin, 7 parts of acrylonitrile-butadiene-styrene copolymer, 8 parts of polyetherimide, 25 parts of silane coupling agent KH560, and 20 parts of polyether modified silicone;

[0078] The B component comprises 21 parts of petroleum resin, 6 parts of rutile titanium dioxide, 48 parts of 100-200 mesh superfine calcium carbonate powder, and 20 parts of reflective glass microbeads with a size of 50-60 microns.

[0079] The surface coating pretreatment of the reflective glass microbeads comprises the following steps:

[0080] S1. After the reflective glass microbeads are cleaned and dried, they are placed in a low-temperature plasma treatment machine, vacuumed to 400 Pa, and oxygen is introduced at a flow rate of 80 sccm for 4 minutes.

[0081] S2. The hyperbranched polyurethane resin is diluted with ethanol to a solid content of 65%, and 2% aluminum powder by mass of the hyperbranched polyurethane resin is added and mixed, and then the mixture is sprayed onto the surface of the reflective glass microbeads treated in step S1 to a thickness of 15 microns, solidified, polished, and the reflective glass microbeads coated with hyperbranched polyurethane resin are obtained.

[0082] A preparation method of a durable road marking paint, comprising the following steps:

[0083] (1) Preparing raw materials: preparing raw materials according to the above proportions;

[0084] (2) Preparing the B component: the reflective glass microbeads are pretreated by surface coating with hyperbranched polyurethane, and then rutile titanium dioxide and superfine calcium carbonate powder are added and mixed uniformly; the petroleum resin is hot-melted, and then the mixed powder is added uniformly to obtain the B component;

[0085] (3) Preparing the A component: polyvinyl chloride, styrene-acrylic resin, acrylonitrile-butadiene-styrene copolymer, polyetherimide, silane coupling agent, and polyether-modified silicone are mixed uniformly, heated and stirred until the solid components are completely melted, and then sheared, cooled, and ground to obtain the A component;

[0086] (4) Mixing the A component and the B component at a mass ratio of 5:95, and stirring uniformly at 160 DEG C to obtain the product.

[0087] The product obtained above is subjected to reverse reflection coefficient and durability detection, and the results are shown in Table 1.

[0088] Table 1

[0089] Treatment Retroreflective coefficient (mcd - 1 x -1 ·m -2 )]]> Wear / mg Durability / d Example 1 332.5 50.1 1258 Example 2 315.8 50.8 1248 Example 3 324.6 49.6 1264 Comparative Example 1 273.7 58.7 1089 Comparative Example 2 310.4 57.2 1126

[0090] In the present application, the surface coating treatment of the reflective glass microbeads can improve the adhesion of the reflective glass microbeads, reduce the shedding rate, thereby prolonging the service life, and improving the reflectivity of the marking line.

[0091] The polytetrafluoroethylene added in the present application can improve the reflection of light and heat radiation, reduce the absorption of the coating to light and heat radiation, thus reducing the aging problem caused by solar radiation, thereby improving the durability. The addition of spherical silicon powder can increase the heat insulation of the coating due to its special spherical structure, thus playing a shielding role, thereby reducing the thermal aging problem caused by heat and improving the durability.

Claims

1. A durable road marking paint, characterized in that: The invention comprises component A and component B in a mass ratio of (4-5): (95-96), wherein, by mass fraction, component A comprises: 15-30 parts of polyvinyl chloride, 15-20 parts of styrene-acrylic resin, 5-10 parts of acrylonitrile-butadiene-styrene copolymer, 5-10 parts of polyetherimide, 20-30 parts of silane coupling agent, and 15-30 parts of polyether-modified silicone; component B comprises 10-15 parts of petroleum resin, 5-10 parts of polytetrafluoroethylene, 5-8 parts of rutile titanium dioxide, 38-42 parts of ultrafine calcium carbonate powder, 5-10 parts of nano-spherical silicon powder, and 18-20 parts of reflective glass microbeads; The reflective glass microbeads are pretreated by surface coating with hyperbranched polyurethane, comprising the following steps: S1. After cleaning and drying the reflective glass beads, place them in a low-temperature plasma processor, evacuate to 400-500Pa, introduce oxygen at an oxygen flow rate of 50-100sccm, and process for 3-5min. S2. The hyperbranched polyurethane resin was diluted with a solvent, aluminum powder was added and mixed, and then sprayed on the surface of the reflective glass beads after treatment in step S1, with a spray thickness of 10-20 μm, cured, and polished to obtain a surface-coated hyperbranched polyurethane resin reflective glass beads; The solvent is ethanol or acetone, which is diluted to a solid content of 60-70%, and the amount of aluminum powder added is 2-3% of the hyperbranched polyurethane resin.

2. A durable road marking paint according to claim 1, characterized in that: The particle size of the ultrafine calcium carbonate powder is 100-200 meshes; the SiO2 content in the nano-spherical silicon powder is ≥99.6%; and the particle size of the reflective glass microbeads is 50-60 μm.

3. The durable road marking paint according to claim 1, characterized in that: The silane coupling agent is one or any combination of silane coupling agent KH550, silane coupling agent KH560, silane coupling agent KH570, and silane coupling agent KH792.

4. The method for preparing a durable road marking paint according to claim 1, wherein: The following steps are involved: (1) Prepare raw materials: prepare, by mass, 15-30 parts of polyvinyl chloride, 15-20 parts of styrene-acrylic resin, 5-10 parts of acrylonitrile-butadiene-styrene copolymer, 5-10 parts of polyetherimide, 20-30 parts of silane coupling agent, 15-30 parts of polyether-modified silicone; 10-15 parts of petroleum resin, 5-10 parts of polytetrafluoroethylene, 5-8 parts of rutile titanium dioxide, 38-42 parts of ultrafine calcium carbonate powder, 5-10 parts of nano-spherical silica powder, and 18-20 parts of reflective glass microbeads; (2) Preparation of component B: Pre-treating the surface of reflective glass microspheres by coating with hyperbranched polyurethane, then adding rutile titanium dioxide, ultrafine calcium carbonate powder, and nano-spherical silicon powder and mixing them uniformly; mixing petroleum resin and polytetrafluoroethylene uniformly, hot-melting, and evenly adding the mixed powder to obtain component B; (3) Preparation of component A: polyvinyl chloride, styrene-acrylic resin, acrylonitrile-butadiene-styrene copolymer, polyetherimide, silane coupling agent, and polyether-modified silicone are uniformly mixed, heated and stirred until the solid components are completely melted, and then sheared, cooled, and ground to obtain component A; (4) Component A and component B are mixed in a mass ratio of (4-5): (95-96), and stirred evenly at 160-180° C. to obtain the product.