CN108610699B - Methacrylic resin marking paint and preparation method thereof - Google Patents
Methacrylic resin marking paint and preparation method thereof Download PDFInfo
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- CN108610699B CN108610699B CN201611141794.9A CN201611141794A CN108610699B CN 108610699 B CN108610699 B CN 108610699B CN 201611141794 A CN201611141794 A CN 201611141794A CN 108610699 B CN108610699 B CN 108610699B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
Abstract
The invention belongs to the field of road engineering, and provides a methacrylic resin marking paint which consists of a component A, a component B and a component C, wherein the component A contains 40-60 parts of methacrylic resin, 1-3 parts of anti-precipitation auxiliary agent, 5-15 parts of pigment, 40-100 parts of filler, 0.4-1 part of ultraviolet stabilizer and 0.5-1.5 parts of accelerator; the component B comprises 40-60 parts of methacrylic resin, 1-3 parts of anti-precipitation auxiliary agent, 5-15 parts of pigment, 40-100 parts of filler and 0.5-1 part of ultraviolet stabilizer, and the component C is curing agent. The marking paint provided by the invention can be quickly cured on asphalt or cement pavements after being uniformly mixed, and a coating film with excellent comprehensive performance is formed. The marking paint is a thermosetting material, and a coating film after curing has excellent mechanical strength and toughness, high adhesion with asphalt or cement pavements, good heat resistance and wear resistance, can be used as a flocculent or punctiform marking to be applied to a drainage asphalt pavement, has a drainage function, and can also be used as a bridge deck waterproof adhesive layer to protect a bridge deck.
Description
Technical Field
The invention belongs to the field of road engineering, and particularly relates to a marking paint containing a thermosetting polymer, and a preparation method and application thereof.
Background
The road marking is an important part of the road and is an important guarantee for traffic guidance and safe driving. The road marking is a paint film formed by coating marking paint on the surface of a road through a professional construction vehicle and drying, and the surface of the road marking is often damaged due to the fact that the road marking paint is often rolled by the vehicle and is also corroded by environmental factors (such as heat, sun, rain, engine oil, snow melting agent and the like), and the road marking can fall off from the road surface quickly, so that the road marking is unclear and the driving safety is influenced.
The existing marking paint is mainly a hot-melt resin marking material, wherein the resin is mainly petroleum resin (carbon five, carbon nine or modified carbon five resin, etc.) and modified rosin resin, and calcium carbonate, barium sulfate, titanium dioxide, quartz powder, etc. are added as fillers, and the fillers are coated on roads after being uniformly hot-melted and stirred. The marked lines are quick in construction, short in maintenance period and relatively low in manufacturing cost, but the marked lines are easily adhered to the surface after being irradiated by the sun and rolled by wheels in summer, road surface dust and tire marks are often adhered to the surface to pollute the marked lines, the marked lines are often easily dropped off after being soaked by rain in rainy seasons, the marked lines are relatively fragile in winter, and the marked lines are easily cracked and dropped off after being rolled by the wheels, so that the service life of the marked lines is often influenced. And traditional marking does not possess the ability of permeating water, when drainage bituminous paving applied, near marking and peripheral have produced and have blocked water and have crowded water problem, lead to the splash and the smooth problem on road surface, still can make near marking produce the reflection of light, be unfavorable for the visuality of marking, influence traffic safety and road surface comfortable. The re-painting of the marking line on the opened road has an influence on traffic driving, particularly road sealing and the like. Therefore, the heat resistance, the adhesive force, the rain soaking resistance and other performances of the marking paint can be improved, and the improvement of the service durability of the marking paint is very significant.
Disclosure of Invention
Aiming at the technical defects of the existing pavement marking paint, the invention provides a methacrylic resin marking paint which comprises the components of methacrylic resin, pigment, filler, accelerator, curing agent, stabilizer and the like.
The invention also aims to provide a preparation method of the methacrylic resin marking paint.
The technical scheme for realizing the above purpose of the invention is as follows:
a methacrylic resin marking paint consists of a component A, a component B and a component C,
the component A comprises the following components in parts by mass: 40-60 parts of methacrylic resin, 1-3 parts of anti-precipitation auxiliary agent, 5-15 parts of pigment, 40-100 parts of filler, 0.4-1 part of ultraviolet stabilizer, 0.5-1.5 parts of accelerator and 0.005-0.007 part of polymerization inhibitor;
the component B comprises the following components in parts by mass: 40-60 parts of methacrylic resin, 1-3 parts of anti-precipitation auxiliary agent, 5-15 parts of pigment, 40-100 parts of filler and 0.5-1 part of ultraviolet stabilizer;
the component C is a curing agent.
Further, the pigment is rutile titanium dioxide or iron oxide yellow, the filler is one of precipitated barium sulfate powder, magnesium hydroxide and white carbon black, and the particle size of the filler is 1-10 microns.
Preferably, the ultraviolet stabilizer is a benzotriazole ultraviolet absorber and a hindered amine light stabilizer, and the mass ratio of the benzotriazole ultraviolet absorber to the hindered amine light stabilizer is 1: 0.6 to 1.5.
Both the benzotriazole ultraviolet light absorber and the hindered amine light stabilizer are commonly used as additives for preventing ultraviolet light aging in polymethacrylate polymers, but the two types of ultraviolet light absorbers have different reaction mechanisms to ultraviolet light, and the two types of ultraviolet light absorbers and the hindered amine light stabilizer are matched to play a good synergistic effect when used together.
According to a preferable technical scheme, the component A comprises the following components in parts by mass: 45-55 parts of methacrylic resin, 2-3 parts of modified fumed silica anti-precipitation auxiliary agent, 7-10 parts of pigment, 50-80 parts of filler, 0.4-0.6 part of ultraviolet stabilizer, 1-1.5 parts of accelerator (N, N-dimethyl-p-toluidine) and 0.004-0.006 part of polymerization inhibitor.
Wherein the component B comprises the following components in parts by mass: 45-55 parts of methacrylic resin, 2-3 parts of modified fumed silica anti-precipitation additive, 7-10 parts of pigment, 50-80 parts of precipitation-process barium sulfate and 0.4-0.6 part of ultraviolet stabilizer.
Wherein the curing agent is dibenzoyl peroxide (BPO), and the ratio of the component A to the component B to the component C is 100: 95-100: 1 to 3.
The preparation method of the methacrylic resin marking paint comprises the preparation of a component A and a component B,
preparation of component A: dispersing methacrylic resin and anti-settling agent at high speed to be viscous, adding pigment, filler, ultraviolet stabilizer, accelerant and polymerization inhibitor into the system, dispersing uniformly at high speed, pouring into a horizontal sand mill, grinding to the fineness of less than 100 micrometers, filtering and discharging;
preparation of the component B: dispersing methacrylic resin and anti-settling agent at high speed to be viscous, adding pigment, filler and ultraviolet stabilizer into the system, dispersing uniformly at high speed, pouring into a horizontal sand mill, grinding to the fineness of less than 100 micrometers, filtering and discharging.
The methacrylic resin can be obtained by a method known in the art. There is provided a preferred method of preparation of the invention:
the methacrylic resin is prepared by the following method:
1) putting methyl methacrylate, hydroxyethyl methacrylate, butyl methacrylate, isooctyl acrylate, triethylene glycol dimethacrylate and a polymerization inhibitor into a reaction kettle, and stirring;
2) adding the ethylene methyl acrylate copolymer into the reaction kettle, and keeping constant temperature and stirring at a medium speed until the ethylene methyl acrylate copolymer is completely dissolved;
the material feeding amount of each material is 20-30 parts of ethylene methyl acrylate copolymer, 30-35 parts of methyl methacrylate, 10-20 parts of hydroxyethyl methacrylate, 20-30 parts of butyl methacrylate, 15-20 parts of isooctyl acrylate, 2-4 parts of triethylene glycol dimethacrylate and 0.001 part of polymerization inhibitor.
Wherein the ethylene methyl acrylate copolymer is cut into rubber blocks with the size of less than 2.0cm, and the polymerization inhibitor is ZJ 701.
After materials are added in the step 1), the reaction kettle is heated to 75-80 ℃, the temperature of 75-80 ℃ is kept constant in the step 2), and after the reaction in the step 2), the materials are filtered and discharged.
The invention has the beneficial effects that:
the marking paint provided by the invention comprises components such as methacrylic resin, pigment, filler, accelerator, curing agent, stabilizer and the like. After being uniformly mixed, the components can be quickly cured on asphalt or cement pavements to form a coating film with excellent comprehensive performance. The marking paint is a thermosetting material, and once cured, a coating film has excellent mechanical strength and toughness, high adhesion with asphalt or cement pavements, good heat resistance, good wear resistance, stable surface without adhesion reversion at high temperature, good ultraviolet resistance, long-term surface without discoloration, and good corrosion resistance to chemical media such as acid and alkali salts. Compared with the existing hot-melt type marking paint, the marking paint has obviously prolonged service life. The asphalt pavement waterproof adhesive can be used as a flocculent or punctiform marking to be applied to a drainage asphalt pavement, has a drainage function, and can also be used as a bridge deck waterproof adhesive layer to protect a bridge deck.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The raw materials used in the examples:
rutile type titanium dioxide TIONA595, iron oxide yellow Bayer pattern 4960,
Benzotriazole ultraviolet light absorber UV327, hindered amine light stabilizer GW508,
modified gas phase method silicon dioxide anti-precipitation assistant AEROSIL R972, precipitation method barium sulfate powder with the granularity of 6000 meshes, N-dimethyl-p-toluidine as an accelerant, a polymerization inhibitor ZJ701,
and the component C is dibenzoyl peroxide Perkadox CH-50X diluted by a solid plasticizer.
Example 1: preparation of methacrylic resins
Cutting 20 parts of ethylene methyl acrylate copolymer into small blocks with the particle size of less than 2cm,
putting 30 parts of methyl methacrylate, 15 parts of hydroxyethyl methacrylate, 25 parts of butyl methacrylate, 18 parts of isooctyl acrylate, 3 parts of triethylene glycol dimethacrylate and 0.001 part of polymerization inhibitor (ZJ701) into a reaction kettle, starting stirring, and heating the materials at 75-80 ℃;
putting the cut ethylene methyl acrylate copolymer small rubber blocks into a reaction kettle, and keeping constant temperature and stirring at medium speed until the rubber blocks are completely dissolved;
and discharging after filtering.
EXAMPLE 2 methacrylic resin Performance test
The methacrylic resin prepared in example 1 was mixed with a curing agent (BPO powder) and an accelerator (N, N-dimethyl-p-toluidine) at a mass ratio of 100:2:1, the curing agent and the resin were uniformly stirred until the colorless powder completely disappeared, and then the mixture was uniformly stirred with the accelerator and knife-coated on a tetrafluoroethylene plate with a thickness of about 1.5mm, and the film was cured for 24 hours and then subjected to a performance test, with the following results:
TABLE 1 methacrylic resin Performance test results
| Serial number | Item | Test results | Inspection method |
| 1 | Appearance of the product | Uniform and consistent | Visual inspection of |
| 2 | Solid content (%) | 95 | GB/T 1725 |
| 3 | Surface dry time (min, 23 + -2 deg.C) | 30 | GB/T 1728 |
| 4 | Actual drying time (min, 23 + -2 deg.C) | 50 | GB/T 1728 |
| 5 | Tensile Strength (MPa) | 12 | GB/T 528 |
| 6 | Elongation at Break (%) | 100 | GB/T 528 |
| 7 | Low temperature flexibility (-10 ℃, phi 20,90 degree) | Without cracks | GB/T 6742 |
| 8 | Heat resistance (100 ℃,2h) | Flowing without bubbling and bubbling | GB/T 16777 |
EXAMPLE 3 methacrylic resin based marking paint preparation
The component A comprises:
50 parts of the methyl methacrylate resin prepared in example 1 above and 2 parts of a modified fumed silica anti-settling agent (AEROSIL R972) were dispersed at high speed to a viscous state,
10 parts of titanium dioxide (TIONA595), 50 parts of superfine barium sulfate powder (6000 meshes), 0.3 part of UV327, 0.3 part of GW508, 1.2 parts of N, N-dimethyl-p-toluidine and 0.006 part of ZJ701 are added into the system, and the mixture is uniformly dispersed at a high speed.
Grinding with horizontal sand mill to fineness below 100 μm, filtering, and discharging
And B component:
50 parts of the methyl methacrylate resin prepared in example 1 above and 2 parts of a modified fumed silica anti-settling agent (AEROSIL R972) were dispersed at high speed to a viscous state;
adding 10 parts of titanium dioxide (TIONA595), 60 parts of superfine barium sulfate powder (6000 meshes), 0.3 part of UV327 and 0.3 part of GW508 into the system, and uniformly dispersing at a high speed;
grinding with horizontal sand mill to fineness below 100 μm, filtering, and discharging.
C component
Dilute dibenzoyl peroxide (Perkadox CH-50X) was dispensed directly.
EXAMPLE 4 methacrylic resin based marking paint preparation
The component A comprises:
55 parts of the methyl methacrylate resin prepared in example 1 and 2 parts of a modified fumed silica anti-settling agent (AEROSIL R972) were dispersed at high speed to give a viscous,
20 parts of iron oxide yellow (Bayer 4960), 40 parts of superfine barium sulfate powder (6000 meshes), 0.3 part of UV327, 0.2 part of GW508, 1.2 parts of N, N-dimethyl-p-toluidine and 0.006 part of ZJ701 are added into the system, and the mixture is uniformly dispersed at a high speed.
Grinding with horizontal sand mill to fineness below 100 μm, filtering, and discharging
And B component:
55 parts of the methyl methacrylate resin prepared in example 1 above and 2 parts of a modified fumed silica anti-settling agent (AEROSIL R972) were dispersed at high speed to a viscous state;
adding 20 parts of iron oxide yellow (Bayer 4960), 40 parts of superfine barium sulfate powder (6000 meshes), 0.2 part of UV327 and 0.3 part of GW508 into the system, and uniformly dispersing at a high speed;
grinding with horizontal sand mill to fineness below 100 μm, filtering, and discharging.
The C component was the same as in example 3.
Example 5 methacrylic resin based reticle coating Performance test
The ABC component is uniformly mixed and stirred according to the weight ratio of 100:98:2, the BC component is uniformly mixed, then the mixture is uniformly mixed with the A component, and the mixture is spread on a tetrafluoroethylene board and a cement asbestos board, wherein the thickness of the mixture is about 2 mm.
The coating film was cured at room temperature for 24 hours and then tested, and the results are shown in the following table.
Table 2 coating film test results
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. It will be apparent to those skilled in the art that variations, or modifications, derived or suggested from the disclosure and general knowledge, that achieve the same function and result as described herein, may be substituted for those of ordinary skill in the art, and that all such variations, modifications, and equivalents may be substituted for elements thereof without departing from the scope of the present disclosure.
Claims (7)
1. A methacrylic resin marking paint is composed of a component A, a component B and a component C and is characterized in that,
the component A comprises the following components in parts by mass: 45-55 parts of methacrylic resin, 2-3 parts of modified gas-phase-method silica anti-precipitation agent, 7-10 parts of pigment, 50-80 parts of filler precipitation-method barium sulfate powder, 0.4-0.6 part of ultraviolet stabilizer, 1-1.5 parts of accelerator N, N-dimethyl-p-toluidine and 0.004-0.006 part of polymerization inhibitor;
the component B comprises the following components in parts by mass: 45-55 parts of methacrylic resin, 2-3 parts of modified fumed silica anti-precipitation additive, 7-10 parts of pigment, 50-80 parts of filler precipitation barium sulfate and 0.4-0.6 part of ultraviolet stabilizer;
the component C is a curing agent which is dibenzoyl peroxide, and the weight ratio of the component A to the component B to the component C is 100: 95-100: 1-3;
the methacrylic resin is prepared by the following method:
1) putting methyl methacrylate, hydroxyethyl methacrylate, butyl methacrylate, isooctyl acrylate, triethylene glycol dimethacrylate and a polymerization inhibitor into a reaction kettle, and stirring;
2) adding the ethylene methyl acrylate copolymer into the reaction kettle, and keeping constant temperature and stirring at a medium speed until the ethylene methyl acrylate copolymer is completely dissolved;
the material feeding amount of each material is as follows: 20-30 parts of ethylene methyl acrylate copolymer, 30-35 parts of methyl methacrylate, 10-20 parts of hydroxyethyl methacrylate, 20-30 parts of butyl methacrylate, 15-20 parts of isooctyl acrylate, 2-4 parts of triethylene glycol dimethacrylate and 0.001 part of polymerization inhibitor.
2. The methacrylic resin reticle paint of claim 1, wherein the pigment is rutile type titanium dioxide or iron oxide yellow, and the particle size of the filler is 1 to 10 μm.
3. The methacrylic resin-based reticle coating according to claim 1, wherein the ultraviolet stabilizer is a benzotriazole-based ultraviolet absorber and a hindered amine-based light stabilizer in a mass ratio of 1: 0.6 to 1.5.
4. The method for preparing a methacrylic resin-based reticle coating according to any one of claims 1 to 3, comprising the preparation of the A-component and the B-component,
preparation of component A: dispersing methacrylic resin and anti-settling agent at high speed to be viscous, adding pigment, filler, ultraviolet stabilizer, accelerant and polymerization inhibitor into the system, dispersing uniformly at high speed, pouring into a horizontal sand mill, grinding to the fineness of less than 100 micrometers, filtering and discharging;
preparation of the component B: dispersing methacrylic resin and anti-precipitation auxiliary agent at high speed until the mixture is viscous, adding pigment, filler and ultraviolet stabilizer into the system, dispersing uniformly at high speed, pouring the mixture into a horizontal sand mill, grinding the mixture to the fineness of less than 100 microns, filtering and discharging the mixture.
5. The method according to claim 4, wherein the ethylene-methyl acrylate copolymer is cut into a block having a size of 2.0cm or less, and the polymerization inhibitor is ZJ 701.
6. The preparation method according to claim 4 or 5, characterized in that after the materials are added in the step 1), the reaction kettle is heated to 75-80 ℃, the temperature of 75-80 ℃ is kept constant in the step 2), and after the reaction in the step 2), the materials are filtered and discharged.
7. The methacrylic resin-based marking paint according to claim 1, which is used for a marking of a drainage asphalt pavement, or a marking of a cement concrete pavement, or as a bridge deck waterproof adhesive layer.
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| CN110079138A (en) * | 2019-05-05 | 2019-08-02 | 南宁华之邦交通设施材料有限公司 | A kind of high compactness anti-pollution gage mark coating |
| CN112323623B (en) * | 2020-09-15 | 2022-03-25 | 江苏绿迈环境技术有限公司 | Steel bridge deck pavement structure and pavement process thereof |
| CN112322085B (en) * | 2020-09-15 | 2022-01-04 | 江苏绿迈环境技术有限公司 | PMMA waterproof coating for intercity high-speed railway and urban light rail concrete bridge |
| CN112226133A (en) * | 2020-09-24 | 2021-01-15 | 安徽省沥美道路新型材料有限公司 | Antiskid marble-imitated coating for colored pavement |
| CN112662261A (en) * | 2020-12-31 | 2021-04-16 | 山西中涂交通科技股份有限公司 | Self-cleaning road marking paint and preparation method thereof |
| CN113061207B (en) * | 2021-03-30 | 2022-10-18 | 四川君尚新材料科技有限公司 | Composite resin material and preparation method and application thereof |
| CN115595028B (en) * | 2022-10-09 | 2023-06-09 | 天途路业集团有限公司 | Punctiform coating suitable for road scribing vehicle |
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| CN101514266A (en) * | 2009-03-05 | 2009-08-26 | 常州市福莱姆汽车涂料有限公司 | Solvent-free road marking dope cured under normal temperature and preparation method thereof |
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