Stain preventive and stainproof coating material for road marking

Description: TECHNICAL FIELD [Detailed description of the invention]

【0001】

[Technical field to which the invention belongs]

The present invention relates to an antifouling modifier and an antifouling paint for road markings containing the antifouling modifier, and the antifouling paint can be used for road center lines, pedestrian crossings, instruction lines, speed markings, etc. It is used as a paint when applying road markings.

【0002】

[Conventional technology]

Road marking paints have yellow or white central dividers or pedestrian crossings on the road surface so that vehicles and pedestrians can safely travel on the road, or road traffic law markings such as pauses and speed limits. It is widely used as a paint for applying, and also for applying pedestrian crossings for orderly aligning vehicles in parking lots and the like.

【0003】

These road marking paints are roughly classified into the following four types. (1) Room temperature drying type road marking paint: A room temperature drying type paint containing a quick-drying synthetic resin as a vehicle component, which is currently the most widely used. (2) Heat-curable road marking paint: A fast-curing paint containing a thermosetting resin as a vehicle component. (3) Hot-melt type road marking paint: A paint that contains a thermoplastic resin that is solid at room temperature as a vehicle component. It is heated and melted and then poured onto the road surface as it is, or applied using a hot spray gun. It solidifies and dries extremely quickly, is easy to apply thick film, and has excellent durability. (4) Water-based road marking paint: A water-based resin is used as a vehicle component, and a curable paint is usually used. Compared to solvent-type road marking paints, there is no danger of ignition, workability is good, and the environment is good, but there are drawbacks that it takes a long time to dry.

【0004】

The above road marking paint is required to have sufficient wear resistance to withstand friction when vehicles pass through, and because it is directly exposed to sunlight and rain and wind, it does not deteriorate or fade even in those harsh environments. It is required to have excellent adhesion that does not come off from the surface and visibility that allows the marking to be confirmed even during rainfall or at night.

【0005】

In addition, in order to improve the visibility of road markings, it has been attempted to mix fluorescent pigments, phosphorescent pigments, glass beads, etc. with the paint, and immediately after marking the road surface, the pigments emit good light. Demonstrates excellent visibility. However, while exposed to the harsh environment as described above, the marking is significantly contaminated by tire marks and asphalt spilled oil, and the marking function is lost in a relatively short time.

【0006】

Therefore, as a means for suppressing the deterioration of the marking function due to such pollution, a large amount of calcium carbonate, magnesium carbonate, aluminum oxide, etc., which are general extender pigments, are blended in the road marking paint to make the paint itself hard and brittle. A method of improving antifouling property by giving self-wearing property has also been proposed.

【0007】

[Problems to be Solved by the Invention]

However, in the above method, the antifouling effect is exhibited only when the marking surface is deteriorated, and until the deterioration, the tire marks and asphalt spilled oil are soiled, and the deterioration of the visual field cannot be avoided. In addition, since the antifouling effect is exerted by self-wear, there is a problem in durability in a place with heavy traffic, and there is a problem that marking construction must be repeated frequently.

【0008】

In addition, a method of improving antifouling property by blending an appropriate amount of silicone oil with the marking paint and exuding the silicone oil to the paint surface has been tried, but the silicone oil is directly added to the road surface paint. When used, the adhesion between the road surface and the paint is deteriorated, and a fatal defect occurs in which the marking is easily peeled off from the road surface.

【0009】

The present invention has been made in view of such an actual situation, and imparts a property to the paint so that it exhibits excellent adhesion to the road surface and can maintain excellent antifouling property for a long period of time. It is an object of the present invention to provide an antifouling modifier capable of providing an antifouling modifier, and by adding the antifouling modifier, an antifouling paint for road marking having excellent antifouling durability.

【0010】

[Means for solving problems]

The antifouling modifier of the present invention capable of achieving the above object has a gist that the silicone oil-containing component is coated with a silicate. In addition, an antifouling modifier in which silicone oil is sealed in the pores of the inorganic porous material, and silicone oil is sealed in the pores of the inorganic porous material, and the outer surface thereof is coated with silicate. Similarly, the effect of the present invention can be achieved with the antifouling modifier.

【0011】

Further, the silicone oil preferably contains one or more selected from dimethyl silicone oil, methyl phenyl silicone oil, and amino-modified silicone oil, and contains dimethyl silicone oil, methyl phenyl silicone oil, and amino-modified silicone oil. Is even more preferable.

【0012】

In addition, the silicate containing sodium silicate and / or potassium silicate, It is preferable that the porous material is ceramics. The ceramics preferably contain one or more of calcium carbonate, aluminum oxide, and silicon oxide, and more preferably contain calcium carbonate, aluminum oxide, and silicon oxide.

【0013】

On the other hand, it is preferable to construct the road marking using the antifouling paint for road marking containing the antifouling modifier of the present invention.

【0014】

BEST MODE FOR CARRYING OUT THE INVENTION

The present inventors have studied from various angles in order to solve the above problems. As a result, after applying the paint to the road surface, if an antifouling modifier having the property of allowing silicone oil to gradually exude to the surface of the marking paint is added to the paint, there is a problem of poor adhesion to the road surface. It was found that the antifouling property was improved without causing the above-mentioned problems, and the above-mentioned problems could be solved brilliantly. The antifouling modifier and the antifouling paint for road marking according to the present invention will be described in detail below.

【0015】

The antifouling modifier of the present invention is characterized in that it is provided with a mechanism such that silicone oil exudes to the marking surface after road marking construction, and the first example thereof is that the silicone oil-containing component is a silicate. It is covered with. The silicate has heat resistance and heat insulating properties, and does not deteriorate the silicone oil. In addition, for example, when the paint temperature is cooled to 70 ° C or less after performing hot-melt type road marking construction, the silicate film is cracked in a milky manner, and the silicone oil enclosed inside is the silicate film. It gradually exudes to the surface of the marking paint and forms an antifouling film on the marking surface. That is, since the silicone oil is sealed by the silicate film at the time of marking construction and does not diffuse into the paint, the problem of poor adhesion between the road surface and the paint as described above does not occur. Moreover, after the marking coating, the silicone oil gradually exudes due to the cracks in the silicate film, so that excellent antifouling durability is exhibited.

【0016】

Further, as a second example of the present invention, there is an antifouling modifier in which silicone oil is sealed in the pores of the inorganic porous substance. In this type of antifouling agent, silicone oil is sealed in the pores of the inorganic porous material, so even if this is mixed in the paint, there is a problem that the adhesion between the road surface and the paint deteriorates. Moreover, after the road marking is applied, the silicone oil in the pores gradually exudes to the marking surface to form an antifouling film, so that the antifouling property of the road marking can be maintained for a long period of time.

【0017】

Further, in the third example of the present invention, silicone oil is sealed in the pores of the inorganic porous substance, and the outer surface thereof is coated with silicate, so that the most excellent performance is exhibited. In other words, when an inorganic porous material in which silicone oil is sealed in the pores is coated with silicate, the silicate film is cracked due to the temperature change of the paint after construction, and the silicone oil sealed in the pores gradually becomes. It exudes and gives antifouling properties to the marking surface. In this type of antifouling modifier, silicone oil is coated with silicate in a state of being sealed in the pores of the porous substance, so that the problem of poor adhesion during construction can be reliably prevented and also prevented. It is preferable as a stain modifier because it is a product having excellent impact resistance and handleability.

【0018】

The silicone oil used in the present invention is a general term for silicone-based oils that exude to the marking surface and exhibit antifouling performance, and the type thereof is not particularly limited, and various silicone-based oils can be used. it can. Specific examples thereof include dimethyl silicone oil, methylphenyl silicone oil, amino-modified silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, fluorosilicone oil, fatty acid-modified silicone oil, and epoxy-modified silicone oil. These can be used alone, or if necessary, two or more types can be used in combination as appropriate. Among them, the one in which three kinds of dimethyl silicone oil, methyl phenyl silicone oil, and amino-modified silicone oil are used in combination is particularly preferable, and the mixture of these three kinds of silicone oils secures the adhesion at the time of marking construction. Immediately after construction, it is recommended that it exhibits excellent antifouling properties and also exhibits excellent antifouling durability.

【0019】

The preferable mixing ratio when using the above three types of silicone oil in combination varies depending on the main vehicle components and pigments that make up the marking paint, the type of inorganic porous substance, and the conditions of use, so it cannot be determined uniformly. The standard compounding composition is 50 parts by mass or more and 70 parts by mass or less for dimethyl silicone oil, more preferably 60 parts by mass or less, and 30 parts by mass or more, more preferably 40 parts by mass or more and 50 parts by mass for methylphenyl silicone oil. The range is 10 parts by mass or less, more preferably 45 parts by mass or less, amino-modified silicone oil 10 parts by mass or more, 20 parts by mass or less, and more preferably 13 parts by mass or less.

【0020】

By the way, if the compounding ratio when the above three types of silicone oils are used in combination is explained in more detail, if the amount of dimethyl silicone oil is less than 50 parts by mass, the exudation to the marked coating surface becomes insufficient, and conversely, if it exceeds 70 parts by mass. It becomes prone to excessive exudation. Further, if the amount of methylphenyl silicone oil is less than 30 parts by mass, the antifouling effect on asphalt is reduced, and if it exceeds 50 parts by mass, it causes a defective coating film. Further, if the amount of the amino-modified silicone oil is less than 10 parts by mass, the antifouling durability effect becomes low, and if it exceeds 20 parts by mass, it causes the coating film to become brittle.

【0021】

The type of silicate is not particularly limited, but it has been found that (1) sodium silicate or (2) potassium silicate, or (3) a mixed salt of sodium silicate and potassium silicate is preferable. When the surface of the silicone oil-containing component or the inorganic porous substance in which the silicone oil is sealed in the pores is coated with the silicate aqueous solution of (1) to (3) above, the road marking paint has excellent antifouling property. An antifouling modifier can be obtained. The case of using these three types of silicates will be described in more detail as follows.

【0022】

(1) When sodium silicate (No. 1 to 3) is used, it is preferable to coat it with an aqueous solution containing 50 to 70% by mass. If sodium silicate (No. 1 to 3) is less than 50% by mass, the coating film strength is insufficient, and conversely, if it exceeds 70% by mass, the coating film strength is excessive.

【0023】

(2) When potassium silicate is used, it is preferable to coat it with an aqueous solution containing 50 to 90% by mass. If potassium silicate is less than 50% by mass, the coating film strength is insufficient, and if it exceeds 90% by mass, the coating film strength is excessive.

【0024】

(3) When a mixed salt of sodium silicate and potassium silicate is used, it is preferable to coat it with an aqueous solution containing 50 to 70% by mass of a mixed salt of 50% by mass of sodium silicate and 50% by mass of potassium silicate. The reason why the mixing ratio of 50% by mass of sodium silicate and 50% by mass of potassium silicate is good is that the coating film strength is appropriate. Further, in the case of a mixed salt, an aqueous solution containing a mixed salt in an amount of less than 50% by mass causes an insufficient coating film strength, and an aqueous solution containing a mixed salt in an amount of more than 70% by mass causes an excessive coating film strength.

【0025】

The method of coating the silicone oil-containing component with silicate is also not particularly limited, but a method of spraying an aqueous silicate solution on the silicone oil-containing component while stirring, adhering the silicate to the surface, and drying to form a film. Can be exemplified. When applying paint by high-temperature melting (180 to 200 ° C), the silicone oil-containing component coated with silicate is heated to 250 to 280 ° C in an inert gas to improve heat resistance. It is preferable to add an antifouling modifier.

【0026】

The inorganic porous material used in the present invention is not particularly limited, but oxides such as aluminum, calcium, magnesium, zirconium, and silicon, and zeolites, sepiolites, silimanites, kaolinites, wollastonites, etc., which are mixtures of these oxides, and the like. Can be mentioned. Among these, the porous material is preferably ceramics in consideration of processability and production cost.

【0027】

The raw materials for these ceramics are not particularly limited as long as they do not deteriorate the properties of the silicone oil and have heat resistance, but the main component is calcium carbonate, which is particularly preferable in terms of cost and performance. , Aluminum oxide and silicon oxide are contained in one or more kinds, and among them, powdered ceramics containing these three kinds in the following ratios are recommended as particularly preferable ones.

【0028】

When the above three types of oxides are contained, preferably calcium carbonate is 10 parts by mass or more, more preferably 20 parts by mass or more, 30 parts by mass or less, more preferably 25 parts by mass or less, and aluminum oxide is 30 parts by mass or more. More preferably 35 parts by mass or more, 50 parts by mass or less, more preferably 40 parts by mass or less, nitrogen oxide is 20 parts by mass or more, more preferably 25 parts by mass or more, 30 parts by mass or less, respectively 10 parts by mass or more and 20 parts by mass. It is mixed to a mass of parts or less, more preferably 15 parts by mass or less, clayified, made into a lump or a plate, dried, and then fired in a temperature range of 800 to 1000 ° C. Then, several tens of μm or more, more preferably. It is produced by pulverizing to 100 μm or more, about 1 mm or less, and more preferably 200 μm or less.

【0029】

At this time, if the amount of calcium carbonate is less than 10 parts by mass, the amount of pores generated is small, and if it exceeds 30 parts by mass, the pores become coarse. If the amount of aluminum oxide is less than 30 parts by mass, it becomes soft ceramics, and if it exceeds 50 parts by mass, it causes firing failure. Further, if the amount of nitrous oxide is less than 20 parts by mass, it causes ceramics having a small pore ratio, and if it exceeds 30 parts by mass, it causes the generation of sealed ceramics. Further, if the amount of water is less than 10 parts by mass, it causes molding failure, and if it exceeds 20 parts by mass, it causes molding failure.

【0030】

In order to obtain an inorganic porous substance in which silicone oil is sealed, a method of immersing the porous substance in the silicone oil or spraying the silicone oil on the porous substance can be exemplified.

【0031】

When an appropriate amount of the antifouling modifier thus obtained is contained in various general road marking paints, the antifouling property of the paint after the marking work can be remarkably and efficiently improved. That is, as described above, the antifouling modifier in which the silicone oil is coated with a silicate, or the antifouling modification in which the silicone oil is sealed in the pores of the inorganic porous material and the outer surface thereof is coated with the silicate. Antifouling modifiers coated with silicates, such as pledges, can be added to all road paints, but paints that are applied to paints that are heated during construction (eg hot melt). Shows even better performance by blending with mold paint, etc.). On the other hand, the antifouling modifier in which silicone oil is sealed in the pores of the inorganic porous substance is preferably added to a paint used in a painting method that does not require heating during construction, such as a water-based road surface paint. ..

【0032】

The type of road marking paint containing the above antifouling modifier is not particularly limited, and can be applied to all the above-mentioned types (1) to (4). Examples of the main vehicle components of each paint are as follows.

【0033】

As the room temperature dry type road surface marking paint described in (1) above, quick-drying synthetic resins such as acrylic resin, unsaturated polyester resin, polyurethane resin, epoxy resin, cashew resin (artificial lacquer), and vinyl chloride resin are the main vehicle components. Examples include those containing.

【0034】

The above-mentioned (2) thermosetting paint for road surface marking has thermosetting properties such as urea resin, melamine resin, phenol resin, epoxy resin, unsaturated polyester resin, alkyd resin, urethane resin, and benzoguanamine resin as main vehicle components. It contains resin.

【0035】

As the hot-melt road marking paint described in (3) above, petroleum resin is generally used as the main vehicle component, but raw rosin, maleated rosin, maleated rosin ester, polyamide resin, unsaturated polyester resin, and xylene. It contains a thermoplastic resin such as a resin.

【0036】

The above-mentioned (4) water-based road marking paint uses an aqueous resin such as acrylic acid resin, alkyd resin, synthetic drying oil, synthetic latex, modified casein, modified starch, and modified nikawa as a cross-linking agent as a vehicle component. ..

【0037】

Further, the road marking paint generally contains pigments, fillers, glass beads, etc. in addition to the above-mentioned main vehicle components, and through a primer to improve the adhesiveness with the road surface, etc. during construction. It is applied to the road surface and the like.

【0038】

Examples of the primer include organic solvents such as toluene, xylene, acetone, and ethyl acetate. As the pigment, white pigments such as titanium oxide, zinc oxide and lithopone, and yellow pigments such as chrome yellow and titanium yellow are used. As the filler, calcium carbonate, silica sand, cold water sand, talc and the like are used. In addition, as an additive, wax of an antioxidant or an antioxidant, or a plasticizer such as a vegetable oil, a vegetable oil-modified alkyd resin, or a phthalate ester may be blended in an appropriate amount as needed.

【0039】

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples do not have properties that limit the present invention, and any design change according to the gist of the above or the following is technical of the present invention. It is included in the range.

【0040】

[Example]

Porous ceramics were used as the porous material, and silicone oil was impregnated into the porous ceramics and coated with a silicate to obtain an antifouling modifier.

【0041】

Porous ceramics are made by adding 25% by mass of calcium carbonate, 35% by mass of aluminum oxide, 30% by mass of silicon oxide, and 10% by mass of water, clayizing the ceramics, drying them, and then firing and crushing them at 850 to 900 ° C. The processed one was used.

【0042】

As the silicone oil, a mixture of 50% by mass of dimethyl silicone oil, 40% by mass of methylphenyl silicone oil, and 10% by mass of amino-modified silicone oil was used.

【0043】

As the silicate, an aqueous solution containing 50% by mass of a mixture of 50% by mass of sodium silicate and 50% by mass of potassium silicate was prepared. The aqueous solution is sprayed on the stirred porous ceramic particles, and the unfired antifouling modifier whose surface is coated and the unfired antifouling modifier are heated at 250 to 280 ° C to improve heat resistance. A fired antifouling modifier was prepared.

【0044】

For road marking paints, as hot melt type paints, bonline (white), mistline (white), mistline (yellow) (all manufactured by Shingokizai Co., Ltd .; the main components are vehicle components, petroleum resin, and soybean oil modification. Alkyd resin, polyethylene wax, low molecular weight polyethylene, titanium oxide as the pigment, calcium carbonate as the constitution material, glass beads as the reflective material, etc.) were used. Also, as a hot or room temperature melt type paint, Hardline C-4000 (white) (manufactured by Atomics Co., Ltd .; the main components are modified epoxy resin for vehicle component, titanium oxide for pigment, extender pigment, anti-precipitation agent for auxiliary agent, Bonpaint Eco (white) (manufactured by Signal Equipment Co., Ltd .; the main ingredients are a special synthetic resin emulsion for the vehicle component, titanium oxide for the pigment, and an extender pigment, as a paint for water-based road surface marking using a film swelling inhibitor, solvent). Dispersants, preservatives, antifoaming agents were used as auxiliary agents, and volatile organic solvents and water were used as solvents.

【0045】

An example of the present invention is a bonline (white), a mist line (white), and a mist line (yellow) to which 1 to 5 parts by mass of a fired antifouling modifier is added, and a mistline (yellow) to which no antifouling modifier is added is used. It was used as a comparative example. Further, as an example of the present invention, 1 to 5 parts by mass of an unfired antifouling modifier was added to Hardline C-4000 (white) and Bonpaint Eco (white), and no antifouling modifier was added. The one was used as a comparative example.

【0046】

When bonline (white) was used, the work (specimen) was melt-coated at 180 ° C, and when mistline (white) and mistline (yellow) were used, it was melted at 180-200 ° C. The work was spray-coated with a hot spray gun. When using Hardline C-4000 (white), apply it at room temperature, bake it at 200 ° C, dry it, and cool it for 10 minutes or more. After coating with, the work was naturally dried for 24 hours. The work was fixed to the pedestal of the turning test machine, and contamination measurement was performed by the tire turning method.

【0047】

Contamination measurement of the tire turning method was performed as follows. Using NBR (nitrile butadiene rubber) tires (diameter 100 mm, width 20 mm, thickness 50 mm), swivel diameter φ130 mm, load pressure 200 kg / cm², Turn on the work for 2 hours at 100r.pm and transfer the tire marks to the work surface. After washing the tire marks with water, the degree of contamination of the paint-coated surface was visually evaluated. Tires with virtually no stains (excellent antifouling properties) are rated as "1", and those with significant stains remaining (poor antifouling properties) are rated as "5". Was evaluated on a 5-point scale. The results are shown in Table 1.

【0048】

[table 1]

<img file="JP2002121539A_D0001.tif" />【0049】

As can be seen from Table 1, when 1 part by mass of the antifouling modifier of the present invention was added to the road marking paint, the antifouling effect was exhibited in all the paints. In particular, when Bonline (white), Mistline (white), Mistline (yellow), and Bonpaint Eco (white) are used, an excellent effect can be obtained by adding 2 parts by mass of the antifouling modifier of the present invention. It is possible to substantially prevent non-adhesion of dirt. When Hardline C-4000 (white) is used, adding 5 parts by mass of an antifouling modifier exerts an excellent effect and prevents non-adhesion of stains.

【0050】

[Effect of the invention]

Provided is an antifouling modifier capable of exhibiting excellent adhesion to the road surface and imparting properties such that excellent antifouling property can be maintained for a long period of time to the paint, and by extension, the antifouling modifier. By blending the above, it was possible to provide an antifouling paint for road marking with excellent antifouling durability.