WO2020138355A1

WO2020138355A1 - Paint composition set, method for forming multilayer coating film, road marking method, and method for removing road marking

Info

Publication number: WO2020138355A1
Application number: PCT/JP2019/051282
Authority: WO
Inventors: 健二高口; 圭太内川
Original assignee: 日本ペイント・インダストリアルコーティングス株式会社
Priority date: 2018-12-27
Filing date: 2019-12-26
Publication date: 2020-07-02
Also published as: JP6662996B1; JP2020105368A

Abstract

The purpose of the present invention is to provide a road marking paint composition, wherein the degradation and wear of a coating film formed from the road marking paint composition can be suppressed, and the formed coating film can be easily removed. The present invention pertains to a paint composition set for forming a multilayer coating film having a first coating film and a second coating film, the paint composition set comprising: a first paint composition for forming the first coating film; and a second paint composition for forming the second coating film, wherein the first paint composition contains a first coating film-forming component (A1), a dry coating film of the first paint composition has a thermal conductivity of 0.01-0.5 W/m·K, and the second paint composition contains a second coating film-forming component (A2), a foaming agent (B), and a carbonization agent (C).

Description

Paint composition set, multilayer coating film forming method, road marking and road marking removing method

The present disclosure relates to a coating composition set, a multilayer coating film forming method, a road marking and a road marking removing method.

A coating film that can be formed from the coating composition, such as a road marking, can be used as a lane on the road surface, such as a white line. In addition to normal road surfaces, road marking for temporary installation of lanes is necessary not only on road surfaces under construction. For example, various coating compositions can be used as a boundary line (white line or the like) for displaying a temporary lane different from the original lane.
Furthermore, even temporary road markings need to be visible to drivers, pedestrians, etc. during construction.
On the other hand, after the completion of construction, it is necessary to remove the temporary lane or take some measures so that it cannot be seen by the observer.

For example, Japanese Unexamined Patent Application Publication No. 2005-154672 (Patent Document 1) provides a marking material for road surface temporary construction having a thermal expansion layer containing a binder, a pigment, and thermally expandable microspheres.

JP, 2005-154672, A

In recent years, a lot of repair work for road maintenance has been performed. At that time, it is necessary to rewrite the road markings to change the lanes, etc. Therefore, during the repair work, the road markings (hereinafter, also referred to as coating films) are rewritten more than once several times. In such a case, there is a case where the coating film must be rewritten and erased every several days to several months depending on the usage period, which is significantly shorter than the service life of the coating film, or the situation.
However, on such a road surface, if a usual road marking coating composition is used, the removal of the coating film such as the white line is polished by using a rotating grindstone such as a grinder, or by shot blasting or water jet. There is a problem that the coating film needs to be scraped off, the road surface is damaged, and the removing work requires a lot of labor.
It is also practiced to coat a temporary white line with a coating composition having the same color as the road surface (black, gray, etc.) to hide the temporary coating film. However, the coating film may peel off due to the passage of vehicles, and hidden white lines may appear.

On the other hand, road markings have also been formed with temporary road surface coating compositions. For example, the temporary marking material described in the above-mentioned Patent Document 1 contains thermally expandable microspheres in addition to the matrix resin in order to easily remove the coating film from the road surface.
However, such marking material for temporary road surface cannot sufficiently suppress deterioration and wear due to passage of vehicles. For example, when used in units of several years, it is necessary to frequently repair and repaint road markings.
Similarly, an easily peelable adhesive tape may be used as a temporary white line. However, when the adhesive tape is used on a road with a large amount of traffic (also referred to as a road with heavy traffic), peeling from the road surface, misalignment, etc. are likely to occur.

Thus, in view of the situation of the road business in recent years, characteristics that are not conventional, that is, deterioration and wear of the coating film formed from the road marking composition can be sufficiently suppressed for a long period of time, In addition, the coating composition is required to have contradictory properties such that the formed coating film can be easily removed.

The present disclosure aims to solve the above problems, and provides a coating composition set that can suppress deterioration and wear of a coating film formed from the coating composition and can easily remove the formed coating film. The purpose is to do. Furthermore, it aims at providing a multilayer coating film forming method, a road marking, and a road marking removing method.

In order to solve the above problems, the present disclosure provides the following aspects.
[1] The present disclosure provides a coating composition set for forming a multilayer coating film having a first coating film and a second coating film,
The coating composition set includes a first coating composition forming a first coating film and a second coating composition forming a second coating film,
The first coating composition contains a first coating film forming component (A1),
The thermal conductivity of the dry coating film of the first coating composition is 0.01 W/m·K or more and 0.5 W/m·K or less,
The second coating composition is
Second coating film forming component (A2),
Foaming agent (B),
Carbonizing agent (C)
including.
[2] In one embodiment, the hydroxyl value of the carbonizing agent (C) is 500 mgKOH/g or more and 1,900 mgKOH/g or less.
[3] In one embodiment, the total hydroxyl value of the second coating film forming component (A2) and the carbonizing agent (C) represented by the following formula in the second coating film is 40 mgKOH/g or more 1. Below 600 mg KOH/g:
Total hydroxyl value (mgKOH/g)=[hydroxyl value of (A2)×(A2) mass+(C) hydroxyl value×(C) mass]/total mass of the second coating film.
[4] In one embodiment, the foaming agent (B) contains at least one selected from the group consisting of a phosphoric acid compound (B1), a nitrogen-containing compound (B2) and a halogen compound (B3).
[5] In one embodiment, the second coating film forming component (A2) is an acrylic resin (A2-1), a polyurethane resin (A2-2), an epoxy resin (A2-3), a petroleum resin (A2-4), It contains at least one selected from the group consisting of a cellulose resin (A2-5) and a (meth)acrylate monomer and/or oligomer (A2-6) having at least one (meth)acryloyl group.
[6] In one aspect, the second coating composition further contains a reaction initiator (D).
[7] In one embodiment, the carbonizing agent (C) is pentaerythritol, dipentaerythritol, tripentaerythritol, neopentaerythritol, ditrimethylolpropane, trimethylolpropane, dioxane glycol, sorbitol, xylitol, inositol, mannitol, glucose, It contains at least one selected from the group consisting of fructose, cellulose, lignin, chitin and derivatives thereof.
[8] In one embodiment, the phosphoric acid compound (B1) is phosphoric acid, polyphosphoric acid, ammonium phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, dimelamine pyrophosphate, guanidine phosphate, guanylurea phosphate, It is at least one selected from the group consisting of ammonium polyphosphate and melamine polyphosphate.
[9] In one aspect, the nitrogen-containing compound (B2) is at least one selected from the group consisting of melamine, dicyandiamide, azobistetrazole, azodicarbonamide, urea, thiourea, and derivatives thereof.
[10] In one embodiment, the amount of the carbonizing agent (C) in the second coating composition is 3 parts by mass with respect to 100 parts by mass of the second coating film forming component (A2) contained in the second coating composition. And more than 500 parts by mass.
[11] In one embodiment, the coating composition set of the present disclosure is a coating composition set for road marking.
[12] In another embodiment, the present disclosure is a method for forming a multilayer coating film using the above-mentioned coating composition set, wherein the first coating composition in the coating composition set is applied onto an object to be coated. Forming the first coating film by the step (1), and forming the second coating film by coating the second coating composition in the coating composition set on the first coating film obtained by the step (1). A method for forming a multilayer coating film including the step (2) of
For example, in the method for forming a multilayer coating film according to the present disclosure, as described in [1] above, the first coating film has a dry coating film having a thermal conductivity of 0.01 W/m·K or more and 0.5 W/m or more. m·K or less, and the second coating composition contains the second coating film forming component (A2), the foaming agent (B), and the carbonizing agent (C).
In one aspect, the method for forming a multilayer coating film according to the present disclosure can form a multilayer coating film using the coating composition set according to at least one of the above [2] to [11].
[13] In one aspect, the multilayer coating film formed by the method for forming a multilayer coating film may be a road marking.
[14] In another embodiment, the present disclosure is a method of forming a road marking, which uses the above-mentioned road marking coating composition set,
A step of coating the first coating composition in the coating composition set on a substrate to form a first coating film;
A step of coating the second coating composition in the coating composition set to form a second coating film on the first coating film obtained by the step, and a second coating film formed in the step Before drying, the reflecting material is sprayed on the second coating film to fix the reflecting material on the surface of the second coating film.
including,
A method of forming a road marking is provided.
[15] In another aspect, the present disclosure provides a pavement marking removing method, which further comprises removing the pavement marking formed by the above forming method by heating.

The coating composition set of the present invention can cope with heavy traffic and can form a multilayer coating film having excellent durability. Further, the multilayer coating film formed from the coating composition set of the present disclosure can be easily removed.

The background of the invention will be described. The temporary marking material disclosed in Patent Document 1 has a large amount of heat-expandable microspheres added to a known coating film-forming resin, and is physically peeled by physically suppressing the durability of the coating film-forming resin. It improves the sex. On the other hand, in the coating composition, as the durability of the coating film is improved, easy peeling of the coating film tends to be difficult.
As described above, in the coating composition, for example, the coating composition for road marking, there is a trade-off relationship between the durability of the coating film and the easy removal property (easy peeling property).

The present inventors aimed to develop a coating composition set in which the durability and releasability of a coating film are compatible with each other in order to solve the above-mentioned novel problems.
As a result, the inventors
A coating composition set for forming a multilayer coating film comprising a first coating film and a second coating film,
The coating composition set includes a first coating composition forming a first coating film and a second coating composition forming a second coating film,
The first coating composition contains a first coating film forming component (A1),
The thermal conductivity of the dry coating film of the first coating composition is 0.01 W/m·K or more and 0.5 W/m·K or less,
The second coating composition is
Second coating film forming component (A2),
Foaming agent (B),
Carbonizing agent (C)
including,
With the coating composition set of the present disclosure, it has been found that the durability and easy removability of a coating film can be provided in a well-balanced manner and the above problems can be solved, and the present invention has been completed.
By including a predetermined first coating composition and a second coating composition according to the present disclosure in combination, a multilayer coating film that can be visually recognized well by a driver, a pedestrian, etc., and can also suppress deterioration and wear. Can be formed. Moreover, the formed multi-layer coating film can be easily removed as compared with the conventional coating film.

Further, according to another aspect of the present disclosure,
Step (1) of forming a first coating film by coating the first coating composition on an object to be coated, and coating the second coating composition on the first coating film obtained by the step (1) And a step (2) of forming a second coating film, the method comprising:
The first coating film has a dry coating film having a thermal conductivity of 0.01 W/m·K or more and 0.5 W/m·K or less, and the second coating composition is
Second coating film forming component (A2),
Foaming agent (B),
Carbonizing agent (C),
A method for forming a multilayer coating film is provided, which comprises:
By including a predetermined first coating composition and a second coating composition according to the present disclosure in combination, a multilayer coating film that can be visually recognized well by a driver, a pedestrian, etc., and can also suppress deterioration and wear. Can be formed. Moreover, the formed multilayer coating film can be easily removed.

Although not to be construed as a specific mechanism, in a multilayer coating film formed from the coating composition set of the present disclosure, for example, a multilayer coating film for road marking, when the coating film is peeled off, the coating film forming temperature is By including a heating step higher than that, it is possible to embrittle the coating film by foaming due to thermal decomposition of the foaming agent (B) contained in the coating film, and at the same time, by the interaction of carbonization of the carbonizing agent (C). Since it can be peeled off with a brush and removed by suction, the coating film can be removed more easily. That is, in the case of the coating composition of the present disclosure, it is not necessary to remove the coating film by polishing with a rotating grindstone such as a grinder, or to scrape off, damage the road surface, and a great deal of labor is required for the removal work. Can solve problems.
Further, in the present disclosure, the thermal conductivity measured for the dry coating film in the first coating composition is 0.01 W/m·K or more and 0.5 W/m·K or less, and further, the second coating film. By being formed from a predetermined coating composition, at least the second coating film can be efficiently foamed and carbonized.

In the present disclosure, by including a predetermined first coating composition and a second coating composition in combination, a multi-layer coating film that can be satisfactorily visually recognized by a driver, a pedestrian, or the like, and further can be suppressed from deterioration and wear. Can be formed.
More specifically, when a multilayer coating film formed by the coating composition set of the present disclosure is used for, for example, road marking, the resulting multilayer coating film sufficiently suppresses deterioration and wear due to vehicle traffic and the like. it can. For example, even when used in units of several years, it is not necessary or difficult to frequently repair and repaint road markings. Further, even when it is used on a road with heavy traffic, it is possible to suppress separation from the road surface, positional deviation, and the like.
Further, by providing the specific first coating film, the second coating film can be easily foamed and carbonized in a short time, and the formed multilayer coating film, particularly the second coating film, can be easily removed. it can.
In addition, at least the second coating film can be easily removed if it is a multilayer coating film formed by the coating composition set of the present disclosure. Therefore, a multilayer coating film for road marking is compared with a conventional coating film. In addition, it can be removed in a short time, and moreover, the damage on the road surface can be suppressed.
As described above, in the case of the multilayer coating film formed by the coating composition set of the present disclosure, deterioration and wear of the formed coating film can be sufficiently suppressed for a long period of time, and further, the formed coating film. It is possible to satisfy contradictory characteristics such as easy removal of the film.

According to the coating composition set and the multilayer coating film forming method according to the present disclosure, the coating composition set includes a predetermined first coating composition forming a first coating film and a predetermined first coating composition forming a second coating film. 2 coating composition.
In one aspect, in the coating composition set according to the present disclosure, the first coating film is disposed adjacent to the object to be coated, and the second coating film is the surface of the first coating film opposite to the object to be coated. It is arranged above, that is, above the first coating film. According to this aspect, for example, when the coating composition set according to the present disclosure is used for road marking, the second coating film is a coating film on the side visually recognized by a driver, a pedestrian, or the like.
Further, in the coating composition set for forming a multilayer coating film, the amount of the first coating composition forming the first coating film and the amount of the second coating composition forming the second coating film are required. It can be appropriately selected according to the film thickness of the first coating film and the second coating film.

Hereinafter, in the present disclosure, the second coating composition that forms the second coating film will be described, and then the first coating composition that forms the first coating film will be described.

[Second coating composition]
The second coating composition according to the present disclosure includes a second coating film forming component (A2), a foaming agent (B) and a carbonizing agent (C).

Second coating film forming component (A2)
The second coating film forming component (A2) according to the present disclosure is an acrylic resin (A2-1), a polyurethane resin (A2-2), an epoxy resin (A2-3), a petroleum resin (A2-4), a cellulose resin ( A2-5), at least one selected from the group consisting of (meth)acrylate monomers and/or oligomers (A2-6) having at least one (meth)acryloyl group.
Further, the second coating film forming component (A2) may be used in combination with a cross-linking agent (for example, amino resin, block polyisocyanate compound, amine cross-linking agent, polyamide cross-linking agent, polyvalent carboxylic acid cross-linking agent, etc.), if necessary. May be.

Acrylic resin (A2-1)
In one aspect, the second coating film forming component (A2) contains an acrylic resin (A2-1). By including the acrylic resin (A2-1), the second coating film forming component (A2) according to the present disclosure can form a coating film that can suppress deterioration and wear. As the acrylic resin contained in the second coating film forming component (A2), a known acrylic resin can be used.
Furthermore, in the embodiment in which the second coating composition contains an acrylic resin (A2-1), the second coating composition further contains a foaming agent (B) and a carbonizing agent (C), and the second coating film further comprises: Since it is formed on the predetermined first coating film, the removal of the second coating film and the removal of the multilayer coating film can be performed more easily.
Furthermore, by including the acrylic resin (A2-1), the weather resistance of the obtained coating film is improved, and the deterioration of the coating film can be further suppressed.
In one aspect, the second coating film forming component (A2) is an acrylic resin (A2-1).

In one aspect, the hydroxyl value of the acrylic resin (A2-1) is 0 mgKOH/g or more and 500 mgKOH/g or less, for example, 0 mgKOH/g or more and 250 mgKOH/g or less, and in another aspect, 0 mgKOH/g or more and 100 mgKOH/g or less. Is. When the hydroxyl value of the acrylic resin (A2-1) is within such a range, the strength and durability of the resulting coating film can be improved. For example, it is possible to form a coating film which is excellent in coating film strength and durability and which is also excellent in visibility. In the present disclosure, the hydroxyl value represents the solid content hydroxyl value and can be measured according to the measuring method described in JIS K 0070.

Here, in the present disclosure, “excellent in durability” means that it can be used as a road marking such as a white line for at least one week and two years. That is, unlike the conventional usage period of temporary road markings (for example, several hours to one month), it can withstand long-term use unless it is heated at 270° C. or higher for the purpose of peeling. A coating film can be formed.

Further, by combining the acrylic resin (A2-1) having a hydroxyl value within the above range, the foaming agent (B) according to the present disclosure, and the carbonizing agent (C), a coating film can be more effectively formed. It can be made brittle. Due to such characteristics, road markings such as white lines can be easily removed. For example, the paint film as a road marking can be removed without polishing or scraping it off with a grinder, etc., so that scratches on the road surface and scattering of the road surface material removed with the paint film can be suppressed, and health damage to workers can be suppressed. Also, the environmental load can be suppressed. Further, the work of removing the coating film can be greatly suppressed. Furthermore, high water resistance can be imparted to the obtained coating film, and it can withstand long-term use as a road marking material.

In one aspect, the total hydroxyl value of the second coating film forming component (A2) represented by the following formula and the carbonizing agent (C) in the second coating film is 40 mgKOH/g or more and 1,600 mgKOH/ g or less:
Total hydroxyl value (mgKOH/g)=[hydroxyl value of (A2)×(A2) mass+(C) hydroxyl value×(C) mass]/total mass of the second coating film The total hydroxyl value of the second coating film-forming component (A2) represented by the above formula and the carbonizing agent (C) in the second coating film is 100 mgKOH/g or more and 1200 mgKOH/g or less. It is 200 mgKOH/g or more and 1000 mgKOH/g or less. In one aspect, the total hydroxyl value of the second coating film forming component (A2) represented by the above formula and the carbonizing agent (C) in the second coating film is 200 mgKOH/g or more and 750 mgKOH/g or less. Yes, for example, 200 mgKOH/g or more and 500 mgKOH/g or less.
By having such a relationship, the strength, durability, water resistance and the like of the obtained coating film can be improved. For example, it is possible to form a coating film which is excellent in coating film strength, durability and water resistance and is also highly visible. Moreover, the coating film can be peeled off safely and easily without impairing the physical properties of the various coating films described above.
Here, in the calculation of the hydroxyl value based on the above formula, the hydroxyl value of the carbonizing agent (C) means the hydroxyl value of the carbonizing agent (C) contained in the second coating film. For example, when the first coating composition may contain a carbonizing agent (C), the hydroxyl value of the carbonizing agent (C) contained in the first coating composition (first coating film) should be considered in order to facilitate calculation. You don't have to.
Further, the calculation of the hydroxyl value in the second coating film is performed by a known method in the state of the solid content after heating (drying) the second coating film forming component.

The weight average molecular weight of the acrylic resin (A2-1) is, for example, 20,000 or more and 200,000 or less, and in one embodiment, 30,000 or more and 80,000 or less. When the weight average molecular weight is in such a range, a coating film having excellent coating film strength and durability can be formed. Furthermore, the gas foamed by the foaming agent (B) according to the present disclosure can be efficiently captured in the entire coating film. As a result, the coating film can be more effectively embrittled when the coating film is foamed.
In addition, it is possible to obtain a second coating composition having excellent coating workability, particularly spray coating workability. In the present disclosure, the weight average molecular weight can be calculated from the measurement result of gel permeation chromatography (GPC) using polystyrene as a standard.

The glass transition temperature of the acrylic resin (A2-1) is 5 to 120° C., for example, 20 to 100° C. in one embodiment. When the glass transition temperature of the acrylic resin (A2-1) is within such a range, appropriate flexibility and hardness can be imparted to the coating film in a well-balanced manner, and a coating film having excellent durability, such as road marking, can be obtained. Can be formed. Furthermore, when the coating film is embrittled by heating, the coating film is likely to soften, and excellent removability can be obtained. In the present disclosure, the glass transition temperature can be measured using a differential scanning calorimeter (DSC) according to JIS K7121.

The acrylic resin (A2-1) according to the present disclosure can be obtained, for example, by polymerizing a hydroxyl group-containing monomer and, if necessary, a polymerizable monomer that can be copolymerized with the hydroxyl group-containing monomer, by a conventional method.

The hydroxyl group-containing monomer is not particularly limited, and examples thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxypropyl (meth)acrylate, and 2-hydroxyethyl ( Examples thereof include those obtained by ring-opening (meth)acrylate with ε-caprolactone (Placcel FA and FM series manufactured by Daicel Chemical Industries Ltd.). These monomers may be used alone or in combination.

In the acrylic resin (A2-1) according to the present disclosure, the amount of the hydroxyl group-containing monomer is 0 parts by mass or more and 40 parts by mass or less based on 100 parts by mass of the monomer component constituting the acrylic resin (A2-1). For example, it is 0 parts by mass or more and 30 parts by mass or less. Since the acrylic resin (A2-1) has such a relationship, the hardness and finish of the coating film can be improved. Further, an acrylic resin (A2-1) having a hydroxyl value within the above range can be obtained, and the strength and durability of the coating film can be improved.

In one embodiment, the acrylic resin (A2-1) according to the present disclosure is obtained by polymerizing, for example, a monomer not containing a hydroxyl group and, if necessary, a polymerizable monomer copolymerizable with a monomer not containing a hydroxyl group, by a conventional method. Obtainable. By including such a monomer, the hardness and finish of the coating film can be improved. Furthermore, the water resistance of the coating film can be further improved.
For example, the acrylic resin (A2-1) having no hydroxyl group may be prepared by combining plural kinds of monomers having no hydroxyl group.

The polymerizable monomer copolymerizable with the hydroxyl group-containing monomer and/or the monomer having no hydroxyl group is not particularly limited, and examples thereof include carboxylic acid group-containing monomers such as (meth)acrylic acid, maleic acid and itaconic acid, and glycidyl (meth). In addition to epoxy group-containing monomers such as acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, vinyltoluene, vinyl acetate, Examples thereof include vinyl propionate, styrene, methylstyrene, butylstyrene, decylstyrene, vinylnaphthalene, vinyltoluene, vinylxylene, methylvinyltoluene, methylvinylxylene, ethylstyrene, ethylvinyltoluene and ethylvinylxylene. These may be used alone or in combination of two or more.

In one embodiment, the polymerizable monomer copolymerizable with the hydroxyl group-containing monomer and/or the monomer having no hydroxyl group is styrene, methylstyrene, butylstyrene, decylstyrene, vinylnaphthalene, vinyltoluene, vinylxylene, methylvinyltoluene, methylvinyl. It is an aromatic monomer selected from xylene, ethylstyrene, ethylvinyltoluene, ethylvinylxylene and the like. These may be used alone or in combination of two or more.
By including these aromatic monomers as the polymerizable monomer that can be copolymerized with a hydroxyl group-containing monomer and/or a monomer that does not contain a hydroxyl group, the hardness of the obtained coating film increases and a coating film that can further suppress wear can be formed. Also, the coating film can be removed more easily.

The amount of styrene in the acrylic resin (A2-1) is in the range of 5 to 60 parts by mass, for example, 10 to 50 parts by mass with respect to 100 parts by mass of the monomer component constituting the acrylic resin (A2-1). It is within. With such an amount, a coating film capable of suppressing deterioration and wear can be formed, and the coating film can be removed more easily.

In one embodiment, the polymerizable monomer that can be copolymerized with the hydroxyl group-containing monomer and/or the monomer having no hydroxyl group is an ester of an acid and vinyl alcohol such as vinyl acetate and vinyl propionate. These may be used alone or in combination of two or more. By containing these monomers, it is possible to form a coating film capable of suppressing deterioration and wear, and it is possible to easily remove the coating film.

The acrylic resin (A2-1) containing these monomers can form a coating film that can more effectively suppress deterioration and wear, and can further easily remove the coating film, thereby forming a road marking. It can be preferably used as a product. In addition, the water resistance of the coating film can be improved.

When the second coating film forming component (A2) contains an acrylic resin (A2-1), a curing agent may be contained if necessary. The curing agent may include a known curing agent, and may include, for example, a blocked polyisocyanate compound.

Polyurethane resin (A2-2)
As the polyurethane resin (A2-2) contained in the second coating film forming component (A2), for example, various kinds of acrylic resin having a hydroxyl group, polyester resin having a hydroxyl group, polyether resin having a hydroxyl group, polycarbonate resin having a hydroxyl group, etc. Examples thereof include resins having a urethane bond, which are obtained by reacting the polyol component (a2-1) with the polyisocyanate compound (a2-2).

Examples of the polyisocyanate compound include 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), and a mixture thereof (TDI), diphenylmethane-4,4′. -Diisocyanate (4,4'-MDI), diphenylmethane-2,4'-diisocyanate (2,4'-MDI), and mixtures thereof (MDI), naphthalene-1,5-diisocyanate (NDI), 3,3' -Dimethyl-4,4'-biphenylene diisocyanate (TODI), xylylene diisocyanate (XDI), dicyclohexylmethane diisocyanate (hydrogenated HDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), hydrogenated xylylene diisocyanate Isocyanate (HXDI) etc. can be mentioned.

The polyurethane resin that can be contained in the second coating film forming component (A2) may be a two-component polyurethane resin composed of a main agent and a curing agent. The polyurethane resin as the second coating film forming component (A2) may also be a prepolymer obtained by previously reacting the polyol component (a2-1) with the polyisocyanate compound (a2-2).

Epoxy resin (A2-3)
Examples of the epoxy resin (A2-3) contained in the second coating film forming component (A2) include epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and o-cresol novolac type epoxy resin. One of these epoxy resins may be used alone, or two or more thereof may be used in combination.

The bisphenol A type epoxy resin preferably has an epoxy equivalent of 400 to 2,200 g/eq. As the bisphenol A type epoxy resin, a commercially available one may be used. Specific examples of commercially available bisphenol A type epoxy resins include, for example, Epotote series manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (eg, Epotote YD-014, Epotote YD-017, Epotote YD-904H, Epotote YD-907, etc.), Mitsubishi Examples thereof include jER series (for example, jER1003F, jER1004F, jER1005F, etc.) manufactured by Kagaku Co., Ltd., EPICLON series (for example, EPICLON840, EPICLON850 etc.) manufactured by DIC.
In addition, in the present disclosure, the epoxy equivalent can be measured by a method according to JIS K 7236.

As the bisphenol F type epoxy resin, one having an epoxy equivalent of 800 to 2,500 g/eq is preferable. As the bisphenol F type epoxy resin, a commercially available one may be used. Specific examples of commercially available bisphenol F type epoxy resins include, for example, Epotote series (eg, Epotote YDF-2004H, Epotote YDF-2005RL, etc.) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., jER series (eg, jER4005P) manufactured by Mitsubishi Chemical. , JER4007P, etc.) and the like. These may be used alone or in combination of two or more.

The o-cresol novolac type epoxy resin preferably has an epoxy equivalent of 195 to 220 g/eq. As the o-cresol novolac type epoxy resin, a commercially available one may be used. Specific examples of commercially available o-cresol novolac type epoxy resins include, for example, Epotote series manufactured by Nippon Steel & Sumitomo Metal Corporation (eg, Epotote YDCN-701, Epotote YDCN-703, Epotote YDCN-704, etc.). it can. These may be used alone or in combination of two or more.

As the epoxy resin (A2-3), an epoxy acrylate resin having a plurality of acrylate groups at the terminals can be used in addition to the above epoxy resin. Examples of the epoxy acrylate resin having a plurality of acrylate groups at the terminals include resins obtained by introducing an acrylate group into the terminal epoxy groups of the above epoxy resin. The number of acrylate groups contained in the epoxy acrylate resin is preferably two. The double bond equivalent of the epoxy acrylate resin is preferably 300 to 700, more preferably 400 to 600.

In one embodiment, the softening point of the epoxy resin (A2-3) is in the range of 60 to 120°C. When the softening point is within such a range, appropriate flexibility and hardness can be imparted to the coating film in a well-balanced manner, and road marking excellent in durability can be formed. Furthermore, when the coating film is embrittled by heating, the coating film is likely to soften, and excellent removability can be obtained.

When the coating film forming component (A) contains an epoxy resin (A2-3), a curing agent may be included if necessary. Examples of the curing agent that can be used in combination with the epoxy resin (A2-3) include a phenolic curing agent, an amine curing agent, a thiol curing agent, and an acid anhydride curing agent. One of these curing agents may be used alone, or two or more thereof may be used in combination.

As the phenolic curing agent, a commercially available one may be used. Specifically, for example, jER Cure 171N (phenolic hydroxyl group equivalent weight 200 to 286 g/eq, softening point about 80° C., manufactured by Mitsubishi Chemical), jER Cure 170 (phenolic hydroxyl group equivalent weight 286 to 400 g/eq, softening point about 90° C., manufactured by Mitsubishi Chemical Corporation) and the like. These may be used alone or in combination of two or more.

Examples of the amine curing agent include aliphatic polyamines (eg, ethylenediamine, N-hydroxyethylethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, etc.); alicyclic polyamines (eg, 4,4′-diaminodicyclohexylmethane, 1 , 4-diaminocyclohexane, isophoronediamine, etc.); Aliphatic polyamines having an aromatic ring (eg, xylylenediamine, tetramethylxylylenediamine, etc.); Aromatic polyamines (eg, 4,4′-diaminodiphenylmethane, tolylenediamine) , Benzidine, phenylenediamine and the like); and polyamidoamine obtained by the reaction of the above polyamine and polymerized fatty acid; and the like. A commercially available amine curing agent may be used. Examples of commercially available amine curing agents include jER Cure series manufactured by Mitsubishi Chemical Co., Sunmide series manufactured by Air Products Co. (various amine adducts, polyamide amine resins, etc.), Tomid series manufactured by T&K TOKA (various polyamide amines). ) And the like.

Examples of the thiol curing agent include polythiol compounds and the like. A commercially available thiol curing agent may be used. Examples of commercially available thiol curing agents include Karenz MT series manufactured by Showa Denko KK and jER Cure series manufactured by Mitsubishi Chemical.

Examples of the acid anhydride curing agent include alicyclic acid anhydride compounds and aromatic acid anhydride compounds. As the acid anhydride curing agent, a commercially available one may be used. Examples of commercially available acid anhydride curing agents include RIKACID manufactured by Shin Nippon Rika Co., Ltd., and the like.

The above curing agents may be used alone or in combination of two or more. The amount of the curing agent can be arbitrarily selected according to the type of epoxy resin (A2-3) and the curing agent used. For example, it is preferable to use it in an amount such that the reactive group (active hydrogen equivalent) of the curing agent is 0.5 to 2.0 equivalents relative to 1 equivalent of epoxy groups of the epoxy resin (A2-3), and 0.8 to 1 More preferably, it is used in an amount of 5 equivalents.

A curing accelerator may be used in addition to the above curing agent. Examples of the curing accelerator include imidazoline-based curing accelerators and the like. The imidazoline-based curing accelerator is not particularly limited, and commercially available ones may be used. Specific examples of commercially available imidazoline curing agents include, for example, 2PZL (2-phenylimidazoline, manufactured by Shikoku Chemicals Co., Ltd.), 2E/4MZL (2-ethyl-4-methylimidazoline, manufactured by Shikoku Chemicals Co., Ltd.) and the like. Can be mentioned. These may be used alone or in combination of two or more. When a curing accelerator is used, it is preferably used within a range of 0.1 to 10.0% by mass based on 100 parts by mass of the above curing agent.

As the curing agent that can be used in combination with the epoxy resin (A2-3), it is preferable to use one or more of an amine curing agent, a thiol curing agent and an acid anhydride curing agent. By including these curing agents, it is possible to impart appropriate flexibility and hardness to the coating film, especially the second coating film in a well-balanced manner, and to form a road marking excellent in durability.

Petroleum resin (A2-4)
The petroleum resin (A2-4) that can be contained in the second coating film forming component (A2) is obtained by polymerizing a C9 fraction such as styrene derivative, indene and vinyltoluene in heavy oil by-produced by decomposition of petroleum naphtha. Aromatic petroleum resin; aliphatic petroleum resin obtained by polymerizing C5 fraction such as 1,3-pentadiene and isoprene; copolymer petroleum resin obtained by copolymerizing the above C9 fraction and C5 fraction; cyclo Aliphatic petroleum resin in which conjugated dienes of C5 fraction such as pentadiene and 1,3-pentadiene are partially cyclopolymerized; Resin in which the above aromatic petroleum resin is hydrogenated; Alicyclic polymer in which dicyclopentadiene is polymerized System petroleum resin; acid-modified petroleum resin obtained by acid-denaturing the above-mentioned petroleum resin;

Cellulose resin (A2-5)
The cellulose resin (A2-5) that can be contained in the second coating film forming component (A2) is at least one selected from the group consisting of cellulose acetate butyrate, nitrocellulose, cellulose acetate, and cellulose acetate propionate. Cellulose resins may be mentioned.

Polymerizable monomer and/or polymerizable oligomer (A2-6)
The polymerizable monomer and/or the polymerizable oligomer (A2-6) that can be contained in the second coating film forming component (A2) are compounds having a polymerizable functional group in one molecule. Examples of the polymerizable functional group include an ethylenically unsaturated double bond group-containing group, and a (meth)acryloyl group is more preferable. In addition, in this indication, a (meth)acryloyl group represents an acryloyl group and a methacryloyl group.

As the polymerizable monomer and/or the polymerizable oligomer (A2-6), a compound having one or more (meth)acryloyl group in one molecule can be used. The polymerizable monomer and/or the polymerizable oligomer (A2-6) may be a monomer or an oligomer as long as it is a compound having a (meth)acryloyl group.
By including the polymerizable monomer and/or the polymerizable oligomer (A2-6), the mechanical strength of the obtained coating film, particularly the second coating film, can be further increased.
For example, in the above compound, the number of (meth)acryloyl groups contained in one molecule is 10 or less.

As the polymerizable oligomer, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc. Homopolymers and/or copolymers of (meth)acrylate can be preferably used. In one embodiment, a copolymer of (meth)acrylic acid may be used.

As the polymerizable monomer, acrylonitrile and the like can be used in addition to the above (meth)acrylate and (meth)acrylic acid.

The second coating film forming component (A2) may optionally contain a reaction initiator (D). For example, when the second coating film forming component (A2) contains a polymerizable monomer and/or a polymerizable oligomer (A2-6), a reaction initiator (D) may be contained, if necessary.
By including the reaction initiator (D), for example, in a mode in which the second coating film forming component (A2) contains a polymerizable monomer and/or a polymerizable oligomer (A2-6), the curing time of the second coating film Can be shortened further. Further, the mechanical strength of the obtained coating film, particularly the second coating film, can be further enhanced.

An organic peroxide can be used as the reaction initiator (D). Specific examples of the organic peroxide include benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, tert-butylperoxybenzoate, tert-butylperoxy 2-ethylhexanoate and t-butylperoxide. Examples thereof include oxylaurate, t-butyl hydroperoxide, dicumyl hydroperoxide, 3,3,5-trimethylhexanoyl peroxide, diisopropyl peroxydicarbonate, etc., and cobalt naphthenate for the purpose of further promoting curing. A cobalt salt such as cobalt octylate or an amine compound such as dimethylaniline may be used in combination with the above organic peroxide.

The second coating film forming component (A2) can be used by diluting it with a solvent. The solvent is not particularly limited and can be appropriately selected within a range that does not impair the properties of the coating composition set of the present disclosure. For example, water, an organic solvent, or a mixture thereof can be used.
In one aspect, the second coating film forming component (A2) may have an organic solvent dilutability. Examples of the organic solvent include hydrocarbon solvents such as n-butane, n-hexane, n-heptane, n-octane, cyclopentane, cyclohexane and cyclobutane; aromatic solvents such as toluene and xylene; ketones such as methyl isobutyl ketone. Ether solvents such as n-butyl ether, dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol; ethyl acetate, n-butyl acetate, isobutyl acetate, ethylene Ester solvents such as glycol monomethyl ether acetate and butyl carbitol acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and diisobutyl ketone; alcohol solvents such as ethanol, isopropanol, n-butanol, sec-butanol, isobutanol; N , N-dimethylformamide, N,N-dimethylacetamide, N-methylformamide, N-methylacetamide, N-methylpropioamide, N-methyl-2-pyrrolidone, and other such amide solvents. These can be used alone or in combination of two or more.

In the present disclosure, the total resin solid content of the second coating film forming component (A2) indicates the total solid content of the resin and the curing agent contained in the second coating film forming component (A2).

Foaming agent (B)
The second coating composition contains a foaming agent (B). Inclusion of the foaming agent (B) contributes to easy peeling of the coating film.
In one embodiment, the foaming agent (B) contains at least one selected from the group consisting of a phosphoric acid compound (B1), a nitrogen-containing compound (B2) and a halogen compound (B3).
By including these compounds, the coating film can be peeled off more easily.
In the coating composition set according to the present disclosure, the coating film can be more easily peeled (removed) at least by the synergistic effect with the carbonizing agent (C) described below.

Although not limited to a particular theory, the foaming agent (B) is at least selected from the group consisting of a phosphoric acid compound (B1), a nitrogen-containing compound (B2) and a halogen compound (B3). By including 1 type, when peeling from the road surface, etc., it brings foaming performance to the coating film, and furthermore, it is possible to generate gas and further foam the carbonized layer, so peeling of the coating film is easier You can do it.

In the present disclosure, the “foaming agent” means a component that brings foaming performance to the coating film by the foaming action of the agent contained as the foaming agent or the compound contained as the foaming agent. For example, the foaming agent according to the present disclosure is particularly effective when the coating film is peeled off.
Although it should not be construed as being limited to a particular theory, for example, in a mode in which the coating film forming component has a hydroxyl value in a predetermined range, when the coating film is heated and peeled, a foaming agent and a coating film formation are formed. By interaction with the components, finer foam formation, eg microfoam, can be formed within the coating. Since such a foam can embrittle the coating film more easily than ever before, the generation of scratches on the road surface during the peeling operation of the coating film can be greatly reduced.

Phosphoric acid compound (B1)
In one embodiment, the foaming agent (B) contains a phosphoric acid compound (B1). By containing the phosphoric acid compound (B1), when the coating film is heated with a burner or the like at the time of peeling the coating film (for example, at about 270° C.), a phosphoric acid glassy layer is formed and the coating film becomes brittle, Allows easy disruption of the membrane. Further, since it functions as a dehydration catalyst for dehydrating the organic matter in the coating film component, it is possible to promote the formation of a carbonized layer formed by carbonizing the organic matter in the coating film component.

The phosphoric acid compound (B1) contained in the foaming agent (B) is, for example, phosphoric acid such as orthophosphoric acid, polyphosphoric acid, ammonium phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, dimelamine pyrophosphate, It is one or more phosphate compounds selected from the group consisting of guanidine phosphate, guanylurea phosphate, ammonium polyphosphate (APP) and melamine polyphosphate.
By using these phosphorus compounds, the coating film can be heated at the time of peeling at about 200° C. to 300° C., and the coating film can be peeled more safely as compared with the conventional peeling of the coating film by heating.

The above-mentioned phosphate compound may be in the form of salt or hydrate. The phosphoric acid compound (B1) contains, for example, ammonium polyphosphate. Ammonium polyphosphate may be linear or branched, may have a crosslinked structure, and may be a mixture thereof. By containing ammonium polyphosphate, the formation of the carbonized layer can be promoted more safely, and the coating film can be easily removed.

The phosphoric acid compound (B1) acts as a dehydration catalyst that dehydrates organic components in the coating film when heated (for example, at about 270° C.), thereby promoting the formation of a carbonized layer, The combustion of the coating film can be suppressed.

The phosphoric acid compound (B1) may be a compound in which at least a part of its surface is coated. For example, it is preferable that the phosphoric acid compound (B1) contains a phosphoric acid compound whose surface is at least partially covered with an alkylsilane compound, and ammonium polyphosphate whose surface is at least partially covered with an alkylsilane compound. Is more preferable. For example, ammonium polyphosphate whose surface is at least partially coated with an alkylsilane compound can be prepared by treating with a treating agent containing an alkylsilane compound.

Specific examples of the alkylsilane compound include, for example, alkylsilanes such as butyltrichlorosilane, t-butyldimethylchlorosilane, butylchlorodimethylsilane, chlorotrimethylsilane, chlorohexyltrichlorosilane, chlorohexyltrimethoxysilane, dimethylethylchlorosilane and decyl. Trichlorosilane, triethoxymethylsilane, isobutyltrichlorosilane, trimethoxypropylsilane, triethoxypropylsilane, etc.; arylsilanes and arylalkylsilanes, such as benzylchlorodimethylsilane, benzyltriethoxysilane, chlorodimethyl-3-phenylpropylsilane , Chlorodimethylphenylsilane, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, phenyltrichlorosilane, triethoxyphenylsilane, trimethoxyphenylsilane, etc.; orefinylsilane, such as allyltriethoxysilane, allylchlorodimethylsilane, allyltri. Methoxysilane, allyltrichlorosilane, chlorodimethylvinylsilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, trichlorovinylsilane, vinyltrimethoxysilane, triethoxyvinylsilane, dimethylethoxyvinylsilane; glycidyloxyalkylsilane, eg, diethoxy-3-glycidyloxy. Propylmethylsilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyldimethoxymethylsilane, triethoxy-3-glycidyloxypropylsilane, etc.; acroyloxyalkylsilane and metacroyloxyalkylsilane, such as 3-(tri Methoxysilyl)propyl acrylate, 3-[diethoxy(methyl)silyl]propyl methacrylate, 3-(trimethoxysilyl)propyl methacrylate, 3-[tris(trimethylsilyloxy)silyl]propyl methacrylate, 3-[dimethoxy(methyl)silyl] Propyl methacrylate, 3-(methoxydimethylsilyl)propyl acrylate, 3-(triethoxysilyl)propyl methacrylate and the like; aminoalkylsilanes such as 3-aminopropyltriethoxysilane, 3-2-aminoethylaminopropyltrimethoxysilane, 3-2-aminoethylaminopropyldimethoxymethylsilane, 3-2-aminoethylaminopropyltriethoxysila , 3-aminopropyldimethoxymethylsilane, bis3-trimethoxysilylpropylamine, 3-aminopropyldiethoxymethylsilane, 3-N,N-dimethaminoaminopropyltrimethoxysilane, trimethoxy3-phenylaminopropylsilane, 3-aminopropyltrimethoxysilane, etc.; fluoroalkylsilane, fluoroarylsilane, etc.;

In one embodiment, as the alkylsilane compound, one or more selected from glycidyloxyalkylsilane, acroyloxyalkylsilane and metacroyloxyalkylsilane are used.

The treating agent used for coating at least a part of the surface of the phosphoric acid compound (for example, ammonium polyphosphate) may contain other coating treating agent in addition to the alkylsilane compound. In this case, the compound that coats at least a part of the surface of the phosphoric acid compound (for example, ammonium polyphosphate) may be two or more of the components derived from the alkylsilane compound and the other coating treatment agent. As other coating treatment agents, for example, polyols such as polyethylene glycol and polypropylene glycol and esterified products thereof, monomers such as melamine monomers, surfactants, silicone compounds, epoxy resins, urethane resins, acrylic resins, phenol resins, alkyd resins. , One or more selected from resin components such as urea resin and melamine resin.

As a treatment method for coating at least a part of the surface of a phosphoric acid compound (for example, ammonium polyphosphate), for example, a submerged curing method, a phase separation method, a submerged drying method, a melt dispersion cooling method, a spray drying method, an interface weight Known treatment methods such as a legal method and an in-situ polymerization method can be used.
The coating amount of the treating agent on the phosphoric acid compound is preferably 0.05 to 20 parts by mass, preferably 0.1 to 10 parts by mass, and 0.2 to 100 parts by mass of the phosphoric acid compound. It is more preferably about 5 parts by mass.
You may use a commercial item as a phosphoric acid compound with which at least one part of the surface was coat|covered. Commercially available products in which at least a part of the surface of ammonium polyphosphate is coated are, for example, FR CROS 486, FR CROS 487, TERRJU-C30, TERRJU-C60, TERRJU-C70, TERRJU-C80 (manufactured by Bodenheim), Exolit. AP-462 (manufactured by Clariant Co., Ltd.) and the like can be mentioned.

The amount of the phosphoric acid compound (B1) contained in the second coating composition of the present disclosure is 5 parts by mass or more and 500 parts by mass or less based on 100 parts by mass of the total resin solid content of the second coating film forming component (A2). You can In one embodiment, the amount of the phosphoric acid compound (B1) contained in the second coating composition is 5 parts by mass or more and 300 parts by mass or less based on 100 parts by mass of the total resin solid content of the second coating film forming component (A2). And is, for example, 5 parts by mass or more and 200 parts by mass or less.
In another aspect, the amount of the phosphoric acid compound (B1) contained in the second coating composition is 5 parts by mass or more and 100 parts by mass or more with respect to 100 parts by mass of the total resin solid content of the second coating film forming component (A2). Parts or less, for example, 5 parts by mass or more and 80 parts by mass or less.
By including the phosphoric acid compound (B1) in such a range, the multilayer coating film can be easily embrittled, and the generation of scratches on the road surface during the peeling operation of the coating film can be greatly reduced.
In the present disclosure, in the embodiment in which the second coating film forming component (A2) contains a polymerizable monomer and/or a polymerizable oligomer (A2-6), the term "all resins of the second coating film forming component (A2)" is used. Unless otherwise specified, the solid content of 100 parts by mass also includes the solid content derived from the component (A2-6).

Nitrogen-containing compound (B2)
The foaming agent (B) may include a nitrogen-containing compound (B2). By containing the nitrogen-containing compound (B2), for example, by heating with a burner at the time of peeling the coating film, nitrogen gas can be generated and the carbonized layer can be further foamed, so that the coating film can be peeled off more easily. Further, it is possible to more effectively prevent the coating film from burning vigorously.
The nitrogen-containing compound (B2) contained in the foaming agent (B) is at least one selected from the group consisting of melamine, dicyandiamide, azobistetrazole, azodicarbonamide, urea, thiourea and derivatives thereof.

The content of the nitrogen-containing compound (B2) contained in the coating composition of the present disclosure is 5 parts by mass or more and 500 parts by mass or less based on 100 parts by mass of the total resin solid content of the second coating film forming component (A2). You can In one aspect, the amount of the nitrogen-containing compound (B2) contained in the second coating composition is 5 parts by mass or more and 300 parts by mass or less based on 100 parts by mass of the total resin solid content of the second coating film forming component (A2). And is, for example, 5 parts by mass or more and 200 parts by mass or less.
By including the nitrogen-containing compound (B2) in such a range, the coating film can be peeled off more easily. Further, it is possible to more effectively prevent the coating film from burning vigorously.

Halogen compound (B3)
The foaming agent (B) may include a halogen compound (B3). The halogen compound (B3) contained in the foaming agent (B) is, for example, chlorinated paraffin, chlorinated polyphenyl, diphenyl chloride, triphenyl chloride, pentachlorofatty acid ester, perchloropentacyclodecane or chlorinated halogen compound. Chlorine compounds such as naphthalene and tetrachlorophthalic anhydride; pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A, hexabromocyclododecane, hexabromobenzene, and other bromine compounds. Specific examples of the chlorinated paraffin include carbon chain chlorinated paraffin having 10 to 13 carbon atoms, medium chain chlorinated paraffin having 14 to 17 carbon atoms, and long chain chlorinated paraffin having 18 to 30 carbon atoms. Can be mentioned. Among these, medium-chain chlorinated paraffins having 14 to 17 carbon atoms and long-chain chlorinated paraffins having 18 to 30 carbon atoms are preferable, and long-chain chlorinated paraffin having 18 to 30 carbon atoms is more preferable.

The content of the halogen compound (B3) contained in the coating composition of the present disclosure is 0.5 parts by mass or more and 30 parts by mass or less based on 100 parts by mass of the total resin solid content of the second coating film forming component (A2). And is, for example, 1 part by mass or more and 20 parts by mass or less.
If necessary, in addition to the above halogen compound (B3), antimony trioxide can be used. By using antimony trioxide in combination, it is possible to further prevent the coating film obtained from burning vigorously, and it is possible to obtain an effect that a safe work can be performed.

Carbonizing agent (C)
By including the carbonizing agent (C) in the composition according to the present disclosure, a carbonized layer can be formed by heating with a burner or the like (for example, heating at about 270° C.) during peeling of the coating film. Thereby, the coating film can be made more brittle. For example, when the foaming agent (B) contains a phosphoric acid compound (B1), the carbonizing agent (C) can be dehydrated by the phosphoric acid compound (B1) in the coating film component to form a carbonized layer, resulting in a brittle coating film. Can occur.
In the coating composition set according to the present disclosure, at least the synergistic effect with the foaming agent (B) described above allows the coating film to be more easily peeled (removed).

In one aspect, the hydroxyl value of the carbonizing agent (C) is 500 mgKOH/g or more and 1,900 mgKOH/g or less, for example, 700 mgKOH/g or more and 1850 mgKOH/g or less. In another aspect, the hydroxyl value of the carbonizing agent (C) is 700 mgKOH/g or more and 1,700 mgKOH/g or less, for example, 700 mgKOH/g or more and 1,500 mgKOH/g or less.
When the hydroxyl value of the carbonizing agent (C) is within such a range, the coating film can be efficiently foamed and carbonized, and the coating film can be easily peeled off.

When a plurality of carbonizing agents (C) are included, the hydroxyl value of each carbonizing agent (C) is preferably included in the above range. In another aspect, the average value of the hydroxyl value of each carbonizing agent (C) may be included in the above range. For example, in the aspect including the carbonizing agent (C1) and the carbonizing agent (C2) as the carbonizing agent (C), the hydroxyl value of the carbonizing agent (C) can be calculated based on the following formula.
Hydroxyl value of carbonizing agent (C) (mgKOH/g)=[hydroxyl value of (C1)×(C1) mass+(C2) hydroxyl value×(C2) mass]/[(C1) mass+( Mass of C2)]

In one aspect, as described above, the total hydroxyl value of the second coating film forming component (A2) and the carbonizing agent (C) (see the following formula) in the second coating film is 40 mgKOH/g or more 1 , 600 mgKOH/g or less.
Total hydroxyl value (mgKOH/g)=[hydroxyl value of (A2)×mass of (A2)+hydroxyl value of (C)×(C) mass]/total mass of the second coating film By having, it is possible to improve the strength and durability of the obtained coating film. For example, it is possible to form a coating film which is excellent in coating film strength and durability and which is also excellent in visibility. Moreover, the coating film can be peeled safely and easily without impairing the physical properties of the coating film.
Regarding the total hydroxyl value of the second coating film forming component (A2) and the carbonizing agent (C), for example, the carbonizing agent (C1) and the carbonizing agent as the second coating film forming component (A2) and the carbonizing agent (C) In the aspect including (C2), the hydroxyl value can be calculated as follows.
Total hydroxyl value (mgKOH/g)=[hydroxyl value of (A2)×(A2) mass+(C1) hydroxyl value×(C1) mass+(C2) hydroxyl value×(C2) mass) ]/Total mass of the second coating film.

The carbonizing agent (C) is, for example, a polyhydric alcohol. The polyhydric alcohol as the carbonizing agent (C) can be appropriately selected within a range that does not impair the effects of the present disclosure. For example, from pentaerythritol, dipentaerythritol, tripentaerythritol, neopentaerythritol, ditrimethylolpropane, trimethylolpropane, dioxane glycol, sorbitol, xylitol, inositol, mannitol, glucose, fructose, cellulose, lignin, chitin and derivatives thereof. Includes one or more selected from the group consisting of:
In one embodiment, the polyhydric alcohol as the carbonizing agent (C) is pentaerythritol, dipentaerythritol, tripentaerythritol, neopentaerythritol, dimethylolpropane, trimethylolpropane, dioxane glycol, cellulose, lignin, chitin, xylitol and At least one selected from these derivatives is included.
For example, the polyhydric alcohol as the carbonizing agent (C) includes at least one selected from pentaerythritol, dipentaerythritol, tripentaerythritol, cellulose and derivatives.
By selecting such a carbonizing agent, a carbonized layer can be formed in the coating film when the coating film is peeled off, and the embrittlement of the coating film can be further promoted.

The amount of the carbonizing agent (C) contained in the second coating composition of the present disclosure is 3 parts by mass or more and 500 parts by mass or less based on 100 parts by mass of the total resin solid content of the second coating film forming component (A2). May be In one embodiment, the amount of the carbonizing agent (C) in the second coating composition is 5 parts by mass or more and 500 parts by mass or less based on 100 parts by mass of the total resin solid content of the second coating film forming component (A2). And is, for example, 10 parts by mass or more and 480 parts by mass or less. In another embodiment, the amount of the carbonizing agent (C) in the second coating composition is 15 parts by mass or more and 300 parts by mass with respect to 100 parts by mass of the total resin solid content of the second coating film forming component (A2). It is below, for example, 50 parts by mass or more and 200 parts by mass or less.
In the embodiment in which the second coating film forming component (A2) contains the polyurethane resin (A2-2), the polyol component (a2-1) that may remain during curing of the coating film forming component is the carbonizing agent (C). Can play a role. Further, for example, in an embodiment in which the second coating film forming component (A2) contains the polyurethane resin (A2-2), an excess amount of the polyhydric alcohol is not simply used, but the foaming agent (B) according to the present disclosure is used together. By being included in the coating composition, the coating film can be peeled off safely and easily. With such a composition according to the present disclosure, for example, temporary road marking can be suitably applied.

Additive In addition to the above components, the second coating composition of the present disclosure includes a pigment, an aggregate (sand etc.), a silica, a reflecting material, a matting agent such as alumina, a surface modifier, a viscosity modifier, a preservative, and It may contain additives such as a fungicide, a defoaming agent, a dispersant, a light stabilizer, an ultraviolet absorber, a wax, a dehydrating agent, a leveling agent and an antioxidant, which are added to the coating composition. These additives may be included in the second coating film forming component (A2). For example, it may be contained in at least one of the resin composition and the curing agent composition which are the main components. Further, these amounts can be appropriately adjusted within a range that does not impair the effects of the present disclosure.

For example, the pigment may include at least one selected from the group consisting of carbonate, titanium oxide, zinc oxide, precipitated barium, talc, silica and kaolin. It may also be shellfish powder, egg shell calcium, hollow particles and the like. For example, it may contain at least one selected from the group consisting of carbonates (calcium carbonate, precipitated calcium carbonate, light calcium carbonate, etc.), titanium oxide and talc, or may contain a plurality of carbonates.

When the second coating composition is a coating composition that constitutes a coating composition set for pavement marking, the second coating composition preferably contains a color pigment. The coloring pigment in the present specification is a pigment that imparts visibility as a road marking, and includes both a pigment having a chromatic color and a pigment having an achromatic color. Such a coloring pigment is a pigment having a function of causing human eyes to perceive a chromatic color or an achromatic color by selectively reflecting or absorbing light having a specific wavelength. Examples of the coloring pigment include inorganic coloring pigments such as titanium oxide, carbon black, iron oxide, and yellow iron oxide; and various organic coloring pigments such as phthalocyanine-based pigments such as phthalocyanine blue and phthalocyanine green; azo red and azo yellow. Azo-based pigments such as azo orange; quinacridone-based pigments such as quinacridone red, shinkashared and shinkasha magenta; perylene-based pigments such as perylene red and perylene maroon; carbazole violet, anthrapyridine, flavanthron yellow, isoindoline yellow, indus Ron blue, dibromo anzasulon red, anthraquinone red, diketopyrrolopyrrole and the like.

In one embodiment, the content of the color pigment in the case of containing the color pigment is 0.1 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the total resin solid content of the second coating film forming component (A2). Preferably.

For example, when the second coating composition contains a coloring pigment such as titanium oxide, the coating film formed from the coating composition of the present disclosure can have a white color. In one embodiment, the road marking coating composition can be used for forming a white coating film, for example, a coating film such as a white line. Thus, when the second coating composition is a coating composition that constitutes a coating composition set for road marking, a road surface having excellent visibility can be obtained by including a coloring pigment in the second coating composition. There is the advantage that the indicia can be formed.

The above pigments may include extenders such as calcium carbonate, precipitated barium sulfate, clay and talc, if necessary.

The second coating composition may further include an aggregate. Examples of the aggregate include crushed materials of various materials (for example, crushed materials of waste materials such as ceramics) and sand such as silica sand. When the second coating composition is a coating composition constituting a coating composition set for road marking, the non-slip performance of the road marking formed by the aggregate contained in the second coating composition There is an advantage that can be improved.

In one aspect, the coating composition set of the present disclosure is a coating composition set for pavement marking, for example, a coating composition set for easily removable pavement marking.
The details of the coating composition and each component contained in the coating composition set for easily removable road marking are as described above. The composition of the coating composition in these coating set compositions is as described above.
As described above, the second coating composition contains the second coating film forming component (A2) according to the present disclosure, and the foaming agent (B) and the carbonizing agent (C). A marking coating composition can be obtained.
In the present disclosure, “easy removal” means a property that can be easily removed by heating (for example, heat treatment at 270° C. or higher).
In another aspect, there is provided a pavement marking, eg, a temporary pavement marking, comprising a coating composition set according to the present disclosure.

In one embodiment, the hue of the second coating film has a desired hue. For example, in the embodiment in which the coating composition set of the present disclosure is used for road marking, the second coating film may have a hue such as white line, yellow line, green line, and blue line.
In some embodiments, the second coating can have a different hue than the substrate, for example, a hue that is not similar. By having such a hue, at least the second coating film has a different hue from that of the object to be coated, so that, for example, a driver, a pedestrian or the like can easily make a road marking formed from the coating composition set of the present disclosure. Can be recognized by.

[First coating composition]
The first coating composition contains the first coating film forming component (A1), and the dry coating film of the first coating composition has a thermal conductivity of 0.01 W/m·K or more and 0.5 W/m·K or less. is there.

The thermal conductivity of the dried coating film obtained by drying and curing the first coating composition is 0.01 W/m·K or more and 0.5 W/m·K or less. In one aspect, the thermal conductivity of the dry coating film of the first coating film is 0.05 W/m·K or more and 0.45 W/m·K or less, and for example, 0.10 W/m·K or more and 0.45 W/ m·K or less. In another aspect, the thermal conductivity of the dried coating film obtained by drying and curing the first coating composition is 0.10 W/m·K or more and 0.40 W/m·K or less, for example, 0.10 W/ It is not less than m·K and not more than 0.38 W/m·K.
When the thermal conductivity of the coating film is within the above range, the first coating film can efficiently foam and carbonize the second coating film formed from the predetermined coating composition according to the present invention. ..
Here, the coating composition set of the present disclosure, in which the first coating composition has such a thermal conductivity and further includes the predetermined first coating composition according to the present disclosure, has a durability suitable for heavy traffic. A coating film having excellent properties can be formed. Further, the multilayer coating film formed from the coating composition set of the present disclosure can be easily removed.

The first coating composition contains a first coating film forming component (A1). The first coating film forming component (A1) is used in the coating composition field as long as it does not impair the thermal conductivity of the dry coating film of 0.01 W/m·K or more and 0.5 W/m·K or less. The resin used can be included.
In the present disclosure, the thermal conductivity can be calculated by applying the first coating composition and drying it to prepare a test piece having a dry film thickness of 300 μm.
For example, as the first coating film forming component (A1), the coating film forming component described with respect to the second coating film forming component (A2) may be included. Regarding the physical properties such as molecular weight and hydroxyl value, the description regarding the second coating film forming component (A2) can be applied.

Examples of the first coating film forming component (A1) include acrylic resin, polyurethane resin, epoxy resin, petroleum resin, cellulose resin and the like, like the second coating film forming component (A2). Moreover, you may contain the (meth)acrylate monomer and/or oligomer which has one or more (meth)acryloyl group. As the first coating film forming component (A1), only one type may be used alone, or two or more types may be used in combination.
Further, the first coating film forming component (A1) is, in addition to the above resin, a crosslinking agent (for example, an amino resin, a (block) polyisocyanate compound, an amine crosslinking agent, a polyamide crosslinking agent, a polyvalent carboxylic acid), if necessary. Acid cross-linking agent, etc.) may be used in combination. Further, the first coating film forming component (A1) may contain a two-component polyurethane resin composed of a main agent and a curing agent.

In one aspect, the first coating film forming component (A1) may include the same type of resin as the second coating film forming component (A2), for example, the same as the second coating film forming component (A2). Good. However, the composition of the first coating film forming component (A1) can be appropriately adjusted so that the thermal conductivity measured for the dry coating film is 0.01 W/m·K or more and 0.5 W/m·K or less.

The first coating composition contains, in addition to the first coating film forming component (A1), a foaming agent (B) and a foaming agent (B) described in the second coating composition, if necessary, within a range exhibiting a predetermined thermal conductivity. You may include at least 1 sort(s) among carbonizing agents (C). By including these, the multi-layer coating film, especially the first coating film, can be peeled off more easily.
The foaming agent (B) and/or carbonizing agent (C) that can be contained in the first coating composition is different from the foaming agent (B) and/or carbonizing agent (C) contained in the second coating composition. Well, they may be the same. The amount of the foaming agent (B) and/or the carbonizing agent (C) can be appropriately selected within the range described for the second coating composition.

In one aspect, the first coating composition contains a phosphoric acid compound (B1) as a foaming agent (B). As the phosphoric acid compound (B1), phosphoric acid, polyphosphoric acid, ammonium phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, dimelamine pyrophosphate, guanidine phosphate, guanylurea phosphate, ammonium polyphosphate and melamine polyphosphate It may include at least one selected from the group consisting of:

In one embodiment, the first coating composition contains a polyhydric alcohol as the carbonizing agent (C), and includes at least one selected from pentaerythritol, dipentaerythritol, tripentaerythritol, cellulose and derivatives, for example.
By selecting such a carbonizing agent, a carbonized layer can be formed in the coating film when the coating film is peeled off, and the embrittlement of the coating film can be further promoted.
By using these phosphorus compounds, the coating film can be heated at the time of peeling at about 200° C. to 300° C., and the coating film can be peeled more safely as compared with the conventional peeling of the coating film by heating.

In one embodiment, the first coating composition contains, in addition to the above components, a matting agent such as pigments, hollow particles, resin beads, aggregates (sand, glass beads, etc.), silica, reflectors, alumina, etc., if necessary. Agents, surface modifiers, viscosity modifiers, preservatives, fungicides, defoamers, dispersants, light stabilizers, UV absorbers, waxes, dehydrating agents, leveling agents, antioxidants, etc. The additive may be included.

For example, the first coating composition may include further components in addition to the above components. The pigment may include at least one selected from the group consisting of carbonate, titanium oxide, zinc oxide, precipitated barium, talc, silica and kaolin. In addition, shellfish powder, egg shell calcium, hollow particles and the like may be included.
For example, the pigment may include at least one selected from the group consisting of carbonates, titanium oxide and talc, or may include a plurality of carbonates.
By including such a pigment, the dry coating film formed from the first coating composition can contribute to having a predetermined thermal conductivity.
For example, the pigment may include hollow particles. By including the hollow particles, the thermal conductivity can be controlled more efficiently. The hollow particles may include, for example, organic hollow particles made of acrylic resin or the like and inorganic hollow particles such as shirasu balloon, glass balloon, and fly ash balloon. The average particle size of the hollow particles is preferably 10 to 300 μm. In the present disclosure, the average particle size means the volume average particle size of particles, and can be measured using, for example, a laser diffraction particle size distribution measuring device SALD-2200 (manufactured by Shimadzu Corporation).

For example, the first coating composition may contain the pigment in an amount of 0.05 parts by mass or more and 60 parts by mass or less based on 100 parts by mass of the resin solid content of the first coating film forming component (A1). In one embodiment, the pigment may be contained in an amount of 5 parts by mass or more and 45 parts by mass or less based on 100 parts by mass of the resin solid content of the first coating film forming component (A1). When the amount of the pigment contained in the first coating composition is within the above range, the resulting coating film can have high durability.
In some embodiments, such amounts include hollow particles.
When a plurality of pigments and hollow particles are included, the total amount of each component can be appropriately adjusted so as to fall within the above range.

In one aspect, the hue of the first coating film is transparent or similar to that of the coating object. When the first coating film has such a hue, for example, the second coating film in the multilayer coating film is removed, while at least a part of the first coating film remains on the object to be coated. Drivers, pedestrians, etc. are unlikely to misidentify the first coating film as a road marking. The hue can be colored in a desired range with a coloring pigment or the like.

[Method for preparing coating composition]
The method for preparing the coating composition (the first coating composition and the second coating composition) according to the present disclosure is not particularly limited, and the above-mentioned constituents are mixed and stirred, and if necessary, the additives contained therein are dispersed. The method of making it possible can be exemplified. The stirring method is not particularly limited, and a disper or the like can be used. Further, the dispersing method is not particularly limited, and a device generally used for dispersing the pigment, such as a roll mill, a paint shaker, a pot mill, a disper or a sand grind mill, can be used.

[Subject]
The coating composition (the first coating composition and the second coating composition) according to the present disclosure can be applied to the surface of a pavement such as a road surface or a parking lot in a building. The pavement body is not particularly limited, and examples thereof include asphalt pavement, concrete pavement, brick pavement, and the like.

[Multilayer coating method]
Further, the present invention provides
The step (1) of forming the first coating film by coating the first coating composition on an object to be coated, and the second coating composition on the first coating film obtained by the step (1). And a step (2) of forming a second coating film by coating with.
In such a multilayer coating film forming method, the first coating film has a dry coating film having a thermal conductivity of 0.01 W/m·K or more and 0.5 W/m·K or less, and the second coating composition. The product contains a second coating film forming component (A2), a foaming agent (B), and a carbonizing agent (C).

By forming a multilayer coating film using the predetermined first coating composition and the predetermined second coating composition according to the present disclosure, that is, the coating composition set according to the present disclosure, a driver, a pedestrian, etc. It is possible to form a multilayer coating film which can be visually recognized well, which has sufficient durability and coating film strength, and which can suppress deterioration and wear. Moreover, the formed multilayer coating film can be easily removed.

In one aspect, the present disclosure provides coating a first coating composition according to the present disclosure on a pavement, curing (drying) the first coating film to obtain a first coating film, and And a method of forming a multilayer coating film, which comprises coating the second coating composition according to the present disclosure and curing (drying) the second coating composition to obtain a second coating film.

The method for applying the first coating composition and the second coating composition provides a method for forming a coating film, which is performed by at least one method selected from the group consisting of spray coating, slit coater coating and flow coating.

In one embodiment, when at least one of the first coating composition and the second coating composition contains an acrylic resin, the coating method of the coating composition is selected from the group consisting of air spray, airless spray, slit coater, brush and roller. Can be applied using at least one of

For example, in order to accelerate the drying property of the first coating composition, it is preferable to use spray coating as the coating method of the first coating composition. Similarly, in order to accelerate the drying property of the second coating composition, it is preferable to use spray coating as the method for coating the second coating composition.

The drying conditions of the first coating composition are not particularly limited as long as the coating composition does not become brittle, and may be room temperature drying, for example. Moreover, you may force-dry by a well-known technique according to conditions, such as air temperature and pavement temperature.

The first coating composition is preferably applied in an amount such that the film thickness after drying and curing is in the range of 50 to 2,000 μm, more preferably in the amount of 100 to 800 μm. When the dry film thickness is within the above range, the effect that the second coating film can be efficiently foamed and carbonized) can be obtained.
After forming the first coating film in this manner, the second coating composition can be applied thereon. The coating of the second coating composition is preferably performed after the first coating composition has been dried by touch. By doing so, the second coating film can be easily foamed and carbonized, exhibiting excellent easy-removability, and can be applied before the coating film is completely cured. Therefore, the effect that the coating work can be performed in a short time is obtained.
In addition, the touch-dry in the present disclosure means a dry state in which a fingerprint is not attached even when the obtained coating film is pressed with a finger.

The second coating composition is preferably applied in an amount such that the film thickness after drying and curing is in the range of 30 to 1,000 μm, more preferably in the amount of 50 to 500 μm. When the dry film thickness is within the above range, it is possible to obtain the second coating film having good durability and further the multilayer coating film. In addition, the coating film can be easily foamed and carbonized, and excellent removability can be exhibited.

The contents described above can be appropriately incorporated into the respective components contained in the first coating composition and the second coating composition.

[Road marking method]
In one aspect, the present disclosure provides a pavement marking obtained by the method for forming a multilayer coating film. The present disclosure also provides a method for forming a multilayer coating film (that is, road marking), which is a method for forming a multilayer coating film for road marking. The above-mentioned steps, compositions, and the like can be applied to the method for forming the road marking.

As one aspect of the method of forming the road marking, for example,
A step of coating the first coating composition in the coating composition set on a substrate to form a first coating film;
A step of coating the second coating composition in the coating composition set to form a second coating film on the first coating film obtained by the step, and a second coating film formed in the step Before drying, the reflecting material is sprayed on the second coating film to fix the reflecting material on the surface of the second coating film.
And a method of forming a road marking, which includes In this forming method, the article to be coated is preferably a road surface. In addition, in this forming method, except that the reflecting material is sprinkled on the second coating film before the drying (curing) of the second coating composition to fix the reflecting material on the surface of the second coating film. The process, composition, etc. of can be used.

As the above-mentioned reflective material, for example, glass beads, glass powder, etc. which have been conventionally used can be used. The glass beads preferably have a refractive index of 1.5 to 2.5 and an average particle diameter of 0.1 to 1.5 mm. When the refractive index is 1.5 or more, good visibility can be secured. Further, when the refractive index is 2.5 or less, good retroreflective performance can be ensured, and thus, there is an advantage that good visibility (particularly night visibility) can be secured. Further, when the average particle diameter of the glass beads is 1.5 mm or less, there is an advantage that the second coating film can favorably hold the glass beads and ensure good visibility.

The above-mentioned reflective material means a material that has the property of reflecting light to reflect in the same direction as the incident light (retroreflection performance). In the above forming method, the first coating film is first formed on an object to be coated such as a road surface. Next, the second coating composition is applied onto the obtained first coating film to form the second coating film. Then, before the second coating film is dried, the reflecting material is sprinkled on the second coating film and dried and cured, so that the reflecting material is fixed on the surface of the second coating film. Accordingly, it is possible to form a road marking having particularly good night visibility. As a preferable mode in which the reflecting material is fixed on the surface of the second coating film, for example, a state in which about 1/3 to 2/3 of the volume of the reflecting material is fixed by being buried in the second coating film is mentioned. To be

In one aspect, it is preferable that the amount of the reflective material sprayed is 0.1 kg/m ² or more and 0.8 kg/m ² or less. Good visibility can be ensured when the amount of the reflection agent applied is within the above range.

[Film removal method]
The present disclosure further provides a coating removal method, eg, a road marking removal method.
In one aspect, the present disclosure provides a pavement marking removal method, which further comprises removing the pavement marking formed by the above-described method for forming a multilayer coating film by heating.
A multi-layer coating film comprising the first coating composition and the second coating composition, for example, road marking is performed by heating at a temperature higher than the curing temperature of the multi-layer coating film by using an open fire, an infrared heater or the like. The second coating film formed from the second coating composition foams and further carbonizes, and the coating film becomes brittle. For example, heating may be performed at about 270° C., and the heating temperature can be set according to the resin used, the thickness of the coating film, and the like.

The coating film that has been embrittled by an arbitrary method can be easily removed by rubbing it with a brush or removing it by suction. For example, the second coating film can be easily removed by rubbing it with a brush or the like, or removing it by suction. As described above, the multi-layer coating film formed from the coating composition set according to the present disclosure can remove the coating film in a short time.

In one aspect, there is provided a road marking removing method that enables deletion of a road marking.
For example, in the case of a multi-layer coating film formed by using the coating composition set of the present disclosure, for example, road marking, the first coating film is formed on the road surface and the second coating film is formed on the first coating film. .. In such road marking, the second coating film surface may be heated to preferentially remove the second coating film. In one aspect, the first coating film may be removed after removing the second coating film, or the first coating film may be removed together with the second coating film.
In one aspect, the hue of the first coating film is transparent or similar to that of the coating object, so the second coating film is removed, while at least part of the first coating film remains on the coating object. Even if it does, a driver, a pedestrian, etc. are unlikely to misidentify the first coating film as a road marking (not recognized as a road marking).
Further, for the purpose of explanation, the foaming and carbonization of the second coating film are described, but the foaming agent (B) and/or the carbonizing agent (for the first coating composition are also included within the scope of the present invention. C) may be included. Therefore, the first coating film formed from the first coating composition can be easily embrittled similarly to the second coating film.

The second coating composition according to the present disclosure may contain any pigment within a range that does not deviate from the effects of the present invention, so that repainting of road markings can be easily performed.
For example, according to the present disclosure, the second coating film (white coating film) according to the present disclosure including a white content is removed, and another hue (for example, yellow) is exhibited on the first coating film that may remain on the road surface. The second coating composition can be applied. Therefore, for example, the change from the white second coating film to the yellow second coating film can be easily performed. Further, the required position change of the road marking can be easily performed.

The present disclosure will be described more specifically by the following examples, but the present disclosure is not limited thereto. In the examples, "parts" and "%" are based on mass unless otherwise specified.

The components used to prepare the coating composition are as follows.

(Production Example 1)
Preparation of acrylic resin (A1-1) A reaction vessel equipped with a stirrer, a temperature controller, a cooling tube, a nitrogen introducing tube and a dropping funnel was charged with 35 parts by mass of toluene and heated to 110°C while stirring under a nitrogen atmosphere. Kept warm. To this, a monomer solution consisting of 0.49 parts by mass of acrylic acid, 33 parts by mass of methyl methacrylate, 35.44 parts by mass of butyl acrylate and 29.07 parts by mass of styrene, 15 parts by mass of toluene and azobis as an initiator. An initiator solution composed of 2 parts by mass of isobutyl nitrile was simultaneously added dropwise at a constant rate over 3 hours through separate dropping funnels. After the dropping was completed, stirring was continued for another 3 hours. Then, the mixture was cooled to 80° C., 50 parts by mass of ethyl acetate was added, and the mixture was kept stirring for 1 hour. Acrylic resin (A1-1) (hydroxyl value: 0 mgKOH/g, weight average molecular weight: 45,000, solid content concentration: 50 parts by mass) %) was obtained.

Acrylic resin (A2-11)
The same acrylic resin (A1-1) (hydroxyl group value: 0 mgKOH/g, weight average molecular weight: 45,000, solid content concentration: 50% by mass) was used.

Acrylic resin (A2-12)
Acridic WDU-573; manufactured by DIC, hydroxyl value: 70 mgKOH/g, solid content concentration: 50% by mass

Polyurethane resin (A2-21)
The polyurethane resin (A2-21) was used as a two-component polyurethane resin composed of the following polyol component (a2-1) and polyisocyanate compound (a2-2). The compounding was carried out by mixing the hydroxyl groups of (a2-1) and the isocyanate groups of (a2-2) in an equivalent ratio (OH/NCO) of 1.0.
Polyol component (a2-1): Acridic WDU-573 (acrylic resin having hydroxyl group (A2-12)); manufactured by DIC, hydroxyl value: 70 mgKOH/g, solid content concentration: 50% by mass
Polyisocyanate compound (a2-2): Coronate HXLV (aliphatic isocyanate: hexamethylene diisocyanate trimer); Nippon Polyurethane Co., solid content concentration: 100% by mass

Phosphoric acid compound (B1-1)
Ammonium polyphosphate: Exolit AP462; Phosphoric acid compound (B1-2) manufactured by Clariant Chemicals
Tris(chloropropyl)phosphate: TMCPP; manufactured by Daihachi Chemical Co., Ltd.

Nitrogen-containing compound (B2-1)
Azodicarbonamide: Uniform AZ; nitrogen-containing compound (B2-2) manufactured by Otsuka Chemical Co., Ltd.
p,p'-oxybisbenzenesulfonyl hydrazide: Celmic S; Sankyo Kasei halogen compound (B3-1)
Chlorinated paraffin: Empala 70; manufactured by Ajinomoto Fine-Techno Co., Inc.

Carbonizing agent (C-1)
Dipentaerythritol: Dipentalit 300M; manufactured by Koei Chemical Co., hydroxyl value: 1,324 mgKOH/g
Carbonizing agent (C-2)
Crystalline cellulose: Theolus TG-101; manufactured by Asahi Kasei, hydroxyl value: 1,039 mgKOH/g
Carbonizing agent (C-3)
Ditrimethylol propane: manufactured by Mitsubishi Gas Chemical Company, hydroxyl value: 896 mg KOH/g
Carbonizing agent (C-4)
Dioxane glycol: manufactured by Mitsubishi Gas Chemical Company, hydroxyl value: 514 mg KOH/g
Carbonizing agent (C-5)
Xylitol: manufactured by Tokyo Chemical Industry Co., Ltd., hydroxyl value: 1,844 mgKOH/g

Other components Reaction initiator (D): Niper NS (benzoyl peroxide); NOF resin beads: GANTZ Pearl GM-5003; Aika Kogyo Co., Ltd. heat-expandable particles: Matsumoto Microsphere FN-100MD; Matsumoto Yushi-Seiyaku Co., Ltd. Calcium carbonate: Super 2000; Calcium Maruo carbon black: MA-100; Mitsubishi Chemical hollow particles: inorganic hollow particles, 3M Glass Bubbles K15; 3M particle size: 60 μm
Titanium oxide: Taipaque CR-95; manufactured by Ishihara Sangyo Co., Ltd. Curing catalyst: dibutyltin laurate Organic solvent: xylene

(Example 1)
Preparation of First Coating Composition As shown in Table 1, a first coating composition containing 100 parts by mass of an acrylic resin (A1-1) was prepared.

Preparation of Second Coating Composition 100 parts by mass of acrylic resin (A2-11), 50.0 parts by mass of dipentaerythritol (C-1) as carbonizing agent (C), ammonium polyphosphate (B1) as phosphoric acid compound (B1) -1) was mixed with 50.0 parts by mass, titanium oxide as a pigment 10.0 parts by mass, and calcium carbonate 50.0 parts by mass as a pigment to prepare a second coating composition having foamability and carbonization properties.

Formation of multi-layer coating film The first coating composition was applied to an asphalt pavement using an air spray so that the dry film thickness was 300 μm. The first coating composition was dried and cured at 20° C. for 15 minutes to form a first coating film.
Then, the second coating composition was applied onto the first coating film by using air spray so that the dry film thickness was 300 μm. The second coating composition was dried and cured at 20° C. for 15 minutes to form a second coating film.

Evaluation of each of the obtained coating films and multilayer coating films was performed as follows. The results are shown in Table 1.

Measurement of thermal conductivity of the first coating film A polypropylene plate was used as an object to be coated, and the first coating composition was uniformly coated by the same coating method as in Example 1 so that the dry film thickness was 300 μm, and the temperature was 23° C./relative. It was aged for 7 days in an atmosphere of 50% humidity RH to form a first coating film.
After that, the first coating film was peeled off from the polypropylene plate to obtain a free film, and the thermal conductivity was measured by an unsteady method fine wire heating method. A quick thermal conductivity meter QTM-500 (manufactured by Kyoto Electronics Manufacturing Co., Ltd.) was used as a measuring instrument.

Total hydroxyl value of the second coating film forming component (A2) and carbonizing agent (C) The total hydroxyl value in the second coating film was calculated based on the following formula.
Total hydroxyl value (mgKOH/g)=[hydroxyl value of resin (A2)×(A2) mass in second coating film+hydroxyl value of carbonizing agent (C)×(C) mass in second coating film) ]/Total mass of the second coating film.

Carbonization and Foaming Property of Coating Film The obtained multilayer coating film was heated with a gas burner from a height of 20 cm for 1 minute to confirm the carbonization property and foaming property of the second coating film. As the gas burner, a propane gas burner RM-41000 (manufactured by Shin Fuji Burner Co., Ltd.) for road marking was used.
・Evaluation of foamability and carbonization ◎: The entire coating film is foamed and carbonized within 30 seconds after heating ○: The entire coating film is foamed and carbonized within 1 minute after heating ×: 1 minute has elapsed after heating Even if there is no foaming or charring

Removability of coating film The obtained coating film was heated with a gas burner from a height of 20 cm for 1 minute, and carbonization and foaming property of the coating film were confirmed. Then, it was rubbed with a brush to confirm whether it could be removed by suction. When it cannot be removed by heating once, burner heating and brush removal are repeated to confirm how many times the coating film can be removed. In this evaluation of removability, it was judged that the coating film could be removed at least when the second coating film could be removed.
In the table, for example, Example 1 shows that it can be removed once and the heating time is within 30 seconds, and Example 3 shows that it can be removed once and the heating time (30 seconds to 1 minute). ) Was shown.
・Removability evaluation ◎: 1 time (heating time: within 30 seconds)
○: 1 time (heating time: 30 seconds to 1 minute)
×: 2 to 5 times ×: 6 times or more, could not be removed

Coating durability (wear resistance)
The coating durability of the multilayer coating film was evaluated according to the method specified in JIS K 5600-5-9 Abrasion resistance (wear ring method). A rotary ablation tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used as a test machine, and CS-17 (manufactured by TABER Co., Ltd.) was used as a wear wheel. The wear loss was measured when rotating 200 times at a load of 1 kg and 60 rpm. evaluated.
Abrasion loss (mg) = mass of test plate before test-mass of test plate after test ◎: 30 mg or less ○: 40 mg or more, 55 mg or less Δ: 55 mg or more, 65 mg or less ×: 65 mg or more

Black and white hiding (visibility)
Visual property of JIS K 5600-4-1 coating film Visibility was evaluated according to method B (hiding ratio test paper) defined in hiding power (for light color paint).
Using a 20 mil applicator, the first coating composition and the second coating composition were coated at room temperature on black-and-white hiding rate test paper (manufactured by Nippon Test Panel Co., Ltd.).
A color difference meter CR-400 (manufactured by Konica Minolta Co., Ltd.) was used for the hue measurement, and the evaluation was performed according to the following criteria.
○: Hiding rate 97% or more ×: Hiding rate less than 97%

(Examples 2 to 23, 25 to 27, Comparative Examples 1 to 4)
A first coating composition and a second coating composition were prepared in the same manner as in Example 1 except that the type and amount of each component were changed as shown in Table 1, Table 2 and Table 3, and A multilayer coating having a coating and a second coating was formed. In addition, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1. In addition, the compounding amount described in the following table shows a packing form, and, for example, in the case of acrylic resin (A1-1), the compounding amount (mass part) obtained by adding the resin solid content mass and the solvent content mass is shown.

(Example 24)
A first coating composition was prepared in the same manner as in Example, except that the types and amounts of the components of the first coating composition were changed as shown in Table 1.
Further, 100 parts by mass of the acrylic resin (A2-11) as the polyol component (a2-1), 50.0 parts by mass of the crystalline cellulose (C-2) as the carbonizing agent (C), and ammonium polyphosphate as the phosphoric acid compound (B1). (B1-1) 50.0 parts by mass, titanium oxide 5.0 parts by mass, and dibutyltin laurate as a curing catalyst 0.01 parts by mass were mixed to prepare a main agent. This base material and 11.0 parts by mass of Coronate HXLV, which is a polyisocyanate compound (a2-2) as a curing agent, were mixed immediately before coating and used as a second coating composition.
A multilayer coating film was formed in the same manner as in Example 1 using the first coating composition and the second coating composition. In addition, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 2.

(Example 28)
A road marking was formed using the first coating composition and the second coating composition prepared in Example 1.
The first coating composition was applied onto an asphalt pavement using air spray so that the dry film thickness was 300 μm. The first coating composition was dried and cured at 20° C. for 15 minutes to form a first coating film.
Next, the second coating composition was applied onto the first coating film by using an air spray so that the dry film thickness was 300 μm to form the second coating film. Then, within 2 seconds after the application of the second coating composition, 0.42 kg/m ^{2 of} glass beads SGBT153T (manufactured by Potters Barottini Co., Ltd., glass beads), which is a reflecting material, was applied onto the undried second coating film. The amount of Then, the road marking having the second coating film in which the reflecting material is fixed to the surface by drying and curing the second coating film at 20° C. for 15 minutes, and the first coating film as the lower layer of the second coating film. Formed.

In the road marking evaluation items formed in Example 28, coating film durability (wear resistance) evaluation and black-and-white hiding (visibility) evaluation were not performed. The reason is that the wear loss is measured in the coating film durability (wear resistance) evaluation, and therefore the wear loss of the second coating film itself cannot be measured in the state where the reflective material is adhered to the surface. This is because the hiding property (visibility) is measured by using a color-difference meter, and therefore the hue cannot be measured by the color-difference meter when the reflective material is fixed to the surface and the surface has unevenness.

In Comparative Example 5, a coating film (single layer) was formed in the same manner as in Example 1 except that a load line 7000 manufactured by Nippon Liner Co., Ltd. and an acrylic resin road marking composition was used. The results are shown in Table 3.

The example is a coating composition set including a first coating composition for forming a first coating film and a second coating composition for forming a second coating film, which is a dry coating film of the first coating composition. The thermal conductivity is 0.01 W/m·K or more and 0.5 W/m·K or less, and the second coating composition comprises the second coating film forming component (A2), the foaming agent (B) and the carbonizing agent (C )including. Such a coating composition set according to the present disclosure can cope with heavy traffic and can form a multilayer coating film having excellent durability. Furthermore, the multilayer coating film formed from the coating composition set according to the present disclosure can be easily removed and, in addition, it is excellent in black-and-white hiding property (visibility).

On the other hand, Comparative Example 1 does not contain the carbonizing agent (C), so the carbonization and foaming properties are poor, the coating film cannot be easily removed, and the road surface must be physically abraded using a grinder or the like for coating. The film cannot be removed.
Comparative Example 2 did not include the first coating composition for forming the first coating film, and thus the carbonization property and the foaming property were poor, and the coating film could not be easily removed.
In Comparative Example 3, the dry coating film of the first coating composition had a thermal conductivity outside the range of the present invention, and thus the carbonization property and the foaming property were poor, and the coating film could not be easily removed.
In Comparative Example 4, since the foaming agent (B) was not contained, carbonization and foamability were poor, and the coating film could not be easily removed.
Comparative Example 5 is a general-purpose road marking composition, and the coating film cannot be easily removed, and the coating film cannot be removed unless the road surface is physically shaved using a grinder or the like.

The coating composition set of the present disclosure can cope with heavy traffic and can form a multilayer coating film having excellent durability. Further, the multilayer coating film formed from the coating composition set of the present disclosure can be easily removed.

Claims

A coating composition set for forming a multilayer coating film comprising a first coating film and a second coating film,
The coating composition set includes a first coating composition that forms the first coating film and a second coating composition that forms the second coating film,
The first coating composition contains a first coating film forming component (A1),
The thermal conductivity of the dry coating film of the first coating composition is 0.01 W/m·K or more and 0.5 W/m·K or less,
The second coating composition is
Second coating film forming component (A2),
Foaming agent (B),
Carbonizing agent (C),
including,
Paint composition set.
The coating composition set according to claim 1, wherein the carbonizing agent (C) has a hydroxyl value of 500 mgKOH/g or more and 1,900 mgKOH/g or less.
In the second coating film, the total hydroxyl value of the second coating film forming component (A2) and the carbonizing agent (C) represented by the following formula is 40 mgKOH/g or more and 1,600 mgKOH/g or less. The coating composition set according to claim 1 or 2, wherein:
Total hydroxyl value (mgKOH/g)=[hydroxyl value of (A2)×(A2) mass+(C) hydroxyl value×(C) mass]/total mass of the second coating film.
4. The foaming agent (B) contains at least one selected from the group consisting of a phosphoric acid compound (B1), a nitrogen-containing compound (B2) and a halogen compound (B3). The coating composition set described in 1.
The second coating film forming component (A2) is an acrylic resin (A2-1), a polyurethane resin (A2-2), an epoxy resin (A2-3), a petroleum resin (A2-4), a cellulose resin (A2-5). ), at least one selected from the group consisting of (meth)acrylate monomers and/or oligomers (A2-6) having at least one (meth)acryloyl group. The described coating composition set.
The coating composition set according to any one of claims 1 to 5, wherein the second coating composition further contains a reaction initiator (D).
The carbonizing agent (C) is pentaerythritol, dipentaerythritol, tripentaerythritol, neopentaerythritol, ditrimethylolpropane, trimethylolpropane, dioxane glycol, sorbitol, xylitol, inositol, mannitol, glucose, fructose, cellulose, lignin, The coating composition set according to any one of claims 1 to 6, comprising at least one selected from the group consisting of chitin and derivatives thereof.
The phosphoric acid compound (B1) is phosphoric acid, polyphosphoric acid, ammonium phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, dimelamine pyrophosphate, guanidine phosphate, guanylurea phosphate, ammonium polyphosphate or polyphosphoric acid. The coating composition set according to any one of claims 4 to 7, which is at least one selected from the group consisting of melamine.
9. The nitrogen-containing compound (B2) is at least one selected from the group consisting of melamine, dicyandiamide, azobistetrazole, azodicarbonamide, urea, thiourea, and derivatives thereof, 9. The coating composition set according to item 1.
The amount of the carbonizing agent (C) in the second coating composition is 3 parts by mass or more and 500 parts by mass or more with respect to 100 parts by mass of the second coating film forming component (A2) contained in the second coating composition. The coating composition set according to any one of claims 1 to 9, wherein the coating composition set is at most parts by mass.
The coating composition set according to any one of claims 1 to 10, which is a coating composition set for road marking.
A method for forming a multilayer coating film, which comprises using the coating composition set according to claim 1.
Step (1) of applying the first coating composition in the coating composition set to form a first coating film on an object to be coated, and the first coating film obtained by the step (1). A step (2) of applying the second coating composition in the coating composition set to form a second coating film thereon;
A method for forming a multilayer coating film containing.
The method for forming a multilayer coating film according to claim 12, wherein the multilayer coating film is road marking.
A method for forming a road marking using the road marking coating composition set according to claim 11.
A step of coating the first coating composition in the coating composition set on a substrate to form a first coating film;
A step of coating the second coating composition in the coating composition set to form a second coating film on the first coating film obtained in the step, and a second coating film formed in the step Before drying, the reflective material fixing step of spraying a reflective material on the second coating film to fix the reflective material on the surface of the second coating film,
including,
Road marking method.
A road marking removing method, which further comprises removing the road marking formed by the forming method according to claim 13 or 14 by heating.