JPH11130992A - Luminous coating composition, method for forming luminous coating film, and luminous coated article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating compsn. which provides a coating film which facilitates night-time visual recognition of a coated article by incorporating a luminous agent mainly comprising a compd. represented by a specific formula into the compsn. and by specifying the brightness of the coating film. SOLUTION: This compsn. contains a luminous agent mainly comprising a compd. represented by the formula: MAl2 O4 (wherein M is Ca, Sr, or Ba) and a reflective agent, and hence the afterglow luminance is enhanced and a luminous coating film with a long afterglow time is formed. The brightness of the coating film is 4 or higher. Both the agents are used each in an amt. of 2-80 pts.wt. based on 100 pts.wt. solid content of the compsn, and the wt. ratio (solid basis) of the luminous agent to the reflective agent is (9/1)-(6/4). The luminous agent. e.g. CaAl2 O4 , contains 0.5 mol of Eu as the activator and has an average particle size of 5-25 μm. Pref., the reflective agent, e.g. glass beads, is pearly and has an average particle size of 5-100 μm. A vehicle comprising a thermosetting resin (e.g. an acrylic resin) and a curing agent is used as a compsn. into which the luminous agent is incorporated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a light-emitting coating composition,
The present invention relates to a method for forming a light-emitting coating and a light-emitting coating, and more particularly to a light-emitting coating composition, a method for forming a light-emitting coating, and a light-emitting coating that facilitate the visual recognition of an object to be coated at night.

[0002]

2. Description of the Related Art Conventionally, phosphorescent pigments (long afterglow phosphors) have been used.
For example, ZnS: Cu and (Ca, Sr) S: Bi are known, and ZnS: Cu phosphors are widely used in luminous paints. Such a luminous pigment absorbs light such as sunlight or fluorescent light, excites (stores light), and emits light in a dark place. And the luminous pigment has a light absorption-
Since phosphorescence-emission can be repeated as many times as possible,
Widely used for a wide range of applications, such as signs and signs for disaster prevention and safety, information signs for various places in the car interior and buildings, accessories such as tie pins and pendants, clock faces, floats, fishing lures such as lures, etc. .

The notation ZnS: Cu or ZnS / Cu indicates that the host crystal is ZnS (zinc sulfide) and the activator is Cu (copper). Hereinafter, the same applies. The activator forms a luminescent center in the host crystal. Here, the emission center means a local place in the crystal where the excitation energy is finally converted into light.

[0004] For example, Japanese Patent Application Laid-Open No. 61-40382 discloses a "luminous spray paint" which includes a luminous pigment, a synthetic resin,
A luminescent spray paint containing a light-permeable powder and an organic solvent has been proposed. Here, as a luminous pigment,
Sulfides such as zinc, cadmium, and alkaline earth rare metals are exemplified. Examples of the optically transparent powder include inorganic powders such as glass, mica, and silica, and organic powders such as plastic, cellulose, and starch. Further, it is disclosed that 1 to 50 parts by weight of the light-transmitting powder is added to 100 parts by weight of the luminous pigment.

Japanese Patent Application Laid-Open No. 1-301767 discloses a "fluorescent paint" which includes a daylight fluorescent pigment and contains a hollow glass powder.

Here, Rhodamine B,
Rhodamine 6G, Rhodamine S, Eosine, Basic yellow H
G, Brilliantsulfoflavine FF, Thioflavine, Fluore
Fluorescent dyes such as scein are exemplified, and hollow glass powder having an average particle size of about 20 to 50 μm and a thickness of about several μm is exemplified. It is described in the above publication that the hollow glass powder is added in an amount of about 5 to 20% by weight in the fluorescent paint.

Japanese Unexamined Patent Publication (Kokai) No. 3-180605 discloses a composite material in which ceramic particles and inorganic light-emitting particles are mixed in a resin having a light-transmitting property. Have been. Here, as ceramic particles,
Glass-based and alumina-based particles are exemplified, and examples of the particles of the inorganic-based light emitter include tritium, promethium, and other sulfides mixed with a small amount of a radioactive substance.

[0008] Japanese Unexamined Patent Publication (Kokai) No. 3-126772 discloses a "coating method of a fluorescent paint", in which a first base coating film containing a fluorescent pigment is formed on an undercoating film or an intermediate coating film. Forming a second base coating film containing at least a diffuse reflection material composed of mica fragments on the base coating film;
A coating method for forming a clear coating film on a base coating film is disclosed. Here, calcium sulfide / bismuth (CaS / Bi), zinc cadmium sulfide /
Copper ((Zn, Cd) S / Cu) is exemplified.
Mica pieces and aluminum pieces are mentioned as the irregular reflection material.

Japanese Patent Application Laid-Open No. 5-1247 discloses a "luminous paint" in which glass powder is mixed into a luminous paint.

However, the above-mentioned luminous pigments such as ZnS: Cu and the like, fluorescent pigments, fluorescent paints, and inorganic luminous bodies emit light.
The afterglow brightness is extremely low, the afterglow is attenuated rapidly,
In addition, there was no visible luminance overnight. Also, as proposed in JP-A-3-180605,
There is also a method of adding a radioactive substance and exciting the phosphorescent pigment etc. by the radiation to emit light for a long time, but radioactive substances must be handled according to strict safety management standards, and in the case of phosphorescent substances that touch the human body, There is a problem in that the treatment area and the like are limited, and that the disposal of waste requires a large amount of cost.

In recent years, a SrAl ₂ O ₄ phosphor (phosphorescent pigment) has been developed (JP-A-7-11250), and strontium aluminate (SrAl ₂ O ₄ ) is used as a host crystal, and rare earth element europium (Eu) is used. Desprosium (D
y) and the like as an activator (SrAl ₂ O ₄ : Eu ²⁺ :
Dy3 ⁺ ) "N Luminescent Luminova" (Nemoto Special Chemical Co., Ltd.)
Has been attracting attention.

The above-mentioned SrAl ₂ O ₄ phosphorescent pigment is used as a raw material powder in a predetermined amount of SrCO ₃ (purity 99.2%), Al ₂ O ₃ (purity 99.9%) and flux, and an activator such as Eu. Is added, mixed, and calcined at a high temperature of 1200 ° C. or more in a reducing atmosphere for 3 hours.

The luminous pigment SrAl ₂ O ₄ has an emission spectrum similar to that of human luminosity (emission peak wavelength: 520 nm), and has a broad excitation spectrum (emission light) having a high excitation efficiency even for ultraviolet rays in a short wavelength region. It has a peak wavelength of about 365 nm, has excellent basic performance as a luminous pigment, and has an afterglow luminance of about 5 to 10 times that of ZnS: Cu (about 0.4 cd / m ² ) which has been widely used in the past. (2.0 cd / m ² ), which is extremely high, and its afterglow is moderately attenuated (conventional Zn
S: about 5 to 10 times or more (about 2
000 minutes or more).

Here, the afterglow time refers to the time during which the afterglow luminance attenuates to 0.3 mcd / m ² after irradiating with an illuminance of 1000 L × for 5 minutes using a common light source D _65. brightness and uses a conventional light source D _65, was irradiated for 5 minutes at an intensity of 1000 L ×, it refers to afterglow luminance after a lapse of one minute.

Several products using the above-mentioned luminous pigment SrAl ₂ O ₄ have been proposed.

For example, in Japanese Patent Application Laid-Open No. 7-48532, the "decorative member with luminous paint" includes a decorative member such as a clock face, which has a luminous paint having a luminous base made of aluminum strontium oxide on its outer surface. Has been proposed.

Japanese Patent Laid-Open Publication No. 7-313036 discloses a method for attracting insects using a fluorescent substance containing at least SrAl ₂ O ₄ .

[0018] Further, the "light storage medium" disclosed in JP-A-8-207194 has a first surface on a reflective base material layer.
A transparent resin layer, a luminous layer and a second transparent layer are sequentially laminated, and the luminous pigment of the luminous layer is SrAl ₂ O ₄ , and the luminous layer is hermetically covered with the first and second transparent resin layers. A phosphorescent body made of the following has been proposed.

Japanese Unexamined Patent Publication No. Hei 8-127937 discloses a "fiber product having luminous fluorescence" which is a fiber product having luminous fluorescence formed by blending a luminous phosphor with a thermoplastic resin. M _1-X Al ₂ O as a phosphorescent phosphor
A compound having a composition represented by _4-X , wherein M is a compound in which a compound composed of at least one or more metal elements selected from the group consisting of calcium, strontium, and barium is used as a mother crystal, and X is −0. A fiber product using a material in the range of 0.33 ≦ X ≦ 0.60 has been proposed.

[0020]

In recent years, there has been an increasing demand for a coating composition having a strong luminous (or light-emitting) property. However, a luminous paint containing the above-mentioned conventional luminous coating composition and a reflecting agent has been increasing. Or, the fluorescent paint did not fully satisfy the demand.

The present invention has been made in view of the above-mentioned conventional problems, and an object of the present invention is to provide a light-emitting coating composition and a light-emitting coating composition for providing a coating film that facilitates visual recognition of an object to be coated at night. Is to provide a way.

[0022]

In order to achieve the above-mentioned object, a light-emitting coating composition of the present invention comprises MAl ₂ O ₄ (where M is at least one of Ca, Sr and Ba) Contains) a light emitting agent whose main component is the compound represented by
The brightness of the coating film formed by the paint is 4 or more.

Therefore, according to the light-emitting coating composition of the present invention, the coating film automatically emits light when it becomes dark, so that the visibility is improved. Further, once light is absorbed, light is emitted for a while, so that electricity bills can be saved and energy can be saved. Further, the above-mentioned MAl ₂ O ₄ has higher safety than conventional zinc sulfide and the like. Further, it is possible to obtain a light-emitting coating film having an afterglow luminance extremely higher than that of conventional zinc sulfide and the like, and a decay of the afterglow, and having a long-time afterglow. This makes it possible to obtain a painted product having high night visibility.

In addition, the light-emitting coating composition of the present invention contains MAl ₂ O ₄ (where M is at least Ca, S
r or Ba), and a light emitting agent containing a compound represented by formula (1) as a main component, and a reflective agent, and the coating film formed by the coating material has a brightness of 4 or more. I do.

By containing a reflecting agent in addition to the light emitting agent, a light emitting coating film having higher afterglow luminance and a longer afterglow time can be obtained. Particularly, when the lightness of the coating film is 4
Due to the above, the light emitting performance of the light emitting agent is not impaired.

In the light-emitting coating composition of the present invention, the reflecting agent is at least one selected from glass particles and resin beads.

Since the above-mentioned reflecting agent has particularly high reflectivity on the surface of the particles, the coating film formed by the light-emitting coating composition of the present invention further has a higher afterglow luminance and a longer afterglow time. . In the light-emitting coating composition of the present invention, the light-emitting agent and the reflective agent are each contained in an amount of 2 to 80 parts by weight based on 100 parts by weight of the solid content of the coating, and the light-emitting agent is further contained. The solid / weight ratio of the agent / reflecting agent is 9/1 to 6/4.

In the method for forming a light-emitting coating film according to the present invention, MAl ₂ O ₄ (where M is at least Ca, S
r or Ba), after forming a glittering or colored coating film having a brightness of 4 or more with a light-emitting agent containing a compound represented by the following formula as a main component, or a paint containing the light-emitting agent and the reflecting agent: If necessary, a clear coating film is formed.

Accordingly, a glittering or colored coating film containing the light emitting agent alone or both the light emitting agent and the reflecting agent is formed.
This brilliant or colored coating film itself emits light, and it is possible to obtain a painted product that is visible even at night.

In the method for forming a light-emitting coating film according to the present invention, MAl ₂ O ₄ (where M is at least Ca, S
r or Ba) after forming a glittering or colored light-emitting coating film having a brightness of 4 or more with a paint containing at least one kind of a light-emitting agent or a reflective agent containing a compound represented by the following formula: Forming a clear coating film containing at least one of the light emitting agent and the reflecting agent, wherein at least one of the glittering or colored light emitting coating film and the clear coating film contains the light emitting agent. Features.

Therefore, the above-mentioned brilliant or colored coating film contains the above-mentioned light emitting agent and / or reflecting agent, and further forms a light emitting clear coating film containing the light emitting agent and / or reflecting agent. Since the light emitting agent is contained in any of the above coating films, it is possible to obtain a coating film having higher afterglow luminance, a longer afterglow time, and easily visible at night.

The light-emitting coating material of the present invention is a coating material on which a coating film is formed by any one of the above-described methods for forming a light-emitting coating film.

[0033]

BEST MODE FOR CARRYING OUT THE INVENTION <Light Emitting Paint Composition> The light emitting paint composition of the present invention is specifically described below.

(A) Light emitting agent: The light emitting agent is a compound represented by MAl ₂ O ₄ (where M is at least Ca, Sr, Ba)
Is a main component (base crystal), specifically, at least one of CaAl ₂ O ₄ , SrAl ₂ O ₄ , and BaAl ₂ O ₄ . Examples of the activator include europium (Eu), despronium (Dy) and the like. For example, each of Eu and Dy is 0.5 mol based on the host crystal.
It is contained.

The light emitting agent is in the form of particles, and the average particle size of the raw material is 50 to 60 μm. These particles are pulverized and dispersed by a sand grind mill or the like, and have an average particle size of 5
It is preferable to set it to 25 μm. As the light emitting agent, for example, "N Luminescent Luminova" (manufactured by Nemoto Special Chemical Co., Ltd.) can be used as a raw material. The method for producing MAl ₂ O ₄ conforms to the method for producing SrAl ₂ O ₄ described above.

When the average particle size of the light emitting agent is less than 5 μm, there arises a disadvantage that the natural light emission property and the light emission reflectivity are reduced, and on the other hand, the above disadvantage occurs even when the average particle size exceeds 25 μm.

The light emitting agent is contained in an amount of 2 to 80 parts by weight based on 100 parts by weight of the solid content of the coating composition of the light emitting coating composition. When the content of the light emitting agent is less than 2 parts by weight, there arises a problem that the natural light emitting property and the light emitting reflectivity are reduced. The disadvantage of lowering occurs.

(B) Reflecting agent: The reflecting agent is preferably at least one selected from glass particles and resin beads, and is preferably transparent.

The reflecting agent preferably has a true spherical shape, and the average particle diameter is preferably 5 to 100 μm. The refractive index of the reflective agent is preferably 1.5 to 2.0.

When the average particle size of the above-mentioned reflective agent is less than 5 μm, there is a disadvantage that the reflection effect is not sufficiently obtained and the visibility is reduced. The inconvenience that the fixability is reduced occurs.

When the refractive index of the reflective agent is less than 1.5, there is a disadvantage that the light reflectivity is reduced, and when the refractive index exceeds 2.0, the same disadvantage occurs.

The reflective agent is contained in an amount of 2 to 80 parts by weight based on 100 parts by weight of the solid content of the light-emitting coating composition. When the content of the reflecting agent is less than 2 parts by weight, a disadvantage that the reflection effect is not sufficiently obtained and the visibility is lowered occurs. On the other hand, when the content is more than 80 parts by weight, the performance as a coating film is deteriorated. Inconvenience occurs.

When the solid content ratio of the light emitting agent / reflecting agent is 9
/ 1 to 6/4, and the solid content ratio is 9
When the ratio exceeds / 1, there is a disadvantage that the reflection function is not sufficiently obtained and the visibility is reduced. On the other hand, when the ratio is less than 6/4, the light emission function is not sufficiently obtained and the visibility is reduced. Inconvenience occurs.

(C) Vehicle and curing agent: In the present invention, a thermosetting resin and a curing agent are used as a vehicle. As the thermosetting resin, an acrylic resin, a silicon-modified acrylic resin, a polyester resin, and a silicon-modified resin are used. Base resins such as polyester resins and fluororesins can be mentioned. As the curing agent, at least one of an amino resin such as a melamine resin and a guanamine resin, and an isocyanate or a blocked isocyanate compound is used. The curing agent is preferably a melamine resin or a blocked polyisocyanate compound.

The amount of the thermosetting resin is 5 to 30 parts by weight, preferably 8 to 30 parts by weight, based on 100 parts by weight of the solid content of the coating material.
It is 25 parts by weight, more preferably 10 to 20 parts by weight.
The compounding amount of the curing agent is 1 to 50 parts by weight, preferably 3 to 18 parts by weight, more preferably 5 to 15 parts by weight.

On the other hand, a thermoplastic resin can be used as the vehicle in the present invention. Chlorinated olefin resins such as chlorinated polyethylene and chlorinated polypropylene, vinyl chloride resins, vinyl acetate, vinylidene chloride, and vinyl resins obtained by copolymerizing them, cellulose resins, acetal resins, and alkyd resins that can be generally used in the coatings field. And chlorinated rubber resins.

The coating composition of the present invention can be cured by ordinary temperature (natural) drying, forced drying, baking, etc., by selecting the above resin.

Other additives: In the present invention, various pigments such as bright pigments, coloring pigments, extender pigments, rust-preventive pigments and the like can be further added to the above components. However, the brightness of the coating film formed is the brightness scale (V) of JISZ8721.
Is required to be 4 or more, and the brightness is adjusted by selecting the following brilliant pigments and / or coloring pigments.

As the pigment, (1) As the glitter pigment,
For example, aluminum foil having a particle size of 10 to 45 μm, mica foil, bronze foil, tin foil, gold foil, copper foil, metal titanium foil, stainless steel foil, nickel foil, chromium foil, and the above-mentioned metal alloy foil, coated with plastic Metal foil,
Examples include foil-like phthalocyanine blue, cobalt sulfide, manganese sulfide, and titanium sulfide.

Examples of the (2) color pigments include organic azo lake pigments, insoluble azo pigments, condensed azo pigments, phthalocyanine pigments, indigo pigments, perinone pigments, perylene pigments, and dioxazine pigments. Inorganic pigments, quinacridone pigments, isoindolinone pigments, metal complex pigments, etc., such as inorganic graphite, yellow iron oxide, red iron oxide, carbon black, and titanium dioxide.

(3) Calcium carbonate,
Barium sulfate, clay, talc and the like can be used.

(4) Various rust preventive pigments used for paints can be used according to the purpose.

The amount of the pigment to be added is preferably 100 parts by weight or less based on 100 parts by weight of the total of the solid components of the thermosetting resin and the curing agent.

Further, a curing catalyst such as butyltin laurate dodecylbenzenesulfonate, a benzophenol ultraviolet absorber, an antioxidant such as phenol or sulfide, a surface conditioner such as silicone or an organic polymer, and an anti-sagging agent , An additive such as a thickener, a rust preventive such as fumed silica, and the like. These additives, the total of the solid components of the thermosetting resin and the curing agent as 100 parts by weight,
It can be blended in an amount of 5 parts by weight or less.

To adjust the viscosity of the paint, aromatic hydrocarbons such as benzene, toluene, ethylbenzene and chlorobenzene, aliphatic hydrocarbons such as cyclohexane, ethylcyclohexane and perchloroethylene, ethyl acetate, butyl acetate and acetic acid are used. Esters such as isobutyl, acetone, methyl ethyl ketone, methyl isobutyl ketone,
Cyclohexanone, isophorone, ketones such as diacetalcohol, ethers such as carbitol acetate and butyl carbitol, dioxane, tetrahydrofuran, dimethylformamide, nitropropane, styrene, mineral spirits, solvents commonly used in the paint field such as water,
They can be appropriately selected and used alone or in combination.
The solid content at the time of coating is preferably 30 to 80%.

For dispersion of each of the above components, an apparatus such as a paint shaker, a dissolver, a ball mill, a sand grind mill, a kneader and the like which are usually used in the production of paints can be used.

<Method of forming light-emitting coating film> The base material on which the light-emitting coating composition of the present invention can be coated is iron, zinc-iron, zinc-aluminum, zinc-manganese, Including metals such as zinc-cobalt, zinc-nickel-chromium, zinc-nickel-cobalt, zinc-nickel, aluminum, copper and various alloys, inorganic materials such as glass, cement, concrete,
Polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polyamide, polyacryl, polyester,
Examples include resin molded products such as ethylene-polyvinyl alcohol copolymer, vinyl chloride resin, vinylidene chloride resin, polycarbonate, and polyurethane, plastic materials such as various FRPs, wood, and fiber materials. It is optional to perform an appropriate cleaning treatment, chemical conversion treatment, and undercoat treatment on the substrate to be coated in advance. A light emitting agent and / or
Or a reflecting agent-containing base coating film forming step, and a light emitting agent and / or
Alternatively, a reflective agent-containing clear coating film forming step is sequentially performed. However, a light emitting agent is always contained in either the base coating film or the clear coating film. In addition, the coating can be performed directly on the substrate to be coated.
It is preferable to apply an epoxy polyester primer from the viewpoint of rust prevention. In addition, in the case of painting an automobile alone, it is usually preferable to apply an intermediate coat (polyester / melamine-based) after an undercoating with an electrodeposition paint or the like after the surface chemical conversion treatment, and then apply the coating after the coating is cured. In particular, it is preferable to apply a primer to a plastic member such as an automobile bumper from the viewpoint of adhesion.

The thickness of the coating film can be appropriately selected according to the purpose. The format of the multilayer coating is 2 coats 1
The baking method, two-coat two-bake method, three-coat one-bake method, three-coat two-bake method, three-coat three-bake method, or the like can be used.

The light-emitting coating composition of the present invention containing the above-described light-emitting agent is formed as a coating on a surface of various substrates to be coated as a single-layer or multilayer coating. The coating method is not particularly limited, and a common coating means such as air spray coating, air-rez coating, electrostatic coating, roll coat coating, curtain coat coating, and extrusion coating can be used.

In the following method for forming a light-emitting coating film of the present invention, the above-mentioned light-emitting agent and reflecting agent are contained in the coating film in combinations as shown in Table 1.

[0061]

[Table 1] <Light-emitting coated plate> The coated product excellent in light-emitting property according to the present invention comprises a base coating film or a clear coating film containing a light-emitting agent, and a light-emitting and / or reflector-containing base. After forming the coating film, a clear coating film containing a light emitting agent and / or a reflecting agent was formed.

The conditions for baking the coating film are as follows:
C., preferably about 3 to 30 minutes. Depending on the resin type, a coating film can be formed by drying at room temperature.

When the baking temperature is lower than the above range, the coating film is not sufficiently cured, so that the film formation becomes insufficient, the performance as the coating film is not obtained, and the corrosion resistance as the coating film is lowered. On the other hand, when the baking temperature is higher than the above range, the coating film is in a so-called overbaked state, which causes yellowing of the coating film and a decrease in adhesion.

The light-emitting coating material of the present invention includes a door panel, an edge of a staircase, a switchboard, a handrail, a handle, a keyhole, a switch, a guidance display panel, a bumper, a guide rail,
It can be used for emergency equipment, evacuation equipment, automobile bodies and their parts (particularly bumpers), etc.

Next, another preferred embodiment of the present invention will be described below.

1. In the coating composition of the present invention, as the vehicle, any one of [thermosetting resin and curing agent] or [thermoplastic resin] can be used.

2. In the above “1.”, the thermosetting resin is at least one of an acrylic resin, a silicon-modified acrylic resin, a polyester resin, a silicon-modified polyester resin, and a fluororesin.

3. In the above “1.”, as the thermoplastic resin, chlorinated polyethylene, chlorinated olefin-based resin such as chlorinated polypropylene, vinyl chloride resin, vinyl acetate, vinylidene chloride and a vinyl resin copolymerized with these, a cellulose-based resin , Acetal resins, alkyd resins, and chlorinated rubber resins.

4. The light emitting agent is CaAl ₂ O ₄ , SrAl ₂
At least one of O ₄ and BaAl ₂ O ₄ is used as a (base crystal) and contains europium (Eu) and despronium (Dy) as activators.

5. The light emitting agent preferably has an average particle size of 5 to 25 μm.

6. The reflecting agent preferably has a true spherical shape.

7. The reflector has an average particle diameter of 5 to 100.
μm is preferred.

8. The refractive index of the reflector is preferably 1.5 to 2.0.

9. The light-emitting coating composition of the present invention is further added with any one of bright pigments, coloring pigments, and extender pigments.

10. The light-emitting coating composition of the present invention further comprises a curing catalyst such as dodecylbenzenesulfonic acid, butyltin laurate, a benzophenol-based ultraviolet absorber, a phenol-based or sulfide-based antioxidant, a silicone or an organic polymer. And other additives such as a surface conditioner, a sagging agent, a thickener, and a rust preventive such as fumed silica.

11. The light-emitting coating composition of the present invention further includes an aromatic hydrocarbon such as benzene, toluene, ethylbenzene and chlorobenzene, an aliphatic hydrocarbon such as cyclohexane, ethylcyclohexane and perchloroethylene in order to adjust the viscosity of the coating. , Ethyl acetate, butyl acetate, esters such as isobutyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, ketones such as diacet alcohol,
Ethers such as carbitol acetate and butyl carbitol, and solvents usually used in the field of paints such as dioxane, tetrahydrofuran, dimethylformamide, nitropropane, styrene, mineral spirits, and water are appropriately selected and used alone or in combination.

12. The light-emitting coating composition for pre-coating of the present invention is obtained by dispersing the above-mentioned components using a paint shaker, dissolver, ball mill, sand grind mill, or kneader.

13. Substrates that can be coated using the light-emitting coating composition of the present invention are iron, zinc-iron, zinc-aluminum, zinc-manganese, zinc-cobalt,
Zinc-nickel-chromium, zinc-nickel-cobalt,
Including metals such as alloys such as zinc-nickel, aluminum, copper or various alloys, glass, cement,
Inorganic materials such as concrete, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polyamide,
It is any of resin molded products such as polyacryl, polyester, ethylene-polyvinyl alcohol copolymer, vinyl chloride resin, vinylidene chloride resin, polycarbonate, polyurethane, and plastic materials such as various FRPs, wood, and fiber materials.

14. In the method for forming a light-emitting coating film of the present invention, a two-coat one-bake method,
Any one of a coat 2 bake method, a coat 3 bake method, a coat 3 bake method, and a coat 3 bake method is adopted.

15. In the method for forming a light-emitting coating film of the present invention, the coating method is any of air spray coating, air-rez coating, electrostatic coating, roll coating, curtain coating, and extrusion coating.

16. For post-coat, furnace temperature 130 ~
The temperature is preferably set to 200 ° C. for about 3 to 30 minutes.

[0082]

Next, the present invention will be described in detail with reference to examples and comparative examples.

Examples 1 to 29 and Comparative Examples 1 to 3 (1) Preparation of Test Plates; Examples 1 to 19 and Comparative Examples 1 to 3; Bright or colored paints of A or B and, if necessary, clear coating films were formed under the conditions shown in Tables 5, 6, and 8.

Examples 20 to 24: After cold-rolled steel sheets for automobiles were treated with zinc phosphate, an undercoat “Power Top U-600” (cationic electrodeposition paint, manufactured by Nippon Paint Co., Ltd.) was electrodeposited. Thereafter, baking was performed at 170 ° C. for 20 minutes to a dry film thickness of 20 μm, and an intermediate coating “Olga OP-41” (polyester / melamine-based intermediate coating,
Nippon Paint Co., Ltd.) at 140 ° C x 20
Then, the coating was baked so as to have a dry film thickness of 35 μm, and further, a glittering or colored paint of C shown in Table 2 below and, if necessary, a clear coating film were formed under the conditions shown in Table 7.

[0085]

[Table 2] Examples 25 to 29: For automobile bumpers After a member molded from a polyphenylene ether resin and a polyamide resin was degreased with isopropyl alcohol, the following <bumper primer> was applied by air spraying, and
The coating was baked at 40 ° C. for 20 minutes to a dry film thickness of 30 μm, and a glitter or colored paint of C shown in Table 2 above and, if necessary, a clear coating film were formed under the conditions shown in Table 7.

<Bumper Primer> Polyester resin components (component (A)), curing agents (component (B)), pigments (component (C)) and other additives (component (D )) In the proportions shown in Table 3, and based on a total of 100 parts by weight of the components (A) and (B), a polyfunctional cyanate compound and a polyfunctional maleimide were added to the S compound shown in Table 3. A mixture with a compound (component (E)), "BT
-200 "(manufactured by Mitsubishi Gas Chemical Co., Ltd.), and these were placed in a sand grind mill and uniformly stirred and mixed to prepare a coating material.

[0087]

[Table 3] Note) (1): Component (A-1); polyester resin A method for synthesizing the above polyester resin; a mixture shown in Table 4 below was stirred at 210 to 230 ° C., and a dehydration reaction was performed until the acid value reached 10. After cooling, the reaction mixture was diluted with 340 parts by weight of “Solvesso 100” (manufactured by Exxon Chemical Co., Ltd.) to obtain a number average molecular weight of 800 and a nonvolatile content of 70.0.
%, And a polyester resin (A-1) having a viscosity T (Gardner-Holt bubble viscometer).

[0088]

[Table 4] (2): Component (A-2); urethane-modified polyester resin A method for synthesizing the urethane-modified polyester resin; 720 g of “esterdiol 204” (manufactured by Union Carbide) and trimethylolpropane 216 in a reaction vessel.
g, dibutyltin oxide 2 g, and adipic acid 50
4 g, the temperature was raised to 149 ° C., and the acid value was 10
Aged until reduced to Then, 150 g of xylene
Was added, and the temperature was raised to 177 ° C. to ripen until the acid value reached 2. After cooling the reaction mixture to 93 ° C., “Desmozur W” (manufactured by Mobay Chemical Co.) was added dropwise over 1 hour. After completion of the dropwise addition, the reaction was continued at 93 ° C., and it was confirmed from the IR spectrum that the isocyanate group had disappeared. Then, the reaction mixture was diluted with methylaluminum ketone to obtain a polyester resin (A-2) having a nonvolatile content of 70.0% and a viscosity of Z1 (Gardner-Holt bubble viscometer).

(3): A methyl / butyl mixed alkyl etherified methylol melamine resin having a nonvolatile content of 80.0% (“Cymel 202” manufactured by Mitsui Cyanamid Co., Ltd.).

(4): "Epicoat 1001" (manufactured by Yuka Shell Epoxy Co., Ltd.).

(5): butyl acetate / xylene = 1/4 (weight ratio).

(6): A mixture of a polyfunctional cyanate compound and a polyfunctional maleimide compound (BT-200 manufactured by Mitsubishi Gas Chemical Co., Ltd.). Total 1 of component (A) and component (B)
Amount based on 00 parts by weight.

(7): N- (p-methylbenzyl) -N,
N'-dimethylanilinium-P-dodecylbenzenesulfonate. The amount of the component (A), the component (B), and the component (E) in 100 parts by weight in total.

(2) Evaluation method: Table 5, Table 6, Table 7 and Table 8 show the results of evaluation according to the following items.

(I) Spontaneous light emission: Light source: _D65 ordinary light source (illuminance: 400 L × (lux)) Irradiation time: 20 minutes Irradiation was carried out under the above conditions, and the light emission after printing was visually observed.

<Evaluation Criteria> It was visually confirmed that the coating film was shiny and evaluated.

◎: There is a feeling that light is sufficiently emitted. ：: There is a feeling that light is emitted. Δ: Weak, but light is emitted, and recognition is possible. Reflectivity: Light source: 60 W halogen headlamp for automobile The light reflectance was visually observed using the above light source.

<Evaluation Criteria> It was visually confirmed that the coating film was shiny and evaluated.

◎: There is a feeling that light is sufficiently emitted.: There is a feeling that light is emitted. Δ: Weak, but light is emitted, and recognition is possible.

[Table 5]

[Table 6]

[Table 7]

[Table 8] Note) In Tables 5, 6, 6, and 8, [Method of forming coating film] is the method described in Table 1 above.

[Light Emitting Agent] a: SrAl ₂ O ₄ a: CaAl ₂ O ₄ c: BaAl ₂ O ₄ d: SrAl ₂ O ₄ and Eu-Dy (Eu: 0.5mo) as an activator
l, Dy: 0.5 mol) Phosphor e: SrAl ₂ O ₄ and Eu (Eu: 0.5 mol) as an activator
Phosphor F: "GSS" (Zinc sulfide phosphor, manufactured by Nemoto Special Chemicals Co., Ltd.) [Reflecting agent] a: Glass particles b: Acrylic resin beads c: Urethane resin beads.

Average particle size: μm From these results, the light-emitting coating composition and the method for forming a light-emitting coating film of the present invention are superior in spontaneous light-emitting properties and light-emitting reflectivity as compared with the prior art. It has been found that a coated film can be provided.

[0102]

As described above, according to the light-emitting coating composition and the method for forming a light-emitting coating film of the present invention according to the present invention, the coating film automatically emits light when it gets dark, The performance is improved. Further, once light is absorbed, light is emitted for a while, so that electricity bills can be saved and energy can be saved. Further, the above-mentioned MAl ₂ O ₄ has higher safety than conventional zinc sulfide and the like. Further, it is possible to obtain a light-emitting coating film having an afterglow luminance extremely higher than that of conventional zinc sulfide and the like, and a decay of the afterglow, and having a long-time afterglow. This makes it possible to obtain a painted product having high night visibility.

Further, by containing a reflecting agent in addition to the light emitting agent, a light emitting coating film having higher afterglow luminance and a longer afterglow time can be obtained. In particular, the light emission performance of the light emitting agent is not impaired by setting the lightness of the coating film to 4 or more.

Claims (7)

[Claims] 1. MAl ₂ O _{4 wherein} M is at least C
a, Sr, or Ba) as a main component, and the coating has a light-emitting property of 4 or more in brightness. Paint composition. 2. A light-emitting agent containing a compound represented by MAl ₂ O ₄ (where M is at least one of Ca, Sr, and Ba) as a main component, a reflecting agent, And a light-emitting coating composition, wherein the coating has a lightness of 4 or more. 3. The light-emitting coating composition according to claim 2, wherein the reflecting agent is at least one selected from glass particles and resin beads. 4. The light-emitting coating composition according to claim 3, wherein the light-emitting agent and the reflecting agent are contained in an amount of 2 to 80 parts by weight based on 100 parts by weight of the solid content of the coating. Further, a light-emitting coating composition, wherein the weight ratio of the solid content of the light-emitting agent / reflecting agent contained is from 9/1 to 6/4. 5. A light-emitting agent comprising a compound represented by MAl ₂ O ₄ (wherein M is at least one of Ca, Sr and Ba) as a main component, A method for forming a light-emitting coating film, which comprises forming a clear coating film, if necessary, after forming a glittering or colored coating film having a brightness of 4 or more with a coating material containing a light agent and a reflecting agent. 6. A light emitting agent or a reflecting agent mainly composed of a compound represented by MAl ₂ O ₄ (where M is at least one of Ca, Sr, and Ba), is coated on an object to be coated. After forming a glittering or colored light-emitting coating film having a brightness of 4 or more with a paint containing at least one kind, a clear coating film containing at least one kind of the light-emitting agent or the reflecting agent is formed, and at least the glittering property is formed. Alternatively, a method for forming a light-emitting coating film, wherein the light-emitting agent is contained in any of a colored light-emitting coating film and a clear coating film. 7. A light-emitting coated material which is coated by the light-emitting coating film forming method according to claim 5 or 6.