JP2015086312A - Fluorescent coating composition and article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorescent coating composition which is improved in weather resistance of a fluorescent coated film, keeps landscape and aesthetics of the fluorescent coated film and is reduced in frequency of re-coating and an article.SOLUTION: A fluorescent coating composition comprises a fluorine-containing resin (A) consisting of a copolymer (A1) including a structural unit (A1-1) based on a fluoroolefin and a structural unit (A1-2) based on an alkyl vinyl ether type monomer and/or polyvinylidene fluoride (A2) and a fluorescent substance.

Description

  The present invention relates to fluorescent coating compositions and articles.

  To improve visibility and design of road-related products such as bridge protection fences, road fences and instruction posts, interior and exterior of buildings, building-related products such as building materials, lighting equipment, and electrical products such as watches. In addition, a fluorescent paint may be applied.

In fluorescent paints, daylight fluorescent pigments are usually used in which an organic phosphor such as fluorescein, rhodamine, acriflavine, chloroaluminum phthalocyanine is blended with an uncolored resin component.
In addition, since organic phosphors are unstable to light such as ultraviolet rays, inorganic phosphors may be used. For example, Patent Document 1 discloses a fluorescent paint in which an inorganic phosphor and a color pigment are blended in a resin component.

The resin component is blended in order to improve the coating properties of the fluorescent paint and to impart weather resistance, landscape and aesthetics to the fluorescent coating. For example, in the example of this document, ZAFLON FC110 manufactured by Toagosei Co., Ltd., which is a chlorotrifluoroethylene-based fluororesin, is used.
However, when ZAFLON FC110 or the like is used as a resin component, it cannot be said that the weather resistance of the fluorescent coating film is sufficient, so that the landscape and aesthetics of the fluorescent coating film cannot be maintained for a long time, and the repainting frequency is high. high.

JP 11-49989 A

  In view of the above circumstances, the present invention can further improve the weather resistance of the fluorescent coating film by examining the resin component, and can maintain the landscape and aesthetics of the fluorescent coating film for a long period of time. An object is to provide a fluorescent coating composition and an article having a small amount.

The present invention is the fluorescent paint composition and article described in [1] and [2] below.
[1] Any one of a copolymer (A1) having a structural unit (A1-1) based on a fluoroolefin and a structural unit (A1-2) based on an alkyl vinyl ether monomer, and polyvinylidene fluoride (A2) Or the fluorescent paint composition containing both fluororesin (A) and fluorescent substance (B).
[2] An article comprising an object to be coated and a fluorescent coating film formed on the object to be coated with the fluorescent coating composition according to [1].

  According to the fluorescent paint composition and article of the present invention, since the fluorescent coating film is excellent in weather resistance, it is possible to maintain the landscape and aesthetics of the fluorescent coating film for a long period of time, and to reduce the frequency of repainting. .

In the present specification, a part of or all of the functional groups of the repeating unit directly formed by polymerization of the monomer and the repeating unit formed by polymerization of the monomer are chemically converted to other functional groups. These units are collectively referred to as “structural units”.
“(Meth) acrylate” is a general term for acrylate and methacrylate.
Moreover, converting a functional group of a monomer or a copolymer to a functional group other than the functional group is referred to as “functional group conversion”.

<Fluorescent paint composition>
The fluorescent coating composition of the present invention comprises a structural unit (A1-1) based on a fluoroolefin (hereinafter simply referred to as “structural unit (A1-1)”) and a structural unit based on an alkyl vinyl ether monomer (A1- 2) (hereinafter simply referred to as “structural unit (A1-2)”) (A1) (hereinafter referred to as “FEVE (A1)”), and polyvinylidene fluoride (A2) (hereinafter referred to as “the structural unit (A1-2)”). One or both of the fluorine-containing resins (A) (hereinafter referred to as “fluorine-containing resin (A)”) and the phosphor (B).
The form of the fluorescent coating composition may be a solvent system, an emulsion system, or a powder system.

[FEVE (A1)]
FEVE (A1) is a copolymer having a structural unit (A1-1) and a structural unit (A1-2). In order to further improve the weather resistance, the copolymer preferably has a high alternating copolymerization property, and more preferably a complete alternating copolymer.
In addition to the structural unit (A1-1) and the structural unit (A1-2), FEVE (A1) is an arbitrary structural unit (A1) other than the structural unit (A1-1) and the structural unit (A1-2). -3) may be a resin made of a copolymer.

(Structural unit (A1-1))
FEVE (A1) consists of a copolymer having a structural unit (A1-1) based on a fluoroolefin as one of the structural units.
A fluoroolefin is a compound in which one or more hydrogen atoms of an olefin hydrocarbon (general formula C _n H _2n ) are substituted with fluorine atoms.
2-8 are preferable and, as for the carbon atom number of a fluoro olefin, 2-6 are more preferable.
The number of fluorine atoms in the fluoroolefin (hereinafter referred to as “fluorine addition number”) is preferably 2 or more, and more preferably 3-4. When the fluorine addition number is 2 or more, the weather resistance of the fluorescent coating film is improved. In the fluoroolefin, one or more hydrogen atoms not substituted with fluorine atoms may be substituted with chlorine atoms.

Specific examples of the fluoroolefin include tetrafluoroethylene, chlorotrifluoroethylene (hereinafter referred to as “CTFE”), hexafluoropropylene, vinylidene fluoride, and vinyl fluoride. Among these, tetrafluoroethylene and CTFE are preferred, and CTFE is more preferred, which tends to cause alternating copolymerization with the following structural unit (A1-2).
As the structural unit (A1-1), one type of structural unit may be used alone, or two or more types may be used in combination.

(Structural unit (A1-2))
FEVE (A1) consists of a copolymer having a structural unit (A1-2) based on an alkyl vinyl ether monomer as one of the structural units. This structural unit (A1-2) is easy to form an alternating copolymer with the above-mentioned structural unit (A1-1).
Although it does not restrict | limit especially as an alkyl vinyl ether type monomer, For example, the compound (henceforth "compound (1)") represented by the following Formula (1) is mentioned.
CH ₂ = CHOR ¹ (1)
Here, R ¹ represents a hydrocarbon group, and specifically includes a linear, branched, or cyclic alkyl group having 2 to 8 carbon atoms.
Further, the hydrogen atom of the hydrocarbon group of R ¹ may be substituted with a substituent such as a hydroxyl group, a carboxy group, an alkoxysilyl group, an amino group, an epoxy group, an isocyanate group, a halogen atom, a glycidyl group, or an ethylene glycol group. Good. Of these substituents, it is preferably substituted with a crosslinkable group such as a hydroxyl group, a carboxy group, an alkoxysilyl group, an amino group, an epoxy group, or an isocyanate group.

Examples of the alkyl vinyl ether monomer (hereinafter referred to as “hydroxyl group-containing alkyl vinyl ether”) (a1-2-1) in the case where the crosslinkable group is a hydroxyl group include 2-hydroxyethyl vinyl ether and 3-hydroxypropyl vinyl ether. 4-hydroxybutyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxy-2-methylbutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether Hydroxyalkyl vinyl ethers such as diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl Ethylene glycol monomethyl ether and ether, and the like.
The hydroxyl group-containing alkyl vinyl ether (a1-2-1) is a functional group capable of reacting and bonding a crosslinkable group other than the hydroxyl group of the alkyl vinyl ether having a crosslinkable group other than the hydroxyl group with the crosslinkable group other than the hydroxyl group. It may be a hydroxyl group-containing alkyl vinyl ether obtained by functional group conversion with a compound having a group and a hydroxyl group. For example, the hydroxyl group containing alkyl vinyl ether obtained by making ethylene glycol react with the alkyl vinyl ether which has a carboxy group is mentioned.

Examples of the alkyl vinyl ether monomer (hereinafter referred to as “carboxy group-containing alkyl vinyl ether”) (a1-2-2) in the case where the crosslinkable group is a carboxy group include vinyloxyvaleric acid and 3-vinyloxypropion. Examples thereof include saturated carboxylic acid vinyl ethers such as acid 3- (2-vinyloxybutoxycarbonyl) propionic acid and 3- (2-vinyloxyethoxycarbonyl) propionic acid.
The carboxy group-containing alkyl vinyl ether (a1-2-2) includes a carboxy group-containing alkyl vinyl ether (a1-2-1) obtained by reacting an acid anhydride such as a dicarboxylic acid anhydride with the hydroxyl group-containing alkyl vinyl ether (a1-2-1). An alkyl vinyl ether monomer may be used.

Examples of the alkyl vinyl ether monomer (hereinafter referred to as “alkoxysilyl group-containing alkyl vinyl ether”) (a1-2-3) when the crosslinkable group is an alkoxysilyl group include trimethoxysilylethyl vinyl ether, Examples thereof include ethoxysilylethyl vinyl ether, trimethoxysilylbutyl vinyl ether, methyldimethoxysilylethyl vinyl ether, trimethoxysilylpropyl vinyl ether, and triethoxysilylpropyl vinyl ether.
Further, the alkoxysilyl group-containing alkyl vinyl ether (a1-2-3) is a crosslinkable group other than the alkoxysilyl group and a crosslinkable group other than the alkoxysilyl group of the alkyl vinyl ether having a crosslinkable group other than the alkoxysilyl group. It may be an alkoxysilyl group-containing alkyl vinyl ether obtained by functional group conversion with a compound having a functional group capable of reacting with and bonding to an alkoxysilyl group.

For example, when a compound represented by the following formula (2) (hereinafter referred to as “compound (2)”) is used, a crosslinkable group having active hydrogen, such as a hydroxyl group-containing vinyl ether, a carbonyl group-containing vinyl ether, or an amino group-containing vinyl ether. Can be functionally converted into an alkoxysilyl group-containing alkyl vinyl ether (hereinafter referred to as “compound (2) converted vinyl ether”).
OCN (CH ₂ ) _q SiX _p R ² _3-p (2)
(However, in the formula, R ² is a monovalent hydrocarbon group hydrogen atom or a C1-10, X is an alkoxy group having 1 to 5 carbon atoms, p is there an integer from 1 to 3 Q is an integer of 1 to 5.)
For example, a urethane bond (—C (═O) NH—) is formed by a reaction between the hydroxyl group of the hydroxyl group-containing vinyl ether and the compound (2), and the formula —C (═O) NH (CH ₂ ) _q SiX _p R ² It becomes a monomer having a group represented by _3-p .

If the carbon number of the monovalent hydrocarbon group in R ² is 10 or less, the compound (2) is bulky, so that the condensation reaction can be prevented from proceeding due to steric hindrance. It becomes easy to obtain excellent durability, weather resistance, scratch resistance and impact resistance. R ² is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, more preferably a monovalent hydrocarbon group having 1 to 5 carbon atoms, and a methyl group or an ethyl group. Particularly preferred.
If the carbon number of X is 5 or less, the alcohol component generated by the crosslinking reaction with the curing agent (C) is likely to volatilize, and the alcohol component is less likely to remain in the cured fluorescent coating film. Durability such as heat resistance, water resistance and moisture resistance, weather resistance, scratch resistance and impact resistance are improved. X is preferably an ethoxy group or a methoxy group.
q is preferably an integer of 2 to 4.

Specific examples of the compound (2) include 3-isocyanatopropyltrimethoxysilane (X = methoxy group, p = 3, q = 3), 3-isocyanatopropyltriethoxysilane (X = ethoxy group, p = 3, q = 3), 3-isocyanate propyl methyl dimethoxy silane (X = methoxy group, ^{R 2} = methyl group, p = 2, q = 3), 3-isocyanate propyl methyl diethoxy silane (X = ethoxy group, ^{R 2} = methyl group, p = 2, q = 3 ), 3- isocyanate dimethyl silane (X = methoxy group, ^{R 2} = methyl group, p = 1, q = 3 ), 3- isocyanate dimethyl silane (X = ethoxy group, ^{R 2} = methyl group, p = 1, q = 3 ), 4- isocyanate butyl trimethoxysilane (X = methoxy, p = 3, q 4), 4-isocyanatobutyltriethoxysilane (X = ethoxy group, p = 3, q = 4), 2-isocyanatoethyltrimethoxysilane (X = methoxy group, p = 3, q = 2), 2-isocyanate And ethyltriethoxysilane (X = ethoxy group, p = 3, q = 2). Among these, 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane are preferable from the viewpoint of availability.
A compound (2) may be used individually by 1 type, and may use 2 or more types together.

A method of converting the compound (2) into a hydroxyl group-containing vinyl ether with a functional group (hereinafter referred to as “compound (2) conversion method”) is a solvent that does not contain active hydrogen that reacts with the isocyanate group of the compound (2) (for example, acetic acid). For example, ethyl, methyl ethyl ketone, xylene, etc.) by reacting the hydroxyl group-containing vinyl ether with the compound (2).
The ratio of the compound (2) to the hydroxyl group-containing vinyl ether is preferably 0.1 to 10 mol, more preferably 0.5 to 5 mol, per mol of the hydroxyl group. When the amount of the compound (2) is 0.1 mol or more with respect to 1 mol of the hydroxyl group, the amount of the alkoxysilyl group increases, so that the curing at the time of forming the fluorescent coating film easily proceeds. If the amount of the compound (2) is 10 mol or less with respect to 1 mol of the hydroxyl group, the unreacted compound (2) can be prevented from remaining in a large amount in the fluorescent coating film. Scratch resistance and impact resistance are improved.

  The reaction between the hydroxyl group of the hydroxyl group-containing vinyl ether and the isocyanate group of the compound (2) can be carried out in a yield of almost 100%. However, in order to further increase the reaction rate, the compound (2) may be reacted in an excessive state. it can. In that case, after removing the compound (2) from the reaction product, a polymerization reaction may be performed to produce FEVE (A1), and the reaction product still contains the unreacted compound (2). FEVE (A1) may be produced by performing a polymerization reaction in the state.

  The reaction temperature of the reaction between the hydroxyl group-containing vinyl ether and the compound (2) is preferably room temperature to 100 ° C, more preferably 50 to 70 ° C. The reaction is preferably performed in an inert atmosphere such as a nitrogen atmosphere. The reaction time can be appropriately changed according to the progress of the reaction, and is preferably 1 to 24 hours, more preferably 3 to 8 hours. An organic metal catalyst such as an organic tin compound, an organic aluminum compound, an organic zirconium compound, or an organic titanate compound may be present in the reaction system for the purpose of promoting the reaction.

Similar to the compound (2), a compound in which the isocyanate group of the compound (2) is replaced with a functional group reactive with a hydroxyl group such as a carboxy group, a reactive derivative thereof, or an epoxy group may be used instead of the compound (2). A monomer having an alkoxysilyl group can be obtained.
Moreover, you may perform functional group conversion using the crosslinkable group conversion compound which has crosslinkable groups other than an alkoxy silyl group instead of a compound (2). For example, a hydroxyl group can be converted into a carboxy group by reacting a monomer having a hydroxyl group with a polyvalent carboxylic acid anhydride.

Examples of the alkyl vinyl ether monomer (hereinafter referred to as “amino group-containing alkyl vinyl ether”) (a1-2-4) in the case where the crosslinkable group is an amino group include the formula CH ₂ ═CO (CH ₂ ). Examples thereof include amino vinyl ethers represented by _x NH ₂ (x is an integer of 0 to 10).

  Examples of the alkyl vinyl ether monomer (hereinafter referred to as “epoxy group-containing alkyl vinyl ether”) (a1-2-5) when the crosslinkable group is an epoxy group include glycidyl vinyl ether.

  Examples of the alkyl vinyl ether monomer (hereinafter referred to as “isocyanate group-containing alkyl vinyl ether”) (a1-2-6) in the case where the crosslinkable group is an isocyanate group include 2-isocyanate ethyl vinyl ether.

  In addition, the alkyl vinyl ether monomer may not have a crosslinkable group. Examples of the alkyl vinyl ether monomer (a1-2-7) having no crosslinkable group include unsubstituted methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, cyclohexyl vinyl ether, octadecane vinyl ether and the like. Alkyl vinyl ethers; halogen-substituted alkyl vinyl ethers such as chloroethyl vinyl ether and perfluoroalkyl vinyl ether.

In the present specification, the above-mentioned “crosslinkable group other than hydroxyl group”, “crosslinkable group other than carboxy group”, “crosslinkable group other than alkoxysilyl group”, “crosslinkable group other than amino group”, “epoxy group” The crosslinkable groups possessed by the monomer before the functional group conversion such as “crosslinkable group other than” and “crosslinkable group other than isocyanate group” are collectively referred to as “original crosslinkable group”.
Further, the above-mentioned "compound having a functional group capable of reacting with a crosslinkable group other than a hydroxyl group and a hydroxyl group" and "a functional group capable of reacting with a crosslinkable group other than a carboxy group and a carboxy group are combined. A compound having a functional group capable of reacting with a crosslinkable group other than an alkoxysilyl group and an alkoxysilyl group, a functional group capable of reacting with a crosslinkable group other than an amino group, and “Compound having an amino group”, “Compound having a functional group capable of reacting with a crosslinkable group other than an epoxy group and an epoxy group”, “Function capable of reacting with a crosslinkable group other than an isocyanate group to bind The compounds used for functional group conversion such as “compounds having a group and an isocyanate group” are collectively referred to as “crosslinkable group conversion compounds”.
Moreover, the crosslinkable group which the monomer obtained by functional-group-converting the original crosslinkable group with a crosslinkable group conversion compound is generically called "target crosslinkable group".

Examples of the functional group capable of reacting with and binding to the original crosslinkable group in the crosslinkable group converting compound (hereinafter referred to as “functional group capable of binding to the original crosslinkable group”) include the original crosslinkable group. In the case of a hydroxyl group, an isocyanate group, a carboxy group, a reactive derivative group thereof (such as a halocarbonyl group), an epoxy group, and the like can be given. When the original crosslinkable group is a carboxy group, examples thereof include an isocyanate group, an amino group, and an epoxy group. In the case where the original crosslinkable group is an alkoxysilyl group, examples thereof include an isocyanate group. When the original crosslinkable group is an amino group, examples thereof include an isocyanate group, a carboxy group, and an epoxy group. When the original crosslinkable group is an epoxy group, examples thereof include a hydroxyl group, a carboxyl group, and an amino group. When the original crosslinkable group is an isocyanate group, examples thereof include a hydroxyl group, a carboxy group, an amino group, and an epoxy group.
However, in order to prevent the crosslinkable group converting compounds from being polymerized, the “functional group capable of binding to the original crosslinkable group” and the “target crosslinkable group” must be a combination that does not react with each other. It is.

The crosslinkable group converting compound may be a compound that reacts with the crosslinkable group of the copolymer to generate a crosslinkable group different from the crosslinkable group. For example, dicarboxylic acid anhydride is a compound that reacts with a hydroxyl group or the like to generate a carboxy group (target crosslinkable group).
Further, the crosslinkable group converting compound only needs to have at least two groups of a functional group capable of binding to the original crosslinkable group and the target crosslinkable group, that is, three or more including these two groups. A polyfunctional compound having a functional group of
Further, when the structural unit (A1-2) is based on a monomer obtained by functionally converting a crosslinkable group converting compound or the like, the structural unit (A1-2) is obtained by the following “method (α1)”. Or obtained by the following “method (α2)”.

The structural unit (A1-2) is excellent in alternating copolymerization with a fluoroolefin, and is improved in durability, weather resistance, scratch resistance and impact resistance of the formed fluorescent coating film. Vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, ethyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, and compound (2) converted vinyl ether are preferred.
The combination of the structural unit (A1-1) and the structural unit (A1-2) includes a structural unit based on CTFE as the structural unit (A1-1) and 2-hydroxyethyl vinyl ether as the structural unit (A1-2). A combination with a structural unit based on at least one selected from the group consisting of 4-hydroxybutyl vinyl ether, ethyl vinyl ether, 2-ethylhexyl vinyl ether and cyclohexyl vinyl ether is particularly preferred.
As the structural unit (A1-2), one type of structural unit may be used alone, or two or more types may be used in combination.

(Structural unit (A1-3))
FEVE (A1) is preferably a copolymer having a structural unit (A1-3) other than the structural unit (A1-1) and the structural unit (A1-2) as the structural unit.
The structural unit (A1-3) is a structural unit based on a monomer other than the fluoroolefin and the alkyl vinyl ether monomer (hereinafter referred to as “monomer (a3)”). The monomer (a3) can be copolymerized with a fluoroolefin and an alkyl vinyl ether monomer, and does not have a functional group that can be bonded to the crosslinkable group or the original crosslinkable group (a3-1). Is preferred. By using the monomer (a3-1), the adhesion between the object to be coated and the fluorescent coating film is improved.

Examples of the monomer (a3-1) include vinyl esters and allyl ethers.
Examples of vinyl esters include vinyl acetate, vinyl pivalate, and vinyl benzoate. Examples of allyl ethers include ethyl allyl ether, butyl allyl ether, and cyclohexyl allyl ether.
Examples of the monomer (a3) other than the monomer (a3-1) include olefins such as ethylene and isobutylene from the viewpoint of improving the solubility in a solvent.
A monomer (a3) may be used individually by 1 type, and may use 2 or more types together.

(Content of each structural unit)
The content of the structural unit (A1-1) in FEVE (A1) is preferably 38 to 65 mol% with respect to the total content of the structural unit (A1-1) and the structural unit (A1-2). 45-60 mol% is more preferable, and 50-55 mol% is still more preferable. If the said content of a structural unit (A1-1) is 5 mol% or more, the weather resistance of the fluorescent coating film formed will improve. If the content of the structural unit (A1-1) is 95 mol% or less, the compatibility with the curing agent (C) described later is good, and a dense fluorescent coating film can be formed during curing. The heat resistance, moisture resistance, scratch resistance and impact resistance of the formed fluorescent coating film are improved.
The content of the structural unit (A1-1) in the FEVE (A1) is preferably 20 to 99 mol%, and preferably 30 to 98 mol% with respect to the total of all units in the FEVE (A1), from the viewpoint of weather resistance. Is more preferable, and 40 to 95 mol% is particularly preferable.

The content of the structural unit (A1-2) in the FEVE (A1) is preferably 35 to 62 mol% with respect to the total content of the structural unit (A1-1) and the structural unit (A1-2). 40-55 mol% is more preferable, and 45-50 mol% is further more preferable. If the said content of a structural unit (A1-2) is 5 mol% or more, a crosslinking density with the hardening | curing agent (C) mentioned later becomes high, and a dense fluorescent coating film can be formed in the case of hardening. The heat resistance, moisture resistance, scratch resistance and impact resistance of the formed fluorescent coating film are improved. If the said content of a structural unit (A1-2) is 95 mol% or less, stability of FEVE (A1) will improve and the pot life of a fluorescent coating composition will improve.
From the viewpoint of improving the heat resistance, moisture resistance, scratch resistance and impact resistance of the cured fluorescent coating film by increasing the crosslinking density, the content of the structural unit (A1-2) in FEVE (A1) 1-80 mol% is preferable with respect to the sum total of all the units in FEVE (A1), 3-70 mol% is more preferable, and 5-60 mol% is especially preferable.

The content of the structural unit (A1-3) in FEVE (A1) is preferably 0 to 60 mol%, more preferably 0 to 50 mol%, based on the total of all units in FEVE (A1). The structural unit (A1-3) is an optional component, and the content of the structural unit (A1-3) being 0 mol% means that the structural unit (A1-3) is not included. When the structural unit (A1-3) is included, the lower limit of the content is more than 0 mol%, and preferably 0.5 mol%. If content of a structural unit (A1-3) is 60 mol% or less, the adhesiveness with a foundation | substrate will improve, without the weather resistance of a fluorescent coating film falling.
The content of each unit in FEVE (A1) can be controlled by the amount of each monomer charged and the reaction conditions in the polymerization reaction for obtaining FEVE (A1).

(Method for producing FEVE (A1))
Examples of the method for producing FEVE (A1) include the following methods (α1) and (α2).
Method (α1): A method of copolymerizing a fluoroolefin, an alkyl vinyl ether monomer, and a monomer (a3) used as necessary.
Method (α2): a fluoroolefin, an alkyl vinyl ether monomer having the above-mentioned “functional group capable of binding to the original crosslinkable group”, and a monomer (a3) used as needed are copolymerized. Then, the above-mentioned “crosslinkable group conversion compound” is reacted with the obtained copolymer.
Hereinafter, the method (α1) and the method (α2) will be described in detail.

Method (α1):
For the copolymerization in the method (α1), a known radical polymerization method can be adopted, and as its polymerization form, solution polymerization, suspension polymerization, emulsion polymerization and the like can be adopted.
Although the reaction temperature at the time of superposition | polymerization changes also with the radical polymerization initiator to be used, 0-130 degreeC is preferable. The reaction time is preferably 1 to 50 hours.
Examples of the solvent include ion-exchanged water; alcohol solvents such as ethanol, butanol and propanol; saturated hydrocarbon solvents such as n-hexane and n-heptane; aromatic hydrocarbon solvents such as toluene and xylene; methyl ethyl ketone Ketone solvents such as cyclohexanone; ester solvents such as ethyl acetate and butyl acetate can be used.

  Examples of the radical polymerization initiator include peroxydicarbonates such as diisopropyl peroxydicarbonate and di-n-propyl peroxydicarbonate; and peroxydicarbonates such as t-hexyl peroxypivalate and t-butyl peroxypivalate. Oxyesters; Ketone peroxides such as cyclohexanone peroxide and methyl ethyl ketone peroxide; 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, etc. Peroxyketals; peroxycarbonate esters such as t-hexylperoxy-n-butyl carbonate and t-butylperoxy-n-propyl carbonate; diacyl peroxides such as isobutyryl peroxide and lauroyl peroxide Earth; dicumyl peroxide, dialkyl peroxides such as di -t- butyl peroxide and the like can be used.

In the case of emulsion polymerization, the polymerization can be carried out in water and in the presence of an anionic or nonionic emulsifier using an initiator such as a water-soluble peroxide, a persulfate, or a water-soluble azo compound.
Since a trace amount of hydrochloric acid or hydrofluoric acid may be generated during the polymerization reaction, it is preferable to add a buffer in advance during the polymerization.

Method (α2):
The method (α2) includes the following step (α2-1) and step (α2-2).
Step (α2-1): Copolymerizing fluoroolefin, alkyl vinyl ether monomer having the above-mentioned “functional group capable of binding to the original crosslinkable group”, and monomer (a3) used as necessary Process.
Step (α2-2): a step of reacting the “crosslinkable group converting compound” with the copolymer having “functional group capable of binding to the original crosslinkable group” obtained in step (α2-1).

As the alkyl vinyl ether monomer having a “functional group capable of binding to the original crosslinkable group” in the step (α2-1), a hydroxyl group-containing vinyl ether is preferable. As the “crosslinkable group converting compound” in the step (α2-2), the above-mentioned compound (2) is preferable.
In the step (α2-2), all of the functional groups that can be bonded to the original crosslinkable group in the copolymer may be reacted, or a part thereof may be reacted. For example, if a part of the hydroxyl group of the copolymer having a hydroxyl group is reacted with the compound (2), a copolymer having both a hydroxyl group and a group based on the compound (2) can be obtained.
Hereinafter, as an example of the method (α2), a case where a hydroxyl group-containing vinyl ether and the compound (2) are used will be described.

  The copolymerization of the fluoroolefin, the hydroxyl group-containing vinyl ether and the monomer (a3) used as necessary in the step (α2-1) may be performed in the same manner as the copolymerization in the method (α1).

  In the step (α2-2), the reaction between the copolymer obtained in the step (α2-1) and the compound (2) is performed as described above in “Compound” except that the copolymer is used instead of the hydroxyl group-containing vinyl ether. (2) Conversion method ”may be performed.

  When manufacturing FEVE (A1) which has an alkoxy silyl group using a compound (2), it is preferable to manufacture by the method ((alpha) 2) from a point with easy manufacture. In the production by the method (α1) using the compound (2) converted vinyl ether, it is necessary to strictly control and manage the polymerization conditions in order to prevent gelation during the production.

  In addition, acquisition of FEVE (A1) is not limited to the manufacturing method by the method ((alpha) 1) and ((alpha) 2) mentioned above. For example, a commercially available fluororesin such as “Lumiflon (registered trademark)” manufactured by Asahi Glass Co., Ltd. may be used as it is. Alternatively, a crosslinkable group conversion compound such as Compound (2) is reacted with the Lumiflon to produce FEVE (A1 ) May be obtained.

[PVDF (A2)]
The mass average molecular weight of PVDF (A2) is preferably 50,000 to 300,000.
The PVDF used in the production of the fluorescent coating composition may be a commercially available product. For example, “DS203” manufactured by Todake Co., “427144” manufactured by Aldrich, etc. may be used.

[Phosphor (B)]
The phosphor (B) is a component that emits fluorescence, and is dispersed in the fluorescent coating composition.
The phosphor (B) includes an organic phosphor and an inorganic phosphor.
Examples of the organic phosphor include, but are not limited to, brilliant sulfoflavin FF, thioflavine, basic yellow HG, fluorescein, eosin, rhodamine 6G, and rhodamine B.
Examples of the inorganic phosphor include those obtained by adding a rare earth oxide such as heavy metal or europium to a metal oxide or sulfide such as aluminum, calcium, barium, magnesium, zinc, cadmium, or strontium. . Specifically, 3Ca ₃ (PO ₄ ) ₂ · Ca (F, Cl) ₂ : Sb ³⁺ , 3Ca ₃ (PO ₄ ) ₂ · Ca (F, Cl) ₂ : Sb ³⁺ , Mn ²⁺ , BaMg ₂ Al ₁₆ O ₂₇ : Eu ²⁺ , (Sr, Ca) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu ²⁺ , Sr ₄ Al ₁₄ O ₂₅ : Eu ²⁺ , BaMg ₂ Al ₁₆ O ₂₇ : Eu ²⁺ Mn ²⁺ , CaWO ₄ , CaWO _{4 ^{: Pb 2+, Sr 2 P 2}} O 7: Sn 2+, Y 2 O 3: Eu 3+, 3.5MgO · 0.5MgF 2 GeO 2: Mn 4+, Y (PV) O 4: Eu 3+, (Sr, Mg ) ₃ (PO ₄ ) ₂ : Sn ²⁺ , 6MgO · As ₂ O ₅ : Mn ⁴⁺ , (Ca, Sr) SiO ₃ : Pb ²⁺ , Mn ²⁺ , CeMaAl ₁₁ O ₁₉ : Tb ³⁺ , L ^{_{aPO 4: Ce 3+, Tb 3+}} , Zn 2 SiO 4: Mn 2+, Sr 2 P 2 O 7: Eu 2+, (Ba, Sr, Mg) 3 Si 2 O 7: Pb 2+, BaSi 2 O 5: Pb 2+ However, it is not limited to these.
A fluorescent substance (B) may be used individually by 1 type, and may use 2 or more types together.
The type of phosphor (B) is appropriately determined according to the environment in which the article is used, the material of the object to be coated, and the like. For example, when the article is used outdoors, an inorganic phosphor having a high fastness to sunlight is preferable.

  As for content of a fluorescent substance (B), 5-200 mass parts is preferable with respect to 100 mass parts of fluororesin (A), More preferably, it is 30-100 mass parts. If it is more than the said lower limit, fluorescence will become favorable, on the other hand, if it is below the said upper limit, the adhesiveness to a to-be-coated object, a softness | flexibility, and impact resistance will improve.

[Other ingredients]
In addition to the fluorine-containing resin (A) and the phosphor (B), the fluorescent coating composition of the present invention includes a curing agent (C), a curing catalyst (D), another resin (E), a pigment (F), an arbitrary Other components, such as a component (G) and a solvent (H), may be included.

(Curing agent (C))
The fluorescent paint composition of the present invention may contain a curing agent (C).
A hardening | curing agent (C) plays the role which hardens the fluorescent coating film which apply | coated the fluorescent coating composition by reacting with the crosslinkable group which fluororesin (A) has, and forming a crosslinked structure.
Examples of the curing agent include an isocyanate curing agent (C-1), a blocked isocyanate curing agent (C-2), an amino resin (C-3), and a metal alkoxide.

As the curing agent (C), a compound having two or more functional groups having reactivity with the crosslinkable group is appropriately selected according to the type of the crosslinkable group of the fluororesin (A).
For example, when the fluorine-containing resin (A) has a hydroxyl group, the curing agent (C) includes an isocyanate curing agent (C-1), a blocked isocyanate curing agent (C-2), and an amino resin (C-3). Etc.) are preferred.
Moreover, when a fluorine-containing resin (A) has a carboxy group, as a hardening | curing agent (C), an amine-type hardener, an epoxy-type hardener, etc. are preferable.
Moreover, when a fluororesin (A) has an amino group, as a hardening | curing agent (C), a carboxy-group containing hardening | curing agent, an epoxy-type hardening | curing agent, an acid anhydride type hardening | curing agent, etc. are preferable.
Moreover, when a fluororesin (A) has an epoxy group, as a hardening | curing agent (C), a carboxy-group containing hardening | curing agent, an acid anhydride type hardening | curing agent, an amine-type hardening | curing agent, etc. are preferable.
Moreover, when a fluorine-containing resin (A) has an alkoxy silyl group, as a hardening | curing agent (C), a metal alkoxide etc. are preferable.
When the fluororesin (A) has an isocyanate group, the curing agent (C) is preferably a hydroxyl group-containing curing agent, a carboxy group-containing curing agent, or the like.

Isocyanate-based curing agent (C-1):
Examples of the isocyanate curing agent (C-1) include non-yellowing polyisocyanate and non-yellowing polyisocyanate modified.
Examples of the non-yellowing polyisocyanate include alicyclic polyisocyanates such as isophorone diisocyanate (IPDI) and dicyclohexylmethane diisocyanate (HMDI); and aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI).

Examples of the non-yellowing polyisocyanate-modified product include the following modified products (c1) to (c4).
(C1) Isocyanurate of aliphatic diisocyanate or alicyclic diisocyanate.
(C2) A modified product having a structure represented by -YC (= O) NH-, wherein aliphatic diisocyanate or alicyclic diisocyanate is modified with a polyol or polyamine.
(C3) A modified product having a structure represented by -YC (= O) NH-, in which a part of the isocyanate group of an aliphatic diisocyanate or an alicyclic diisocyanate is modified with a polyol.
(C4) A modified product comprising a mixture of the modified product (c1) and the modified product (c2).
However, Y in -YC (= O) NH- is an organic group derived from a polyol or polyamine. The number of functional groups contained in the compound having a hydroxyl group or the compound having an amino group is preferably 2 to 3.

Blocked isocyanate curing agent (C-2):
The blocked isocyanate curing agent (C-2) is a blocked isocyanate curing agent in which the isocyanate group of the isocyanate curing agent (C-2) is blocked.
The isocyanate group can be blocked with epsilon caprolactam (E-CAP), methyl ethyl ketone oxime (MEK-OY), methyl isobutyl ketone oxime (MIBK-OY), pyraridine, triazine (TA) or the like.

Amino resin (C-3):
Examples of the amino resin (C-3) include melamine resin, guanamine resin, sulfoamide resin, urea resin, aniline resin, and the like. Among these, a melamine resin is preferable because it has a high curing rate.
Specific examples of the melamine resin include alkyl etherified melamine resins that are alkyl etherified. Among these, a melamine resin substituted with a methoxy group or a butoxy group is preferable.

Metal alkoxide:
Examples of the metal or metalloid of the metal alkoxide include Al, Ti, Si and the like. Among these, Si is preferable because a harder fluorescent coating film can be formed and durability such as heat resistance, moisture resistance, and water resistance, weather resistance, scratch resistance, and impact resistance are improved.
The alkoxy group of the metal alkoxide is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably a methoxy group or an ethoxy group, and particularly preferably a methoxy group.

As the metal alkoxide, a compound represented by the following formula (3) (hereinafter referred to as “compound (3)”) is preferable.
(R ³ ) _4-k Si (OR ⁴ ) _k (3)
(In the formula (3), R ³ and R ⁴ each independently represent a monovalent hydrocarbon group having 1 to 10 carbon atoms, and k represents an integer of 2 to 4.)

The monovalent hydrocarbon group for R ³ may have a substituent. That is, part or all of the hydrogen atoms of the monovalent hydrocarbon group of R ³ may be substituted with a substituent. The substituent is preferably a halogen atom, more preferably a fluorine atom.
R ³ is preferably a methyl group, an ethyl group, a hexyl group, a decyl group, a phenyl group, or a trifluoropropyl group. When two or more R < ³ > exists in a compound (3), it is preferable that several R < ³ > is mutually the same from the point of the supply property of a raw material. However, several R < ³ > may mutually differ.
The monovalent hydrocarbon group for R ⁴ is an alkyl group having 1 to 10 carbon atoms, preferably a methyl group or an ethyl group, and particularly preferably a methyl group. When two or more R < ⁴ > exists in a compound (3), it is preferable that several R < ⁴ > is mutually the same from the point that the reactivity of an alkoxy group becomes the same and it is easy to form a fluorescent coating film uniformly. However, several R < ⁴ > may mutually differ.
K in a compound (3) is an integer of 2-4, and 3-4 are preferable.

Specific examples of the compound (3) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane; methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, Trifunctional alkoxysilanes such as hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, and trifluoropropyltrimethoxysilane; bifunctional such as dimethyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, and diphenyldiethoxysilane And functional alkoxysilanes. Of these, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and phenyltrimethoxysilane are preferable from the viewpoint of curing speed and physical properties of the resulting fluorescent coating film.
A compound (3) may be used individually by 1 type, and may use 2 or more types together.

Compound (3) may be used as a partially hydrolyzed condensate obtained by partial hydrolysis and condensation. The partial hydrolysis-condensation product is a compound obtained by condensing the compound (3) by partial hydrolysis so that two or more hydrolyzable groups (—OR ⁴ groups) remain in the molecule. It is. Although the overall structure of the partially hydrolyzed condensate is not clear, it is a polysilicate ester composed of a skeleton composed of —Si—O— bonds and an alkoxy group, and the skeleton may be linear or branched. It may be a chain or a cyclic structure.
The partial hydrolysis-condensation product of compound (3) is more preferable as the condensation degree is lower. The lower the degree of condensation of the partially hydrolyzed condensate, the better the compatibility with the fluororesin (A). Moreover, the thermal expansion coefficient of the fluorescent coating film to be formed and the object to be coated on which the fluorescent coating film is formed are closer, and the peeling of the fluorescent coating film from the coating object due to expansion and contraction due to heat is less likely to occur. Become.

  The method for producing the partially hydrolyzed condensate of compound (3) is not particularly limited, and known methods for producing partially hydrolyzed condensates can be employed. For example, the method of adding at least 1 sort (s) of water, an acid, and a solvent to a compound (3), and making it partially hydrolytically condensate is mentioned.

As the partially hydrolyzed condensate of compound (3), those having different degrees of condensation, structure and alkoxy group are commercially available. For example, trade names “KR-500”, “KR-510”, “KR— “213” (manufactured by Shin-Etsu Chemical Co., Ltd.), trade names “MKC silicate MS51”, “MKC silicate MS56” (manufactured by Mitsubishi Chemical Corporation), trade names “M silicate 51”, “ethyl silicate 40”, “ethyl” Condensate having an effective silica content of about 28 to 70% by mass such as silicate 45 "(manufactured by Tama Chemical Industry Co., Ltd.), or trade names" HAS-1 "," condensate dissolved in ethanol or isopropanol " HAS-6 "," HAS-10 "(manufactured by Colcoat Co., Ltd.) and the like. The “effective silica content” is a value indicating the content of silica in terms of SiO ₂ when the polyalkyl silicate contained in the product is 100% by mass.
The partial hydrolysis-condensation product of compound (3) may be used individually by 1 type, and may use 2 or more types together.

Examples of the aluminum alkoxide include aluminum isopropoxide (Al [OCH (CH ₃ ) ₂ ] ₃ ) and the like.
Examples of the titanium alkoxide include titanium butoxide (Ti (OC ₄ H ₉ ) ₄ ).
Moreover, you may use the partial hydrolysis-condensation product which partially hydrolyzed and condensed the said aluminum alkoxide and titanium alkoxide so that two or more hydrolysable groups might remain in a molecule | numerator. These partial hydrolysis-condensation products are more preferable as the degree of condensation is lower from the viewpoint that the compatibility with the fluororesin (A) is improved and the peeling of the fluorescent coating film from the object to be coated hardly occurs.

  The fluorescent coating composition of the present invention may be a composition that does not contain a curing agent (C), and may be a two-component fluorescent coating composition in which a curing agent (C) is added immediately before forming a fluorescent coating film. A one-component fluorescent coating composition containing both the resin (A) and the curing agent (C) may be used. Furthermore, when the fluororesin (A) has an alkoxysilyl group, the alkoxysilyl groups cause a condensation reaction, and therefore it is preferable not to contain the curing agent (C).

The content of the fluorine-containing resin (A) when using the fluorescent paint composition of the present invention is 10 to 90% by mass with respect to the total content of the fluorine-containing resin (A) and the curing agent (C). Preferably, 20-80 mass% is more preferable, and 30-70 mass% is further more preferable.
If the said content of a fluororesin (A) is 10 mass% or more, the weather resistance of a fluorescent coating film will improve. If the content of the fluorine-containing resin (A) is 90% by mass or less, it is easy to suppress the occurrence of cracks in the fluorescent coating, and the adhesion between the fluorescent coating and the layer forming the fluorescent coating is excellent. improves. Moreover, it becomes easy to form a fluorescent coating film excellent in durability, scratch resistance and impact resistance.

  The combination of the fluororesin (A) and the curing agent (C) in the fluorescent coating composition of the present invention has higher hardness, durability such as heat resistance and water resistance, weather resistance, scratch resistance and impact resistance. From the point that it is easy to form a fluorescent coating excellent in properties, (i) a fluorine-containing resin having a hydroxyl group as the fluorine-containing resin (A), an isocyanate-based curing agent (C-1) as a curing agent (C), Fluorescent paint composition using at least one curing agent selected from blocked isocyanate curing agent (C-2) and amino resin (C-3), (ii) alkoxysilyl group as fluororesin (A) And a fluorescent coating composition using a fluorine-containing resin having at least one of hydroxyl group and metal alkoxide as the curing agent (C).

(Curing catalyst (D))
The fluorescent paint composition of the present invention may contain a curing catalyst (D) for the purpose of accelerating the curing reaction and imparting good chemical performance and physical performance to the fluorescent coating film that is a cured product. In particular, when curing at a low temperature in a short time, it is preferable to include a curing catalyst (D).
Examples of the curing catalyst (D) include the following curing catalysts (D-1), (D-2), and (D-3).
Curing catalyst (D-1): A curing catalyst used for a crosslinking reaction between a fluorine-containing resin containing a hydroxyl group and an isocyanate curing agent or a blocked isocyanate curing agent.
Curing catalyst (D-2): A curing catalyst used for a crosslinking reaction between a fluororesin containing at least one of an alkoxysilyl group and a hydroxyl group and a metal alkoxide.
Curing catalyst (D-3): A curing catalyst used for a crosslinking reaction between a fluorine-containing resin containing a hydroxyl group and an amino resin.

As the curing catalyst (D-1), tin catalysts such as tin octylate, tributyltin dilaurate, and dibutyltin dilaurate are preferable.
As the curing catalyst (D-2), acidic phosphoric acid esters such as phosphoric acid monoester and phosphoric acid diester; acidic boric acid esters such as boric acid monoester and boric acid diester; acidic phosphoric acid ester and amine Amine adducts such as addition reaction products, addition reaction products of carboxylic acid compounds and amines; metal esters such as tin octylate and dibutyltin dilaurate; tris (acetylacetonate) aluminum, tetrakis (acetylacetonate) zirconium, etc. And metal alkoxides such as aluminum isopropoxide and titanium butoxide. Among these, from the viewpoint of curability and the smoothness of the fluorescent coating film to be formed, acidic phosphates are preferable. More preferred are 8 monoalkyl phosphates, 1 to 8 carbon dialkyl phosphates, or mixtures thereof.
As the curing catalyst (D-3), a blocked acid catalyst is preferable. Examples of the blocked acid catalyst include various amine salts such as carboxylic acid, sulfonic acid, and phosphoric acid. Particularly preferred are higher alkyl-substituted sulfonic acid amine salts such as p-toluenesulfonic acid and diethanolamine salt of dodecylbenzenesulfonic acid and triethylamine salt.
A curing catalyst (D) may be used individually by 1 type, and may use 2 or more types together.

  The content of the curing catalyst (D) is preferably 0.00001 to 10% by mass with respect to the total solid content of the fluorescent coating composition (including the curing agent (C)) at the time of use. If the content of the curing catalyst (D) is 0.00001% by mass or more, the catalytic effect can be sufficiently obtained. If content of a curing catalyst (D) is 10 mass% or less, the remaining curing catalyst (D) will not affect a fluorescent coating film, and heat resistance and water resistance will improve.

(Other resin (E))
The fluorescent paint composition of the present invention may contain a resin (E) other than the fluorine-containing resin (A).
Other resins (E) include non-fluorine resins such as acrylic resins, polyester resins, acrylic polyol resins, polyester polyol resins, urethane resins, acrylic silicone resins, silicone resins, alkyd resins, epoxy resins, oxetane resins, amino resins, etc. And fluorine resins other than the fluorine-containing resin (A). The other resin (E) may be a resin that has a crosslinkable group and is cured by being crosslinked by the curing agent (C).

In particular, when the fluorescent coating composition contains PVDF (A2), it is preferable to include an acrylic resin in the fluorescent coating composition.
If an acrylic resin is included together with PVDF (A2), the fluorescent coating composition has good adhesion to the object to be coated, flexibility, and impact resistance of the fluorescent coating film. Further, the fluorescent coating composition becomes a solvent-soluble type and is easy to handle. Further, the dispersibility of the phosphor (B) and the pigment (F) is improved.
The acrylic resin is a polymer having a unit derived from (meth) acrylate, and may have a reactive group such as a carboxy group, a hydroxyl group, or a sulfo group.
The glass transition temperature of the acrylic resin is preferably 30 to 60 ° C. If the glass transition temperature is equal to or higher than the lower limit, blocking is difficult. When the glass transition temperature is not more than the above upper limit, the surface smoothness of the fluorescent coating film is excellent.

The number average molecular weight of the acrylic resin is preferably from 5,000 to 100,000, particularly preferably from 30,000 to 100,000. If the number average molecular weight of the acrylic resin is not less than the lower limit, blocking is difficult. If the number average molecular weight of an acrylic resin is below the said upper limit, it will be excellent in the surface smoothness of a fluorescent coating film.
The mass average molecular weight of the acrylic resin is preferably 6,000 to 150,000, more preferably 40,000 to 150,000, and particularly preferably 60,000 to 150,000. If the mass average molecular weight of the acrylic resin is not less than the lower limit, blocking is difficult. If the mass average molecular weight of an acrylic resin is below the said upper limit, it will be excellent in the surface smoothness of a fluorescent coating film.

  When the acrylic resin has a carboxy group, the acid value of the acrylic resin is preferably 150 to 400 mgKOH / g. If the acid value of an acrylic resin is more than the said lower limit, it has the dispersibility improvement effect of a fluorescent substance (B) and a pigment (F). If the acid value of an acrylic resin is below the said upper limit, a fluorescent coating film is excellent in moisture resistance.

When mix | blending other resin (E) with the fluorescent paint composition of this invention, as for content of other resin (E), 1-200 mass parts is preferable with respect to 100 mass parts of fluororesin (A).
Moreover, when a fluorescent coating composition contains an acrylic resin with PVDF (A2), it is preferable that content of an acrylic resin is 20-60 mass parts with respect to 100 mass parts of PVDF. More preferably, it is 30-50 mass parts. If content of an acrylic resin is more than the said lower limit, the dispersibility of a fluorescent substance (B) and a pigment (F) will become favorable. If it is below the said upper limit, a phosphor coating film is excellent in a weather resistance.

  The acrylic resin used in the production of the fluorescent coating composition may be a commercially available product. For example, “Fine Dick (registered trademark) A-249” and “Fine Dick (registered trademark) A-251 manufactured by DIC Corporation” may be used. "Fine Dick (registered trademark) A-266", "Almatex (registered trademark) PD6200" manufactured by Mitsui Chemicals, "Almatex (registered trademark) PD7310", "Sanpex PA-" manufactured by Sanyo Chemical Industries, Ltd. 55 "etc. can be used.

(Pigment (F))
The fluorescent paint composition of the present invention may contain a pigment (F) other than the phosphor (B) for the purpose of rust prevention, coloring, reinforcement and the like of the fluorescent coating film.
The pigment (F) is preferably at least one pigment selected from the group consisting of rust preventive pigments other than the phosphor (B), colored pigments and extender pigments.
The rust preventive pigment is a pigment for preventing corrosion and alteration of the reflective metal layer. Lead-free rust-proof pigments with low environmental impact are preferred. Examples of lead-free rust preventive pigments include cyanamide zinc, zinc oxide, zinc phosphate, calcium magnesium phosphate, zinc molybdate, barium borate, and calcium cyanamide zinc.
The coloring pigment is a pigment for coloring the fluorescent coating film. Examples of the color pigment include titanium oxide, carbon black, and iron oxide.
The extender pigment is a pigment for improving the hardness of the fluorescent coating film and increasing the thickness of the fluorescent coating film. Examples of extender pigments include talc, barium sulfate, mica, and calcium carbonate.

  The content of the pigment (F) in the fluorescent coating composition of the present invention is preferably 50 to 500% by mass with respect to the total solid content of the fluorescent coating composition (including the curing agent (C)) at the time of use. 100 to 400% by mass is more preferable. When the content of the pigment (F) is 50% by mass or more, the function of the pigment (F) is easily obtained. If content of a pigment (F) is 500 mass% or less, it will become difficult for a fluorescent coating film to be cracked or damaged by impacts, such as sand, and the weather resistance of a fluorescent coating film will improve.

(Optional component (G))
In the fluorescent paint composition of the present invention, the fluororesin (A), phosphor (B), curing agent (C), curing catalyst (D), other resin (E) and pigment (F) are optional. Component (G) may be included.
As an optional component (G), a silane coupling agent for improving adhesion of a fluorescent coating film; a light stabilizer such as a hindered amine light stabilizer; a benzophenone compound, a benzotriazole compound, a triazine compound, a cyanoacrylate compound Organic ultraviolet absorbers such as compounds; inorganic ultraviolet absorbers such as titanium oxide, zinc oxide, and cerium oxide; matting agents such as ultrafine powder synthetic silica; nonionic, cationic, or anionic surfactants; A leveling agent etc. are mentioned.
Content of arbitrary component (G) can be suitably selected in the range which does not impair the effect of this invention.

(Solvent (H))
When the form of the fluorescent coating composition is a solution system such as a solvent system or an emulsion system, the fluorescent coating composition can use a solvent (H) as a solvent. In use, a fluorescent coating composition containing a solvent (H) is applied, and then the solvent (H) is removed to form a fluorescent coating film.
As the solvent (H), conventionally used solvents such as toluene, xylene, methyl ethyl ketone, butyl acetate and the like can be used, but weak solvents are preferable from the viewpoint of reducing environmental burden.
The weak solvent is preferably a weak solvent species that can be used in the polymerization of the fluorine-containing resin (A) or solvent substitution, and more preferably mineral spirits and mineral terpenes.
The content of the solvent (H) in the fluorescent paint composition containing the solvent (H) is appropriately determined in consideration of the solubility of the fluororesin (A), the appropriate viscosity when applied as a paint, the coating method, and the like. Is done.

[Method for producing fluorescent coating composition]
As a method for producing the fluorescent paint composition, a method known to those skilled in the art can be employed.
For example, when the form of the fluorescent coating composition is a solvent system or a solution system such as an emulsion system, a method of mixing and dispersing necessary components in a stirrer such as a disper is preferable. In the case of a powder system, the raw material in a powder state in which the respective components are mixed in advance is kneaded with a heated extruder, and the extruded kneaded product is cooled, pulverized and classified to obtain a powder having a desired particle size. It is preferable to obtain a powder coating material comprising a body and further to form a powder-based fluorescent coating composition containing the powder coating material and an additive.
When the coating composition contains a curing agent, the timing of addition can be changed depending on the coating form. For example, in the case of a one-component type paint such as a paint for baking, it is preferable to add a curing agent immediately after the production of the copolymer. In the case of a two-component coating composition in which the curing agent and other components are separated, it is preferable to mix the curing agent and other components immediately before application.

<Article>
The article of the present invention includes an object to be coated and a fluorescent coating film formed on the object to be coated by the above-described fluorescent coating composition. The fluorescent coating film is formed in order to improve visibility and design.

[To be painted]
The object to be painted is not particularly limited. For example, road-related products such as bridge protection fences, road fences, instruction posts, building-related products such as building interiors and exteriors, building members, lighting fixtures, watches, etc. The thing normally used as to-be-coated objects, such as products, is mentioned.
The material of the object to be coated is not particularly limited, and examples thereof include a metal plate, a wooden plate, a plastic plate, a glass plate, asphalt, and concrete. When another fluorescent coating film is already formed on the object to be coated, the fluorescent coating film of the fluorescent coating composition of the present invention may be formed on the fluorescent coating film.

[Thickness of fluorescent coating]
The thickness of the fluorescent coating film formed from the fluorescent coating composition is preferably 5 to 50 μm. If the thickness of the fluorescent coating is equal to or greater than the lower limit, a fluorescent coating with high visibility and design is obtained. On the other hand, if the thickness is equal to or less than the upper limit, there is a difference in the degree of curing between the surface layer of the coating and the inside. And a uniform coating film is obtained.

[Product Manufacturing Method]
Formation of the fluorescent coating film by the fluorescent coating composition of this invention is performed by the formation method of the fluorescent coating film of a normal fluorescent coating. Specifically, the form of the fluorescent paint composition differs depending on whether it is a solvent system or a solution system such as an emulsion system, or a powder system.
For example, when the form of the fluorescent coating composition is a solution system such as a solvent system or an emulsion system, it is necessary to use a coating device such as a brush, a roller, a dipping, a spray, a roll coater, a die coater, an applicator, or a spin coater. It is preferable to employ a method in which a fluorescent coating film is obtained by coating to a thickness of ˜several μm, and then drying at a temperature of about room temperature to about 300 ° C. for a predetermined time.
When the form of the fluorescent paint composition is powder, it is in a powder state (preheated fluid immersion) by electrostatic coating machine, triboelectric charging machine, fluidized immersion, cloud coating machine, electric magnetic brush (painting method similar to dry copy) In the case of coating, it is preferable to employ a method of obtaining a fluorescent coating film by coating in a molten state) and baking at 120 to 300 ° C. for a certain time.

<Operational effects of the present invention>
Since the fluorescent coating composition of the present invention contains FEVE having high alternating copolymerization as a fluorine-containing resin, the fluorescent coating film formed from the fluorescent coating composition is excellent in weather resistance. Moreover, the weather resistance of a fluorescent coating film improves, so that the alternating copolymerization property of FEVE is high.
Moreover, when the fluorescent coating composition containing PVDF is used as the fluorine-containing resin, the weather resistance of the fluorescent coating film is excellent as in the case of containing FEVE.
Moreover, the fluorescent coating composition containing FEVE as the fluorine-containing resin has higher weather resistance of the fluorescent coating film than the fluorescent coating composition containing PVDF.
As described above, since the fluorescent coating film formed from the fluorescent coating composition of the present invention has excellent weather resistance, the landscape and aesthetics of the fluorescent coating can be maintained for a long period of time, and the frequency of repainting is reduced. be able to.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
Example 1
"Manufacture of fluororesin (A)"
In a pressure resistant reactor with a stainless steel stirrer with an internal volume of 2500 mL, 590 g of xylene, 170 g of ethanol, 206 g of ethyl vinyl ether (EVE) as an alkyl vinyl ether monomer (a1-2-7) having no crosslinkable group, hydroxyl group 129 g of 4-hydroxybutyl vinyl ether (HBVE) and 208 g of cyclohexyl vinyl ether (CHVE) (a1-2-1), 11 g of calcium carbonate, and t-butyl peroxypivalate (as a containing alkyl vinyl ether (a1-2-1) 3.5 g of (PBPV) was charged, and dissolved oxygen in the liquid was removed by deaeration with nitrogen.
Next, CTFE (660 g as CTFE amount) containing CF ₂ ═CHCl (0.0012 mol% with respect to the total amount of monomers) was introduced, the temperature was gradually raised, and the reaction was carried out while maintaining the temperature at 65 ° C. Subsequently, a copolymer (A1) was obtained.
After 10 hours, the reaction was stopped by cooling the reactor with water. After cooling the reaction solution to room temperature, the unreacted monomer is purged, the resulting reaction solution is filtered through diatomaceous earth to remove solids, the concentration is adjusted, and the copolymer (A1) has a solid content concentration of 60. A fluorine-containing resin (A) solution contained in mass% (hereinafter referred to as “FEVE (A1) -containing fluorine-containing resin (A) solution”) was obtained.
As a result of measuring the amount of unreacted monomer remaining in the reactor, the copolymer (A1) contains polymerized units based on CF ₂ = CHCl, and CF _{2 with} respect to all units in the copolymer (A1). = Polymerized units based on CHCl were 0.0012 mol% or less. Moreover, the obtained copolymer (A1) was an alternating copolymer.

"Manufacture of fluorescent paint composition"
A fluororesin solution in which a curing agent (Coronate HX manufactured by Nippon Polyurethane Co., Ltd.) was blended to 11 parts by mass with respect to 100 parts by mass of the FEVE (A1) -containing fluororesin (A) solution was obtained. For 100 parts by mass of the fluororesin solution containing this curing agent, an inorganic phosphor (NP-108-03 composition formula 0.8BaO; 1.0MgO; 8.0Al ₂ O ₃ manufactured by Nichia Corporation); 50 parts by mass of 0.1EuO; 0.5MnO) was added and stirred using a stirrer to obtain a fluorescent coating composition.

(Example 2)
18 g of isophorone, 18 g of 2-ethoxyethyl acetate, 26 g of 2-methoxyethyl acetate, and 2 g of dimethyl phthalate were added to a stainless steel stirrer with an internal volume of 2000 mL, and PVDF (manufactured by Todake Co., Ltd., PVDF DS203, mass average molecular weight: 270,000, number average molecular weight: 160,000, melting point: 170 ° C.) and 12 g of Rohm & Haas Japan polymethyl methacrylate copolymer paraloid B-44 are added and mixed to contain PVDF (A2) A fluororesin (A) solution was obtained.
For 100 parts by mass of the fluororesin (A) solution containing the PVDF (A2), an inorganic phosphor (NP-108-03 composition formula 0.8BaO; 1.0MgO; 8.0Al manufactured by Nichia Corporation) 50 parts by mass of ₂ O ₃ ; 0.1EuO; 0.5MnO) was added and stirred using a stirrer to obtain a fluorescent coating composition.

(Comparative Example 1)
A fluororesin solution in which a curing agent (Coronate 2515 manufactured by Toa Gosei Co., Ltd.) was blended to 5 parts by mass with respect to 100 parts by mass of CTFE fluororesin (Zaflon FC110 manufactured by Toa Gosei Co., Ltd.) was obtained.
A fluorescent coating composition was obtained in the same manner as in Example 1 except that the fluororesin solution was used.
As a result of analyzing the composition of ZAFLON FC110 using a nuclear magnetic resonance apparatus (manufactured by JEOL Ltd.), ZAFLON FC110 was a CTFE and vinyl ester resin.

(Accelerated weather resistance evaluation)
For the fluorescent paint compositions of Examples 1 and 2 and Comparative Example 1, accelerated weather resistance evaluation is performed according to the following procedure.
Using a film applicator, the fluorescent coating composition was applied to an aluminum plate (thickness 1 mm, surface chromated) so that the thickness of the fluorescent coating film after drying was 40 μm, and the temperature was 23 ° C. and the humidity 50 % For 2 weeks to obtain a test piece.
Using an accelerated weathering tester (Q-PANEL LAB PRODUCTS, model: QUV / SE), the test plate was exposed for 5000 hours. Measure fluorescence retention before and after exposure.
The fluorescence retention rate (%) is a value representing the fluorescence brightness after exposure with respect to the fluorescence brightness before exposure as a percentage.

As a result of the above evaluation test, the fluorescent coating film of Example 1 using CTFE and a vinyl ether copolymer (A1) as the fluororesin (A) is Comparative Example 1 using CTFE and a vinyl ester resin. It was shown that the weather resistance is higher than
In addition, the fluorescent coating film of Example 2 using PVDF (A2) as the fluorine-containing resin (A) was not as high as Example 1, but it was shown that the weather resistance was higher than that of Comparative Example 1.

  The fluorescent paint composition of the present invention is used for road-related products such as protective fences for roads, road fences and instruction columns, building-related products such as building interiors and exteriors, building members, lighting appliances, watches, etc. Can be used for fluorescent coating.

Claims (2)

  One or both of a copolymer (A1) having a structural unit (A1-1) based on a fluoroolefin and a structural unit (A1-2) based on an alkyl vinyl ether monomer, and polyvinylidene fluoride (A2) A fluorescent paint composition comprising a fluororesin (A) and a phosphor (B).   An article comprising: an object to be coated; and a fluorescent coating film formed on the object to be coated with the fluorescent paint composition according to claim 1.