JP2008169352A - Coating agent - Google Patents

Abstract

Disclosed is a coating agent that has excellent heat resistance and does not select the color of a substrate.
The coating agent of the present invention comprises a fluoropolymer having a perfluoroalkyl group, at least one fluorescent agent having a specific structure, and a solvent.
[Selection figure] None

Description

  The present invention relates to a coating agent.

  Fluoropolymer has water repellency and oil repellency, so it can be used in various applications (for oil barrier, prevention of creeping of resin and oil, insulation protection and moisture proof coating, low friction / sliding and mold release) It is used as a coating agent.

  In general, a fluorine-based polymer has high transparency and has a thin coating thickness when used as a coating agent. Therefore, it is difficult to confirm whether or not a desired coat film is formed at a predetermined site. In order to solve this problem, a technique of incorporating an anthraquinone-based colorant or a coumarin-based fluorescent agent in a coating agent has been proposed (see Patent Document 1).

  However, when the coating agent is colored with a colorant, the coating film is not necessarily sufficiently colored, and when the film thickness is reduced or the object to be coated is small, a desired coating film is formed at a predetermined site. It was difficult to confirm whether it was done or not.

  Further, when a coumarin-based fluorescent agent that emits light when irradiated with ultraviolet rays is used for coloring the coating agent, the coating film emits light when irradiated with ultraviolet rays immediately after coating at room temperature, and the presence or absence thereof can be easily confirmed. However, when the coating film is cured and dried, if heated to 100 ° C. or higher, the fluorescent agent undergoes a sublimation reaction and vaporizes and decomposes. There was an inconvenience that they could not.

In order to solve this problem, a coating agent containing a fluoropolymer having a perfluoroalkyl group and a fluorescent agent that develops blue color by ultraviolet irradiation has been proposed (see Patent Document 2).
JP 2001-27242 A JP 2006-160933 A

  In the coating agent described in Patent Document 2, since the sublimation reaction does not occur even when the coating film is cured and dried at 100 ° C. or higher, the coating film emits light reliably. However, if the content of the fluoropolymer in the coating agent is small, the coating film may not emit light after heating at 150 ° C. for 1 hour, and it may not be possible to confirm the presence or absence (decrease in visibility). Sex was not enough.

  In addition, when this coating agent is used as a base material that reflects excitation light (black light: blue light source) like polished SUS, the entire coating glows blue, making it difficult to confirm the coating film. .

  This invention is completed based on the above situations, Comprising: It aims at providing the coating agent which is excellent in heat resistance and does not choose the color of a base material.

  As a result of intensive studies to achieve the above object, the present inventors have excellent heat resistance and the color of the base material when the fluorescent agent represented by the general formula (1) or (2) is used. It has been found that a coating agent that does not select any of the above can be obtained. The present invention has been made based on this finding.

  That is, the coating agent of the present invention comprises a fluoropolymer having a perfluoroalkyl group, at least one of a fluorescent agent represented by the general formula (1) and a fluorescent agent represented by the general formula (2), and a solvent. And a coating agent obtained by mixing these.

[Wherein, R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an arylalkyl having 7 to 30 carbon atoms which may have a substituent. Group, an optionally substituted aryl group having 6 to 20 carbon atoms, and an optionally substituted heteroaryl group having 5 to 20 carbon atoms, which are bonded to each other to form a ring structure It may be formed or may form a ring structure together with a benzene ring to which a nitrogen atom is bonded.

R ³ is an alkyl group having 1 to 20 carbon atoms which may have a substituent, which contains 2 to 41 fluorine atoms in at least one of the substituent or the alkyl group, and has a substituent. An arylalkyl group having 7 to 30 carbon atoms, which contains 2 to 49 fluorine atoms in at least one of the substituent or the arylalkyl group, or an aryl group having 6 to 30 carbon atoms having a substituent and 2 The thing containing -49 fluorine, the C5-C20 heteroaryl group which has a substituent, and the thing containing 2-31 fluorine are shown.

X is an oxygen atom, a sulfur atom, —NH— or —NR ⁴ — (R ⁴ is an optionally substituted alkyl group having 1 to 10 carbon atoms, and optionally substituted carbon. An aryl group having 6 to 20 carbon atoms, and a heteroaryl group having 5 to 20 carbon atoms which may have a substituent.

Y is an oxygen atom, a sulfur atom, —NH— or —NR ⁶ — (R ⁶ is an optionally substituted alkyl group having 1 to 10 carbon atoms, and optionally substituted carbon. An aryl group having 6 to 20 carbon atoms, and a heteroaryl group having 5 to 20 carbon atoms which may have a substituent. ]

  According to the present invention, it is possible to provide a coating agent that is excellent in heat resistance and does not choose the color of the substrate because it contains at least one of the fluorescent agents represented by the general formulas (1) and (2).

  The coating agent of the present invention comprises a fluoropolymer having a perfluoroalkyl group, at least one of a fluorescent agent represented by the general formula (1) and a fluorescent agent represented by the general formula (2), a solvent, Is a coating agent obtained by mixing.

The fluoropolymer having a perfluoroalkyl group contained in the coating agent of the present invention will be described.
Although it will not specifically limit as a fluorine-type polymer which has a perfluoroalkyl group, if it has a perfluoroalkyl group, For example, the polymer shown by the following formula | equation (4)-(17) is mentioned.

  Polyperfluoroalkyl acrylate, polyperfluoroalkyl methacrylate, poly 2- (perfluoroalkyl) ethyl acrylate, poly 2- (perfluoroalkyl) ethyl methacrylate, etc. mainly containing a repeating unit represented by the following formula (4) polymer.

(In the formula (4), n in (CH ₂ ) n represents an integer of 0 to 6. R ⁷ represents hydrogen or a methyl group. R _f represents a perfluoroalkyl group (C _n F _{2n + 1).} And _n in C _n F _{2n + 1} represents an integer of 0 to 6.)

  An ethylene-tetrafluoroethylene copolymer (ETFE) mainly containing a repeating unit represented by the following formula (5).

  Polyvinyl fluoride (PVF) mainly containing a repeating unit represented by the following formula (6).

  Polyvinylidene fluoride (PVD) mainly containing a repeating unit represented by the following formula (7).

  An ethylene-chlorotrifluoroethylene copolymer (ECTFE) mainly containing repeating units represented by the following formula (8A) and the following formula (8B).

  Polychlorotrifluoroethylene (PCTFE) mainly containing a repeating unit represented by the following formula (9).

  Tetrafluoroethylene-perfluoroalkyl vinyl ether (PFA) mainly containing repeating units represented by the following formula (10A) and the following formula (10B).

(In the formula (10B), R _f represents a perfluoroalkyl group (C _n F _{2n + 1} ) having 2 to 16 carbon atoms, preferably 4 to 12 carbon atoms).

  Polytetrafluoroethylene (PTFE) comprising a repeating unit represented by the following formula (11).

  A tetrafluoroethylene-hexafluoropropylene copolymer (FEP) mainly containing repeating units represented by the following formula (12A) and the following formula (12B).

  Polyperfluoroalkylvinyl mainly containing a repeating unit represented by the following formula (13).

(In the formula (13), R _f represents a perfluoroalkyl group (C _n F _{2n + 1} ) having 2 to 16 carbon atoms, preferably 4 to 12 carbon atoms).

  Poly 2- (perfluoroalkyl) ethyl vinyl mainly containing a repeating unit represented by the following formula (14).

(In the formula (14), R _f represents a perfluoroalkyl group (C _n F _{2n + 1} ) having 2 to 16 carbon atoms, preferably 4 to 12 carbon atoms).

  A polyperfluoroalkyl vinyl ether mainly containing a repeating unit represented by the following formula (15).

(In the formula (15), R _f represents a perfluoroalkyl group (C _n F _{2n + 1} ) having 2 to 16 carbon atoms, preferably 4 to 12 carbon atoms).

  Poly 2- (perfluoroalkyl) ethyl vinyl ether mainly containing a repeating unit represented by the following formula (16).

(In the formula (16), R _f represents a perfluoroalkyl group (C _n F _{2n + 1} ) having 2 to 16 carbon atoms, preferably 4 to 12 carbon atoms).

  Perfluoropolyalkenyl vinyl ether mainly containing a repeating unit represented by the following formula (17).

  (In the formula (17), a = 0 or 1, b = 0 or 1, c = 0, 1, or 2 is shown)

  In addition, the copolymer which has the repeating unit of the said Formula (4)-Formula (17) as a main, and contains another repeating unit can be used if it is a range which does not impair the effect of this invention.

  In the present invention, a polymer mainly containing a repeating unit represented by the formula (4) is preferable from the viewpoint of excellent water and oil repellency, and in particular, poly 2- (perfluoroalkyl) ethyl acrylate, Poly 2- (perfluoroalkyl) ethyl methacrylate is preferred.

  The molecular weight of each of the above-mentioned polymers is not particularly limited, but a polymer having a molecular weight of Mw 3000 to 400000 (where Mw is a weight average molecular weight in terms of polystyrene using GPC (solvent; tetrahydrofuran)) is preferable, and particularly 30000 to 70000. Is preferred. This is because if the molecular weight is smaller than this range, the film tends to become brittle, whereas if the molecular weight is larger than this range, the solubility tends to decrease.

  The solvent used in the coating agent of the present invention is not particularly limited as long as it is a solvent capable of dissolving a fluorine-based polymer. For example, ketones such as acetone, MEK, MIBK, ethyl acetate, acetic acid An ester solvent such as butyl, an ether solvent such as diethyl ether or dioxane, an alkane solvent such as heptane or hexane, or an alcohol solvent such as ethanol or IPA can be used. In particular, a fluorinated solvent is preferred. Use of a fluorine-based solvent is nonflammable, so there is no need to provide a special exhaust / explosion-proof device in the coating facility. Moreover, since the fluorine-based solvent has a high affinity with the fluorine-based polymer, the solubility of the fluorine-based polymer is high.

  The fluorine-based solvent is not particularly limited. For example, perfluorocarbon (PFC), hydrofluorocarbon (HFC), hydrochlorofluorocarbon (HCFC), hydrofluoroether (HFE), perfluoropolyether (PFPE), hydrofluoropoly Ether (HFPE) or the like can be used.

  Next, the fluorescent agent mixed with the coating agent of the present invention will be described. As the fluorescent agent, at least one of those represented by the following general formula (1) and those represented by the following general formula (2) is used.

[Wherein, R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an arylalkyl having 7 to 30 carbon atoms which may have a substituent. Group, an optionally substituted aryl group having 6 to 20 carbon atoms, and an optionally substituted heteroaryl group having 5 to 20 carbon atoms, which are bonded to each other to form a ring structure It may be formed or may form a ring structure together with a benzene ring to which a nitrogen atom is bonded.

R ³ is an alkyl group having 1 to 20 carbon atoms which may have a substituent, which contains 2 to 41 fluorine atoms in at least one of the substituent or the alkyl group, and has a substituent. An arylalkyl group having 7 to 30 carbon atoms, which contains 2 to 49 fluorine atoms in at least one of the substituent or the arylalkyl group, or an aryl group having 6 to 30 carbon atoms having a substituent and 2 The thing containing -49 fluorine, the C5-C20 heteroaryl group which has a substituent, and the thing containing 2-31 fluorine are shown.

X is an oxygen atom, a sulfur atom, —NH— or —NR ⁴ — (R ⁴ is an optionally substituted alkyl group having 1 to 10 carbon atoms, and optionally substituted carbon. An aryl group having 6 to 20 carbon atoms, and a heteroaryl group having 5 to 20 carbon atoms which may have a substituent.

Y is an oxygen atom, a sulfur atom, —NH— or —NR ⁶ — (R ⁶ is an optionally substituted alkyl group having 1 to 10 carbon atoms, and optionally substituted carbon. An aryl group having 6 to 20 carbon atoms, and a heteroaryl group having 5 to 20 carbon atoms which may have a substituent. ]

In the general formulas (1) and (2), R ¹ and R ² are each independently an optionally substituted alkyl group having 1 to 10 carbon atoms and an optionally substituted carbon. An arylalkyl group having 7 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms which may have a substituent, and a heteroaryl group having 5 to 20 carbon atoms which may have a substituent; They may be bonded to each other to form a ring structure, or may be formed together with a benzene ring to which a nitrogen atom is bonded.

The alkyl group may be linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, and various hexyls. Groups, various octyl groups, various decyl groups, cyclopentyl groups, cyclohexyl groups, cyclooctyl groups and the like. The alkyl group may be a partially fluorinated fluorine-containing alkyl group. Examples of the fluorine-containing alkyl group include a trifluoroethyl group, a trifluoropropyl group _{, a} tetrafluorobutyl group _{, and a} hexafluorobutyl group.

  Examples of arylalkyl groups include benzyl, phenethyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenylisopropyl, phenyl-t-butyl, α-naphthylmethyl 1-α-naphthylethyl group, 2-α-naphthylethyl group, 1-α-naphthylisopropyl group, 2-α-naphthylisopropyl group, β-naphthylmethyl group, 1-β-naphthylethyl group, 2-β -Naphthylethyl group, 1-β-naphthylisopropyl group, 2-β-naphthylisopropyl group, 1-pyrrolylmethyl group, 2- (1-pyrrolyl) ethyl group, p-methylbenzyl group, m-methylbenzyl group, o- Methylbenzyl group, p-chlorobenzyl group, m-chlorobenzyl group, o-chlorobenzyl group, p-bromobenzyl group, m-bromine group Benzyl group, o-bromobenzyl group, p-iodobenzyl group, m-iodobenzyl group, o-iodobenzyl group, p-hydroxybenzyl group, m-hydroxybenzyl group, o-hydroxybenzyl group, p-aminobenzyl group M-aminobenzyl group, o-aminobenzyl group, p-nitrobenzyl group, m-nitrobenzyl group, o-nitrobenzyl group, p-cyanobenzyl group, m-cyanobenzyl group, o-cyanobenzyl group, 1 -Hydroxy-2-phenylisopropyl group, 1-chloro-2-phenylisopropyl group and the like. The arylalkyl group may be a partially fluorinated fluorine-containing arylalkyl group. Examples of the fluorine-containing arylalkyl group include 1-phenyldifluoroethyl group, α-naphthyltrifluoromethyl group, p-trifluoromethylbenzyl group and the like.

  Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, and a pyrenyl group.

  Examples of heteroaryl groups include 1-aza-indolizin-2-yl, 1-aza-indolizin-3-yl, 1-aza-indolizin-5-yl, 1-aza-indolizine -6-yl group, 1-aza-indolizine-7-yl group, 1-aza-indolizin-8-yl group, 2-aza-indolizin-1-yl group, 2-aza-indolizine-3 -Yl group, 2-aza-indolizin-5-yl group, 2-aza-indolizin-6-yl group, 2-aza-indolizin-7-yl group, 2-aza-indolizin-8-yl A group, 6-aza-indolizin-1-yl group, 6-aza-indolizin-2-yl group, 6-aza-indolizin-3-yl group, 6-aza-indolizin-5-yl group, 6-aza-indolizine-7-yl group, 6-aza-indolizine- -Yl group, 7-aza-indolizin-1-yl group, 7-aza-indolizin-2-yl group, 7-aza-indolizin-3-yl group, 7-aza-indolizin-5-yl A group, 7-aza-indolizin-6-yl group, 7-aza-indolizin-7-yl group, 7-aza-indolizin-8-yl group, 8-aza-indolizin-1-yl group, 8-aza-indolizin-2-yl group, 8-aza-indolizin-3-yl group, 8-aza-indolizin-5-yl group, 8-aza-indolizin-6-yl group, 8- Aza-indolizin-7-yl group, 1-indolidinyl group, 2-indolidinyl group, 3-indolidinyl group, 5-indolidinyl group, 6-indolidinyl group, 7-indolidinyl group, 8-indolidinyl group, 1-pyrrolyl group, 2-pyrrolyl group, -Pyrrolyl group, pyrazinyl group, 2-pyridinyl group, 3-pyridinyl group, 4-pyridinyl group, 1-indolyl group, 2-indolyl group, 3-indolyl group, 4-indolyl group, 5-indolyl group, 6-indolyl group Group, 7-indolyl group, 1-isoindolyl group, 2-isoindolyl group, 3-isoindolyl group, 4-isoindolyl group, 5-isoindolyl group, 6-isoindolyl group, 7-isoindolyl group, 2-furyl group, 3-furyl group Group, 2-benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group, 5-benzofuranyl group, 6-benzofuranyl group, 7-benzofuranyl group, 1-isobenzofuranyl group, 3-isobenzofuranyl group, 4- Isobenzofuranyl group, 5-isobenzofuranyl group, 6-isobenzofuranyl group, 7-isobenzo Furanyl, 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl, 1-isoquinolyl, 3-isoquinolyl, 4- Isoquinolyl group, 5-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 2-quinoxalinyl group, 5-quinoxalinyl group, 6-quinoxalinyl group, 1-carbazolyl group, 2-carbazolyl group, 3- Carbazolyl group, 4-carbazolyl group, 9-carbazolyl group, 1-phenanthridinyl group, 2-phenanthridinyl group, 3-phenanthridinyl group, 4-phenanthridinyl group, 6-phenanthridinini Group, 7-phenanthridinyl group, 8-phenanthridinyl group, 9-phenanthridinyl group, 10-phenanthridinyl group, -Acridinyl group, 2-acridinyl group, 3-acridinyl group, 4-acridinyl group, 9-acridinyl group, 1,7-phenanthrolin-2-yl group, 1,7-phenanthrolin-3-yl group, 1,7-phenanthrolin-4-yl group, 1,7-phenanthrolin-5-yl group, 1,7-phenanthrolin-6-yl group, 1,7-phenanthrolin-8-yl group Group, 1,7-phenanthrolin-9-yl group, 1,7-phenanthrolin-10-yl group, 1,8-phenanthrolin-2-yl group, 1,8-phenanthrolin-3 -Yl group, 1,8-phenanthroline-4-yl group, 1,8-phenanthrolin-5-yl group, 1,8-phenanthrolin-6-yl group, 1,8-phenanthroline -7-yl group, 1,8-phenanthroline-9-i Group, 1,8-phenanthroline-10-yl group, 1,9-phenanthrolin-2-yl group, 1,9-phenanthrolin-3-yl group, 1,9-phenanthroline-4 -Yl group, 1,9-phenanthrolin-5-yl group, 1,9-phenanthrolin-6-yl group, 1,9-phenanthrolin-7-yl group, 1,9-phenanthroline -8-yl group, 1,9-phenanthrolin-10-yl group, 1,10-phenanthrolin-2-yl group, 1,10-phenanthrolin-3-yl group, 1,10-phen group Nansulolin-4-yl group, 1,10-phenanthrolin-5-yl group, 2,9-phenanthrolin-1-yl group, 2,9-phenanthrolin-3-yl group, 2,9 -Phenanthrolin-4-yl group, 2,9-phenanthrolin-5-yl group, 2, 9-phenanthroline-6-yl group, 2,9-phenanthrolin-7-yl group, 2,9-phenanthrolin-8-yl group, 2,9-phenanthrolin-10-yl group, 2,8-phenanthrolin-1-yl group, 2,8-phenanthrolin-3-yl group, 2,8-phenanthrolin-4-yl group, 2,8-phenanthrolin-5-yl Group, 2,8-phenanthroline-6-yl group, 2,8-phenanthrolin-7-yl group, 2,8-phenanthrolin-9-yl group, 2,8-phenanthroline-10 -Yl group, 2,7-phenanthrolin-1-yl group, 2,7-phenanthrolin-3-yl group, 2,7-phenanthrolin-4-yl group, 2,7-phenanthroline -5-yl group, 2,7-phenanthrolin-6-yl group, 2,7-phenanthro -8-yl group, 2,7-phenanthrolin-9-yl group, 2,7-phenanthrolin-10-yl group, 1-phenazinyl group, 2-phenazinyl group, 1-phenothiazinyl group, 2 -Phenothiazinyl group, 3-phenothiazinyl group, 4-phenothiazinyl group, 10-phenothiazinyl group, 1-phenoxazinyl group, 2-phenoxazinyl group, 3-phenoxazinyl group, 4-phenoxazinyl group, 2-phenoxazinyl group, 2- Oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 2-oxadiazolyl group, 5-oxadiazolyl group, 3-furazanyl group, 2-thienyl group, 3-thienyl group, 2-methylpyrrol-1-yl group, 2- Methylpyrrol-3-yl group, 2-methylpyrrol-4-yl group, 2-methylpyrrol-5-yl group, -Methylpyrrol-1-yl group, 3-methylpyrrol-2-yl group, 3-methylpyrrol-4-yl group, 3-methylpyrrol-5-yl group, 2-t-butylpyrrol-4-yl group 3- (2-phenylpropyl) pyrrol-1-yl group, 2-methyl-1-indolyl group, 4-methyl-1-indolyl group, 2-methyl-3-indolyl group, 4-methyl-3-indolyl group Group, 2-t-butyl 1-indolyl group, 4-t-butyl 1-indolyl group, 2-t-butyl 3-indolyl group, 4-t-butyl 3-indolyl group and the like.

  Each of these groups may have an appropriate substituent. Examples of the substituent include an alkyl group, an alkoxyl group, a halogen atom, a cyano group, an alkoxycarbonyl group, a carboxyl group, an ester group, and an amide group. , Sulfoxyl group, sulfonamide group, nitro group, aryl group, heteroaryl group and the like.

Examples of the alkyl group, aryl group, and heteroaryl group include those described above, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkoxyl group may be linear, branched or cyclic, and may contain fluorine. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, various butoxy, various pentoxy, various hexoxy, various octoxy, various decyloxy, cyclopentyloxy, cyclohexyloxy, benzyloxy Fluorine-containing alkoxyl groups such as trifluoromethoxy group, trifluoroethoxy group, trifluoropropoxy group, O—CH ₂ (CH ₃ ) CF ₃ , O—CH ₂ —C ₃ F _7, etc. Can be mentioned. The sulfonamide group may be either a substituted sulfonamide or an unsubstituted sulfonamide, the amide group may be either a substituted amide or an unsubstituted amide, and these may contain fluorine. . Examples of the substituent for these alkoxyl group, sulfonamide group and amide group include the same as those for R ¹ and R ² . Furthermore, as an example of the alkoxyl group in an alkoxycarbonyl group, the same thing as the above is mentioned. The ester group may be a fluorine-containing ester group represented by COOCH ₂ C ₆ F ₁₃ in addition to an alkyl ester such as COOCH ₃ .

Examples of the ring structure formed by combining R ¹ and R ² together with a nitrogen atom include a 1-pyrrolidinyl group, a piperidino group, and a morpholino group.

Examples of the ring structure formed by R ¹ and R ² together with a benzene ring to which a nitrogen atom is bonded include the following.

R ¹ and R ² are preferably an alkyl group having 4 to 10 carbon atoms and a fluorine-containing alkyl group having 4 to 10 carbon atoms from the viewpoint of high solubility in an organic solvent, and has high solubility in a fluorine solvent. From the viewpoint, a fluorine-containing alkyl group having 4 to 10 carbon atoms is more preferable.

In the general formulas (1) and (2), X represents an oxygen atom, a sulfur atom, —NH— or —NR ⁴ — (R ⁴ represents an optionally substituted alkyl group having 1 to 10 carbon atoms). , An aryl group having 6 to 20 carbon atoms which may have a substituent, and a heteroaryl group having 5 to 20 carbon atoms which may have a substituent.

Examples of the alkyl group, aryl group and heteroaryl group represented by R ⁴ include the same examples as those described above for R ¹ and R ² , and the substituents thereof are also the same.

In the general formulas (1) and (2), Y represents an oxygen atom, a sulfur atom, —NH— or —NR ⁶ — (R ⁶ is an optionally substituted alkyl group having 1 to 10 carbon atoms). , An aryl group having 6 to 20 carbon atoms which may have a substituent, and a heteroaryl group having 5 to 20 carbon atoms which may have a substituent.

Examples of the alkyl group, aryl group and heteroaryl group represented by R ⁶ include the same examples as those described above for R ¹ and R ² , and the substituents thereof are also the same.

  X and Y are preferably oxygen atoms because they are easy to synthesize and have excellent fluorescence, solubility in organic solvents, heat resistance, and light resistance.

In the general formulas (1) and (2), R ³ contains two or more fluorines from the viewpoint of improving solubility in a fluorine-based solvent, and specifically represents the following groups. The upper limit of the number of fluorines is the number of fluorines when fully fluorinated (when the C—H bond is completely substituted with the C—F bond).

R ³ is an alkyl group having 1 to 20 carbon atoms which may have a substituent, which contains 2 to 41 fluorine atoms in at least one of the substituent or the alkyl group, and has a substituent. An arylalkyl group having 7 to 30 carbon atoms, which contains 2 to 49 fluorine atoms in at least one of the substituent or the arylalkyl group, or an aryl group having 6 to 30 carbon atoms having a substituent and 2 Those containing ˜49 fluorine atoms, or a heteroaryl group having 5 to 20 carbon atoms having a substituent and containing 2 to 31 fluorine atoms.

In addition to those exemplified for R ¹ and R ² above, the alkyl group of R ³ includes various undecyl groups, various dodecyl groups, various tridecyl groups, various tetradecyl groups, various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, Examples include those having 11 to 20 carbon atoms such as various octadecyl groups, various nonadecyl groups, and various eicosyl groups, and fluorine-containing alkyl groups (for example, C ₂ H ₄ C ₁₀ F ₂₁ ) in which these are partially fluorinated. It is. These may be linear, branched or cyclic.

The arylalkyl group for R ³ is the same as that exemplified for R ¹ and R ² above.

Examples of the substituent for the alkyl group and arylalkyl group include the same substituents as those exemplified for R ¹ and R ² above, and substituents containing fluorine (described later).

When R ³ is an alkyl group, the alkyl group can contain 0 to 41 fluorine atoms, the substituent can contain 0 to 41 fluorine atoms, and the alkyl group contains fluorine atoms. The sum of the number and the number of fluorine contained in the substituent may be 2 to 41. When R ³ is an arylalkyl group, the number of fluorines that can be included in the arylalkyl group is 0 to 49, and the number of fluorines that can be included in the substituent is 0 to 49, and is included in the arylalkyl group. The sum of the number of fluorine atoms and the number of fluorine atoms contained in the substituents may be 2 to 49.

  Examples of the aryl group having a substituent include those obtained by substituting an aryl group such as a phenyl group, a naphthyl group, an anthryl group, and a pyrenyl group with a substituent containing 2 to 49 fluorine atoms. The aryl group only needs to have at least one substituent containing fluorine, and the total number of fluorine contained in the substituent may be 2 to 49.

Examples of the heteroaryl group having a substituent include those obtained by substituting the heteroaryl group exemplified for R ¹ and R ² with a substituent containing 2 to 31 fluorine atoms. The heteroaryl group only needs to have at least one substituent containing fluorine, and the total number of fluorine contained in the substituent may be 2 to 31.

Now, Examples of the substituent containing a fluorine, trifluoroethyl group, trifluoropropyl _group, tetrafluoro-butyl _group, a fluorine-containing alkyl groups such as hexafluorobutyl group, trifluoromethoxy group, trifluoroethoxy group, trifluoromethyl propoxy Group, fluorine-containing alkoxyl group such as O—CH ₂ (CH ₃ ) CF ₃ , O—CH ₂ —C ₃ F ₇ , fluorine atom, fluorine-containing alkoxycarbonyl group, fluorine-containing amide group such as NHCOCF ₃ , fluorine-containing sulfone Fluorine-containing aryl group such as amide group, phenyl fluoride, fluorine-substituted heteroaryl group, fluorine-containing ester group represented by COOCF ₃ or COO (CH ₂ ) _n R ⁵ (wherein n is an integer of 1 to ⁵ , R ⁵ Is an alkyl group having 1 to 20 carbon atoms which may have a substituent. A group containing 2 to 41 fluorine atoms in at least one of a substituent or an alkyl group, or an arylalkyl group having 7 to 30 carbon atoms which may have a substituent, and at least one of the substituent or the arylalkyl group A C2-C30 aryl group having 2 to 41 fluorine atoms, a C2-C30 aryl group having 2 to 41 fluorine atoms, and a C5-C30 heteroaryl group having a substituent group. And those containing 2 to 41 fluorine atoms). Further, the fluorine-containing substituent may be a fluorinated polyether such as perfluoropolyether or hydrofluoropolyether, such as (CF ₂ O) _p , (CF ₂ CF ₂ O) _p , (CF ₂ CFCF _{3 O) p} such as _{(C q} F 2q _O) those represented by _p may also comprise one or more (p is 1 to 30 integer, q is an integer of 1-6).

Of R ^5, alkyl group, arylalkyl group, an aryl group, a heteroaryl group, a substituted group is the same as those exemplified in R ^3.

Among the above R ³ , an aryl group having 6 to 30 carbon atoms having a substituent containing 2 to 49 fluorine atoms is preferable, and an aryl group having a fluorine-containing ester group represented by the following general formula (3) is more preferable. .

[Wherein Ar represents an aryl group having 6 to 30 carbon atoms, and n represents an integer of 1 to 5. R ⁵ is an alkyl group having 1 to 20 carbon atoms which may have a substituent, which contains 2 to 41 fluorine atoms in at least one of the substituent or the alkyl group, and may have a substituent. Preferred arylalkyl group having 7 to 30 carbon atoms and having 2 to 49 fluorine atoms in at least one of the substituent or arylalkyl group, or an aryl group having 6 to 30 carbon atoms having a substituent and 2 to A compound containing 49 fluorine atoms or a heteroaryl group having 5 to 20 carbon atoms having a substituent and containing 2 to 31 fluorine atoms is shown. ]

In the general formula (3), n is preferably 1 to 5 from the viewpoint of easy esterification reaction, and R ⁵ is C _m F _{2m + 1} (m is ₁ to 16 from the viewpoint of high solubility in a fluorine-based solvent. Is preferably a fluorine-containing alkyl group represented by

  In the present invention, fluorescent compounds represented by the following general formulas (18) and (19) (without X) may be included.

  Furthermore, in the present invention, fluorescent compounds represented by the following general formulas (20) and (21) may be included.

In the general formulas (18) to (21), R ¹ and R ² are each independently an optionally substituted alkyl group having 1 to 10 carbon atoms and an optionally substituted carbon. An arylalkyl group having 7 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms which may have a substituent, and a heteroaryl group having 5 to 20 carbon atoms which may have a substituent; They may be bonded to each other to form a ring structure, or may be formed together with a benzene ring to which a nitrogen atom is bonded.

In the general formulas (18) to (21), R ³ is an alkyl group having 1 to 20 carbon atoms which may have a substituent, and 2 to 41 fluorine atoms in at least one of the substituent or the alkyl group. An arylalkyl group having 7 to 30 carbon atoms which may have a substituent and having 2 to 49 fluorine atoms in at least one of the substituent or arylalkyl group, or a carbon having a substituent An aryl group having 6 to 30 carbon atoms containing 2 to 49 fluorine atoms and a heteroaryl group having 5 to 20 carbon atoms having a substituent and 2 to 31 fluorine atoms are shown.

In general formulas (18) to (21), Y represents an oxygen atom, a sulfur atom, —NH— or —NR ⁶ — (R ⁶ represents an optionally substituted alkyl group having 1 to 10 carbon atoms). , An aryl group having 6 to 20 carbon atoms which may have a substituent, and a heteroaryl group having 5 to 20 carbon atoms which may have a substituent.

In the general formulas (20) and (21), X represents an oxygen atom, a sulfur atom, —NH— or —NR ⁴ — (R ⁴ is an optionally substituted alkyl group having 1 to 10 carbon atoms). , An aryl group having 6 to 20 carbon atoms which may have a substituent, and a heteroaryl group having 5 to 20 carbon atoms which may have a substituent.

R ¹ , R ² , R ³ and Y in the general formulas (18) to (21) are the same as those in the general formulas (1) and (2), and X in the general formulas (20) and (21) Is the same as in general formulas (1) and (2).

Next, the manufacturing method of the fluorescent compound used by this invention is demonstrated.
In the compounds of the general formulas (1) and (2), when X is an oxygen atom, a benzofurano-1,2-naphthoquinone derivative (1a) is first synthesized according to the following reaction formula (A).

(In the formula, M is an alkali metal atom, and R ¹ and R ² are the same as above.)

  As shown in reaction formula (A), a substantially stoichiometric amount of 1,2-naphthoquinone-4-sulfonic acid alkali metal salt (a) and m-substituted phenol (b) are mixed with an appropriate acetic acid or the like. In a solvent, by reacting at a temperature of about 0 to 80 ° C. in the presence of a catalyst such as copper chloride, it has a benzofurano-1,2-naphthoquinone skeleton represented by the general formula (1a), and X is A compound which is an oxygen atom is obtained. At this time, the compound represented by the general formula (1b) is by-produced.

  In the above reaction, 1,2-naphthoquinone may be used in place of the alkali metal salt of 1,2-naphthoquinone-4-sulfonic acid (a). Further, nickel chloride or zinc acetate may be used as a catalyst instead of copper chloride.

  Next, as shown in the reaction formula (B), ammonium acetate and a temperature of about 50 to 100 ° C. in a suitable solvent such as the compound represented by the general formula (1a), p-benzoic aldehyde and acetic acid. In this way, the fluorescent compound represented by the general formula (2a) and the fluorescent compound represented by the general formula (2b) are obtained as a mixture.

Next, as shown in the reaction formula (C), a mixture of the oxazole fluorescent compounds represented by the general formulas (2a) and (2b), R ⁵ I and sodium carbonate are mixed with dimethylformamide (DMF) or the like. By reacting at a temperature of 70 to 120 ° C. in an appropriate solvent, the fluorescent compounds used in the present invention represented by the general formulas (3a) and (3b) are obtained as a mixture.

  Next, the amount of each component mixed in the coating agent of the present invention will be described.

  In the coating agent of the present invention, the amount of the fluorine-based polymer with respect to the total amount of the fluorine-based polymer, the fluorescent agent and the solvent is preferably 0.05 to 30% by weight, more preferably 0.1 to 15% by weight, particularly Preferably it is 0.2-8 weight%. This is because if the amount of the fluorine-based polymer is less than this range, a uniform film cannot be formed and unevenness tends to occur, whereas if it is increased, the film tends to be brittle and easily cracked.

  The fluorescent agent is added in such an amount that the presence or absence of the coat film can be confirmed, that is, sufficient visibility can be secured. In order to ensure sufficient visibility, the conventional fluorescent agent needs to be added in an amount of 500 wt ppm or more with respect to the entire coating agent. When the fluoropolymer content in the coating agent is small (for example, the fluoropolymer content is 1000 wt%). (ppm: 0.1% by weight) has a problem that the film properties of the formed coating film deteriorate because the concentration of the fluorescent agent in the dry film increases.

  However, in the present invention, if the addition amount of the fluorescent agent is 10 wt ppm or more with respect to the total amount (the total amount of the fluoropolymer, the fluorescent agent, and the solvent), it can be confirmed whether or not the fluorescent agent is applied. In addition, if 20 wt ppm or more, sufficient visibility is ensured, so the amount of addition may be smaller than when a conventional fluorescent agent is used.

  In addition, it is also possible to add various additives, such as antioxidant, a ultraviolet absorber, and a filler, to a coating agent, in order to improve practicality.

  Moreover, the coating method to the to-be-coated thing of the coating agent of this invention is not specifically limited, Well-known coating methods, such as a dip (Dip), brush coating, spray, and dispensing, can be used.

  The coating agent of the present invention can be used in a wide range of applications, for example, moisture-proof coating agents for electronic substrates, chemical-resistant protective coating agents that protect substrates from salt water, electrolytes, corrosive gases, etc., and lubricating oils used in micro motor bearings. Oil barrier agent that prevents diffusion, oil barrier agent that prevents the diffusion of lubricating oil used in fluid bearings of HDD motors, leakage prevention agents that prevent leakage of ink such as sign pens and ballpoint pens, and stain prevention agents for connectors and electronic components , Anti-creeping agent for insulation resin, anti-adhesion agent for lead sealing resin of MF capacitor, anti-rust agent for metal parts, dry lubricant for guide rails such as DVD / CD, anti-reflection coating agent, waterproof spray stock solution Can be used for

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, this invention is not limited to a following example.

The fluorescent agent used in the following examples was synthesized by the following procedure.
<Synthesis of fluorescent agent>
Sodium 1,2-naphthoquinone-4-sulfonate (1.0 g, 3.84 × 10 ⁻³ mol) and N, N-dibutyl-3-aminophenol (1.02 g, 4.16 × 10 ⁻³ mol) 30 ml of dimethyl sulfoxide (DMSO) was added to zinc acetate (0.10 g, 3.84 × 10 ⁻³ mol) and stirred at 60 ° C. for 5 hours. After completion of the reaction, the reaction solution was poured into 400 ml of distilled water and the precipitate was filtered off. The product (1) was extracted from the filtrate with dichloromethane, the dichloromethane extract was concentrated under reduced pressure, separated and purified using silica gel column chromatography [dichloromethane / ethyl acetate = 10/1], and a benzofurano-1,2-naphthoquinone derivative. Was obtained in a yield of about 30% (see the following reaction formula A1).

Next, benzofurano-1,2-naphthoquinone derivative (1A) (4.0 g, 1.06 × 10 ⁻² mol) and p-benzoic acid aldehyde (1.92 g, 1.28 × 10 ⁻² mol) were mixed with acetic acid. This was dissolved in 30 ml, and ammonium acetate (16.44 g, 2.14 × 10 ⁻¹ mol) was added thereto and reacted at 90 ° C. for 2 hours. After completion of the reaction, the reaction solution was poured into 200 ml of distilled water and the precipitate was filtered off. The filter cake was washed with dichloromethane to remove impurities, and a mixture of oxazole-based fluorescent dyes (2A) and (2B) in the form of yellow powder was obtained in a yield of 90% (see the following reaction formula B1).

Mixture of oxazole-based fluorescent dyes (2A) and (2B) (1.00 g, 1.97 × 10 ⁻³ mol) and nC ₆ F ₁₃ CH ₂ CH ₂ I (1.87 g, 3.95 × 10 ⁻³ mol) and sodium carbonate (0.418 g, 3.95 × 10 ⁻³ mol) were dissolved in 2.5 ml of DMF and stirred at 100 ° C. for 7 hours. After completion of the reaction, it was poured into 50 ml of distilled water, and the precipitate was filtered off. The product was extracted from the filtrate with dichloromethane, concentrated under reduced pressure, and purified by silica gel column chromatography (developing solvent; dichloromethane) to obtain a mixture of oxazole-based fluorescent compounds (3A) and (3B) as yellow powder crystals. The yield was 70% (see the following reaction formula C1).

<Reference Test Example 1>
1 mg of the mixture of the fluorescent compounds (3A) and (3B) was added to 10 g of a fluorinated solvent, and the solubility was examined. Perfluorocarbon (PFC), hydrofluorocarbon (HFC), hydrofluoroether (HFE), perfluoropolyether (PFPE), hydrofluoropolyether (HFPE) is used as the fluorinated solvent. Dissolved. This is considered to be due to the fact that the fluorescent compounds (3A) and (3B) have a fluorine-containing alkyl group moiety represented by C ₆ F ₁₃ .

<Test Example 1: Coat film visibility evaluation test (influence of substrate color)>
1. Preparation of Coating Agent (A-1) of the Present Invention 0.25 part by weight of poly 2- (perfluoroalkyl) ethyl acrylate was dissolved in 99.75 parts by weight of HFE to obtain a sample solution SA.

  A mixture of the fluorescent compound represented by formula (3A) and the fluorescent compound represented by formula (3B) obtained by the above synthesis method (hereinafter referred to as fluorescent agent A) in 99.99 g of this sample solution. Was added to give a coating agent A-1 (coating agent of the present invention). In this coating agent, the amount of the fluorescent agent is 100 wt ppm with respect to the total amount of poly-2- (perfluoroalkyl) ethyl acrylate, the fluorescent agent and the solvent.

2. Preparation of coating agent (B-1) of Comparative Example 1 Same as coating agent A-1, except that 100 mg of oxazole-based fluorescent agent (trade name: Leuhi marker 108M) was added to 99.9 g of sample solution SA and dispersed. Thus, a coating agent B-1 was prepared. In this coating agent, the amount of the fluorescent agent is 1000 wt ppm with respect to the total amount of poly-2- (perfluoroalkyl) ethyl acrylate, the fluorescent agent and the solvent.

3. Formation of coat film Each coating agent of A-1 and B-1 is put in a container, and the following various base materials are dipped in each coating agent, and then the base material is pulled up from the coating agent and dried at room temperature. (1 dip coat). As a result, a coat film having a thickness of about 0.1 μm was formed on the surface of each substrate.

  The substrate used was a stainless steel plate (SUS plate, length 40 mm × width 15 mm, thickness 0.5 mm), glass plate (length 76 mm × width 26 mm, thickness 1 mm), black resin plate (PET, long 40 mm long × 15 mm wide, 0.5 mm thick), gray resin plate (PET, length 40 mm × width 15 mm, thickness 0.5 mm), white resin plate (PET, length 40 mm × width 15 mm, Thickness 0.5 mm).

4). Evaluation Method of Visibility of Coat Film The coat film formation portion of each substrate was irradiated with black light (wavelength 365 nm), and the color of the coat film was visually observed.
The evaluation at this time was as follows.
A: Color development is clearly observed (the presence of the coat film can be clearly confirmed by color development (high visibility)).
○: Color development is observed.
Δ: Some color development is observed.
X: Color development is not observed at all.
Table 1 shows the evaluation results of the visibility of the coat film.

  When the coating agent of A-1 was used, the formed coating film colored yellow in all the substrates and was clearly observed, so the presence of the coating film could be easily confirmed ( Visibility was high).

  When the coating agent of B-1 was used, visibility was inferior to A-1 in any base material. In particular, no color development was observed on the black resin plate. This is considered to be due to the fact that the fluorescent agent is colored blue.

  From the above, it was found that the coating agent of the present invention can be used regardless of the substrate color.

<Test Example 2: Effect of Heat on Visibility of Coat Film (Heat Resistance)>
After coating agents A-1 and B-1 prepared in Test Example 1 are put in separate containers and a stainless steel plate (SUS, length 40 mm × width 15 mm, thickness 0.5 mm) is immersed, the stainless steel plate is attached. It was lifted from the coating agent and dried. A coat film having a thickness of about 0.1 μm was formed on each stainless steel plate.

  Next, the stainless steel plate on which the coat film was formed was dried at 150 ° C. for 1 hour, and the coat film formation portion was irradiated with black light (wavelength 365 nm), and the color of the coat film was visually observed.

  As a result, the coating film was clearly confirmed on the stainless steel plate using the coating agent A-1, but no color development was observed on the stainless steel plate using the coating agent B-1. From this, it was found that the coating agent of the present invention is excellent in heat resistance.

  <Test Example 3: Effect of Solvent on Visibility of Coat Film (Solvent Resistance)>

  The coating agents A-1 and B-1 prepared in Test Example 1 were put in separate containers, and after the dried glass plate was immersed, the glass plate was pulled up from the coating agent and dried. A coat film having a thickness of about 0.1 μm was formed on each glass plate.

  The glass plate on which the coating film was formed was immersed in each organic solvent (isopropyl alcohol (IPA), ethanol, methanol, hexane, heptane, ethyl acetate, acetone) for 1 hour at room temperature, then taken out from the solvent and dried, The coat film forming portion was irradiated with black light (wavelength 365 nm), and the color of the coat film was visually observed.

  Table 2 shows the results of evaluation by the same evaluation method as the visibility evaluation method of the coating film of Test Example 1.

When the coating agent of A-1 was used, color development was observed even when immersed in an organic solvent excluding ethyl acetate and acetone, indicating that the fluorescent agent was difficult to dissolve in the organic solvent. When the coating agent of B-1 was used, it turned out that a fluorescent agent melt | dissolves in all said organic solvents, and visibility falls.
From the above, it was found that the coating agent of the present invention has high solvent resistance.

<Test Example 4: Examination of concentration of fluorescent agent>
In the coating agent of the present invention, based on the coating agent of A-1 prepared in Test Example 1 (fluorescent agent concentration: 100 wt ppm), a coating agent having the following fluorescent agent concentration was prepared, and sufficient visibility was obtained. The concentration of the obtained fluorescent agent was examined. About the coating agent which added the conventional fluorescent agent, the coating agent of the fluorescent agent density | concentration described below was prepared on the basis of the coating agent of B-1 (fluorescent agent density | concentration 1000 wt ppm) prepared in Test Example 1, The concentration of the fluorescent agent with which sufficient visibility was obtained was examined.

1. Preparation of Coating Agents A-2 to A-6 0.25 parts by weight of poly-2- (perfluoroalkyl) ethyl acrylate was dissolved in 99.75 parts by weight of HFE to obtain a sample solution SA.
5 mg of the fluorescent agent A was added and dispersed in 99.995 g of this sample solution SA to obtain a coating agent A-2. In this coating agent, the amount of the fluorescent agent is 50 wt ppm with respect to the total amount of poly-2- (perfluoroalkyl) ethyl acrylate, the fluorescent agent and the solvent.

  2 mg of fluorescent agent A was added and dispersed in 99.998 g of sample solution SA to obtain coating agent A-3. In this coating agent, the amount of the fluorescent agent is 20 wt ppm with respect to the total amount of poly-2- (perfluoroalkyl) ethyl acrylate, the fluorescent agent and the solvent.

  1 mg of fluorescent agent A was added and dispersed in 99.999 g of sample solution SA to obtain coating agent A-4. In this coating agent, the amount of the fluorescent agent is 10 wt ppm with respect to the total amount of poly-2- (perfluoroalkyl) ethyl acrylate, the fluorescent agent and the solvent.

  0.5 mg of the fluorescent agent A was added and dispersed in 99.9995 g of the sample solution SA to obtain a coating agent A-5. In this coating agent, the amount of the fluorescent agent is 5 wt ppm with respect to the total amount of poly-2- (perfluoroalkyl) ethyl acrylate, the fluorescent agent and the solvent.

  0.1 mg of fluorescent agent A was added and dispersed in 99.9999 g of sample solution SA to obtain coating agent A-6. In this coating agent, the amount of the fluorescent agent is 1 wt ppm with respect to the total amount of poly-2- (perfluoroalkyl) ethyl acrylate, the fluorescent agent and the solvent.

2. Preparation of Coating Agent B-2 to B-6 A coating agent B-2 was prepared by adding and dispersing 50 mg of oxazole-based fluorescent agent (trade name: Leuhi Marker 108M, manufactured by Singleuch Co.) to 99.95 g of the sample solution SA. In this coating agent, the amount of the fluorescent agent is 500 wt ppm with respect to the total amount of poly-2- (perfluoroalkyl) ethyl acrylate, the fluorescent agent, and the solvent.

  20 mg of an oxazole-based fluorescent agent (trade name, Leuhi Marker 108M, manufactured by Singleuch Co., Ltd.) was added to and dispersed in 99.98 g of the sample solution SA to obtain Coating Agent B-3. In this coating agent, the amount of the fluorescent agent is 200 wt ppm with respect to the total amount of poly-2- (perfluoroalkyl) ethyl acrylate, the fluorescent agent, and the solvent.

  10 mg of an oxazole-based fluorescent agent (trade name: Leuhi Marker 108M, manufactured by Singleuch Co., Ltd.) was added to and dispersed in 99.99 g of the sample solution SA to obtain Coating Agent B-4. In this coating agent, the amount of the fluorescent agent is 100 wt ppm with respect to the total amount of poly-2- (perfluoroalkyl) ethyl acrylate, the fluorescent agent and the solvent.

  A coating agent B-5 was prepared by adding and dispersing 5 mg of an oxazole-based fluorescent agent (trade name: Leuhi Marker 108M, manufactured by Singleuch Co.) to the sample solution SA99.995 g. In this coating agent, the amount of the fluorescent agent is 50 wt ppm with respect to the total amount of poly-2- (perfluoroalkyl) ethyl acrylate, the fluorescent agent and the solvent.

  To the sample solution SA99.998 g, 2 mg of an oxazole-based fluorescent agent (trade name: Leuhi Marker 108M, manufactured by Singleuch Co., Ltd.) was added and dispersed to prepare Coating Agent B-5. In this coating agent, the amount of the fluorescent agent is 50 wt ppm with respect to the total amount of poly-2- (perfluoroalkyl) ethyl acrylate, the fluorescent agent and the solvent.

3. Formation of Coat Film A-1 Coating Agent Prepared in Test Example 1, A-2 to A-6 Coating Agents, B-1 Coating Agent Prepared in Test Example 1, and B-2 to B-6 Each coating agent is placed in a container, and each substrate is dipped, and then the substrate is pulled up from the coating agent and dried (one dip coating), and a coating film having a thickness of about 0.1 μm is formed on the surface of each substrate. Formed.

  The used base materials are stainless steel plate (SUS plate, length 40 mm × width 15 mm, thickness 0.5 mm), glass plate (length 76 mm × width 26 mm, thickness 1 mm), steel wire (made of SUS304, diameter 1 mm). Resin plate (made of PET, transparent color, length 40 mm x width 15 mm, thickness 0.5 mm), printed wiring board (comb electrode substrate 2 defined in 6.8 (1) of JISZ3197, length 50 mm x Width 50 mm, thickness 1.6 mm).

4). Evaluation Method for Coat Film Visibility Table 3 shows the results of evaluation by the same evaluation method as the coat film visibility evaluation method of Test Example 1 above.

  In the case of the coating agents A-1, A-2, A-3, the color development is clearly observed in all the base materials, and in the case of A-4, all of them are inferior to A-1 to A-3, In the case of A-5, it was found that color formation was observed on some of the substrates, but it was difficult to confirm the color formation on some of the substrates, but it was found to be in a practical range. In the case of coating agent A-6, the color development was not observable only in the steel wire, but it was found that it was within the usable range. In addition, since the favorable result was obtained in coating agent A-1, it did not test about what has a fluorescent agent density | concentration higher than A-1 ("-" in a table | surface does not test). Show).

  In the case of coating agents B-1 and B-2, the color development can be observed on all the substrates, but in the case of B-3, the color development is difficult to be confirmed on some of the substrates, but it is practical. It turned out to be a range. In the case of coating agent B-4, color development could not be observed only in the steel wire, but it was found that it was within the usable range. With coating agent B-5, a slight color development was observed only with glass. Since the coating agent B-6 was not observable on all the substrates, the test was not performed for the fluorescent agent concentration lower than that of B-6 ("-" in the table indicates the test). Indicates that you are not going).

  From the above, the concentration of the fluorescent agent that can be practically used in the coating agent of the present invention is 10 wt ppm or more, and the concentration that provides sufficient visibility is 20 wt ppm or more, which is practical in the coating agent using the conventional fluorescent agent. It was found that the concentration of the fluorescent agent was 200 wt ppm or more, and the concentration at which sufficient visibility was obtained was 1000 wt ppm or more. That is, in the coating agent of this invention, it turned out that the density | concentration of a fluorescent agent may be less than the conventional coating agent.

<Test Example 5. Study of coating agents using various fluoropolymers>
Next, coating agents using various fluoropolymers were examined.

1. Preparation of coating agent The following resins C-1 to C-9 were used in this test.
Resin C-1; ethylene-tetrafluoroethylene copolymer (ETFE)
Resin C-2: Tetrafluoroethylene-perfluoroalkyl vinyl ether (PFA)
Resin C-3; Polytetrafluoroethylene (PTFE)
Resin C-4; Poly-2- (perfluoroalkyl) ethyl vinyl ether Resin C-5; Polyperfluoroalkyl acrylate Resin C-6; Polyperfluoroalkyl methacrylate Resin C-7; Poly-2- (perfluoroalkyl) ethyl acrylate Resin C-8; Poly 2- (perfluoroalkyl) ethyl methacrylate Resin C-9; Perfluoropolyalkenyl vinyl ether

  A solution was prepared by dissolving 0.25 parts by weight of resin C-1 in 99.75 parts by weight of HFE, and 10 mg of fluorescent agent A was added and dispersed in 99.99 g of this solution to obtain coating agent C-1.

  In this coating agent, the amount of the fluorescent agent is 100 wt ppm with respect to the total amount of the resin C-1, the fluorescent agent, and the solvent.

  A coating agent C-2 was prepared in the same manner as the coating agent C-1, except that the resin C-2 was used instead of the resin C-1.

  Coating agent C-3 was prepared in the same manner as coating agent C-1, except that resin C-3 was used instead of resin C-1.

  Coating agent C-4 was prepared in the same manner as coating agent C-1, except that resin C-4 was used instead of resin C-1.

  Coating agent C-5 was prepared in the same manner as coating agent C-1, except that resin C-5 was used instead of resin C-1.

  Coating agent C-6 was prepared in the same manner as coating agent C-1, except that resin C-6 was used instead of resin C-1.

  Coating agent C-7 was prepared in the same manner as coating agent C-1, except that resin C-7 was used instead of resin C-1.

  Coating agent C-8 was prepared in the same manner as coating agent C-1, except that resin C-8 was used instead of resin C-1.

  Coating agent C-9 was prepared in the same manner as coating agent C-1, except that resin C-9 was used instead of resin C-1.

2. Formation of Coat Film Each coating agent was placed in a container, and using the same substrate as in Test Example 1, a coat film having a thickness of about 0.1 μm was formed on the surface of each substrate.

3. Evaluation Method of Coat Film The visibility of the coat film and the adhesion of the coat film to each substrate were evaluated in the same manner as in Test Example 1.

4). Results Even when any of the coating agents C-1 to C-9 was used, the color of the coat film was clearly observed on all the substrates, and the presence of the coat film could be clearly confirmed by the color development (high visibility) )

<Summary>
The coating agent of the present invention is excellent in heat resistance regardless of the base color used. Moreover, since it is excellent in solvent resistance, it is suitable also for the base material used in the environment which contacts an organic solvent. Furthermore, since the addition amount of the fluorescent agent is small, even when the coating agent has a specification with a low resin content, the influence on the film properties is suppressed.

<Other embodiments>
The present invention is not limited to the embodiments described with reference to the above description and drawings. For example, the following embodiments are also included in the technical scope of the present invention.
(1) In the above examples, a fluorescent agent that develops a yellow color was used. However, by changing R ¹ , R ² , R ³ , X and Y in the general formulas (1) and (2), the emission color can be changed. It is possible to use a fluorescent agent that can change the color and develop color other than yellow.

Claims (8)

A mixture of a fluoropolymer having a perfluoroalkyl group, at least one of a fluorescent agent represented by the following general formula (1) and a fluorescent agent represented by the following general formula (2), and a solvent. Coating agent.

[Wherein, R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an arylalkyl having 7 to 30 carbon atoms which may have a substituent. Group, an optionally substituted aryl group having 6 to 20 carbon atoms, and an optionally substituted heteroaryl group having 5 to 20 carbon atoms, which are bonded to each other to form a ring structure It may be formed or may form a ring structure together with a benzene ring to which a nitrogen atom is bonded.
R ³ is an alkyl group having 1 to 20 carbon atoms which may have a substituent, which contains 2 to 41 fluorine atoms in at least one of the substituent or the alkyl group, and has a substituent. An arylalkyl group having 7 to 30 carbon atoms, which contains 2 to 49 fluorine atoms in at least one of the substituent or the arylalkyl group, or an aryl group having 6 to 30 carbon atoms having a substituent and 2 The thing containing -49 fluorine, the C5-C20 heteroaryl group which has a substituent, and the thing containing 2-31 fluorine are shown.
X is an oxygen atom, a sulfur atom, —NH— or —NR ⁴ — (R ⁴ is an optionally substituted alkyl group having 1 to 10 carbon atoms, and optionally substituted carbon. An aryl group having 6 to 20 carbon atoms, and a heteroaryl group having 5 to 20 carbon atoms which may have a substituent.
Y is an oxygen atom, a sulfur atom, —NH— or —NR ⁶ — (R ⁶ is an optionally substituted alkyl group having 1 to 10 carbon atoms, and optionally substituted carbon. An aryl group having 6 to 20 carbon atoms, and a heteroaryl group having 5 to 20 carbon atoms which may have a substituent. ] 2. The coating agent according to claim 1, wherein R ³ is an aryl group having 6 to 30 carbon atoms having a substituent, and the substituent contains 2 to 49 fluorine atoms. The coating agent according to claim 1, wherein R ³ is a group represented by the following general formula (3).

[Wherein Ar represents an aryl group having 6 to 30 carbon atoms, and n represents an integer of 1 to 5.
R ⁵ is an alkyl group having 1 to 20 carbon atoms which may have a substituent, which contains 2 to 41 fluorine atoms in at least one of the substituent or the alkyl group, and has a substituent. An arylalkyl group having 7 to 30 carbon atoms, which contains 2 to 49 fluorine atoms in at least one of the substituent or the arylalkyl group, or an aryl group having 6 to 30 carbon atoms having a substituent and 2 The thing containing -49 fluorine, the C5-C20 heteroaryl group which has a substituent, and the thing containing 2-31 fluorine are shown. ] The coating agent according to claim 3, wherein R ⁵ in the general formula (3) is a group represented by C _m F _{2m + 1} .
[Wherein, m represents an integer of 1 to 16. ] The coating agent according to any one of claims 1 to 4, wherein the solvent is a fluorinated solvent. The said fluorine-type polymer is a polymer mainly containing the repeating unit represented by following General formula (4), and molecular weight Mw3000-400,000, The any one of Claims 1 thru | or 5 characterized by the above-mentioned. Coating agent.

(Wherein R ⁷ represents hydrogen or a methyl group, R _f represents a perfluoroalkyl group having 2 to 16 carbon atoms, and n represents an integer of 0 to 6)   The coating agent according to any one of claims 1 to 6, wherein the solvent is a fluorinated solvent.   8. The amount of the fluoropolymer with respect to the total amount of the fluoropolymer, the fluorescent agent, and the solvent is 0.05 to 30 wt%. Coating agent.