JP2006008953A - Coating composition for protection and coated product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating composition for protection, which can be used for a coating composition of a photocolor developing or photo-recording coating film and can improve both the light sensitivity and light resistance to ultra-violet rays of the above film simultaneously. <P>SOLUTION: The coating composition for protection is used for a coating film of a coating material containing a color-forming precursor with practically no color. The color-forming precursor can adjust a color phase by application of light energy. The coating composition for protection has the light transmission of at least 65% in a wavelength range used for a color phase adjustment before the adjustment and the transmission decreases after the color phase adjustment. Especially the composition is preferred to have the transmission of the wavelength of 360 nm of at least 65% before the above adjustment and of at most 50% after the adjustment. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a protective coating composition for coatings capable of color development or optical recording, and more specifically, a protective coating composition for improving light resistance against ultraviolet rays and the like while maintaining good photosensitivity of the coating film to be coated, and It relates to a painted article painted with it.

  The present inventor has previously filed a patent application as a novel coating composition capable of photo-coloring or optical recording (see Patent Document 1). A coating film coated with such a coating composition and dried is initially essentially colorless in an untreated state, but can be colored or recorded in an arbitrary hue by applying external energy such as light irradiation. For example, when producing multicolored color products, etc., it has the advantage that it can cope with the production of color products having various colors by preparing only one kind of colorless paint, An extremely useful coating composition is provided.

However, when the color coating film obtained by coloring the paint is exposed to sunlight outdoors or posted indoors for a long time, the background portion is colored by light, or the image portion is discolored or discolored. Had a problem of fading.
In general, as a method for improving the problems of coloring, discoloration or fading as described above, there are many protective coating compositions containing various ultraviolet absorbers, light stabilizers and the like (for example, Patent Documents 2 to 9). It is disclosed.

  However, these conventionally known protective coatings have absorption characteristics with respect to light in the ultraviolet region used for photochromication or optical recording, so that the coating film of the paint capable of photochromication or optical recording is the object of the present invention. In many cases, it has a fatal defect that the photosensitivity is greatly reduced.

Japanese Patent Application No. 2003-272944 JP-A-11-302590 JP-A-11-001640 Japanese Patent Laid-Open No. 09-279093 Japanese Patent Application Laid-Open No. 09-279092 JP 09-241541 A JP 09-059539 A JP 07-278468 A No. 96/036671

  The present invention has been made to solve the above problems, and is a protective coating applied to a coating film of a paint capable of optical recording, without impairing the good photosensitivity of the coating film, An object of the present invention is to provide a protective coating composition capable of improving the light resistance of a coating film against ultraviolet rays and the like.

The above object is achieved by a protective coating composition having the following characteristics.
<1> A protective coating applied to a coating film of a coating containing a substantially colorless dye-forming precursor capable of adjusting the hue by applying light energy, and used at the time of adjusting the hue A protective coating composition, wherein light transmittance in a wavelength region of light is at least 65% or more before the hue adjustment and decreases after the hue adjustment than before the hue adjustment.

<2> The protective coating composition as described in <1> above, wherein the light transmittance at a wavelength of 360 nm is 65% or more before the hue adjustment and 50% or less after the hue adjustment .

<3> Compounds represented by the following general formulas (A-1) to (A-4) and / or compounds represented by the general formula (B) and / or general formulas (C-1) to ( The protective coating composition as described in <1> or <2> above, which comprises a compound represented by C-2).

[In General Formulas (A-1) to (A-4), m represents 1 or 2. When m = 1 in A is formula (A-1), and in the general formula (A-2) ~ (A -4), -SO 2 R, -COR, -CO 2 R, -CONHR, -POR ¹ R ² , —CH ₂ R ³ or —SiR ⁴ R ⁵ R ⁶ , wherein R represents an alkyl group or an aryl group, and R ¹ and R ² are each independently an alkoxy group, an aryloxy group, represents an alkyl group or an aryl group, wherein R ³ represents at least one substituted phenyl group by a nitro group or a methoxy group, an alkyl group or an aryl group, each said R ⁴ to R ⁶ independently. When m = 2 in the general formula (A-1), A represents —SO ₂ R ⁷ SO ₂ —, —CO—, —COCO—, —COR ⁷ CO—, —SO ₂ — or —SO—, Here, R ⁷ represents an alkylene group or an arylene group. ]

[In General Formula (B), m represents 1 or 2, and n represents 0 or 1. A represents —SO ₂ R ¹⁰ , —COR ¹⁰ , —CO ₂ R ¹⁰ , —CONHR ¹⁰ , —POR ¹¹ R ¹² , —CH ₂ R ¹³ , or —SiR ¹⁴ R ¹⁵ R ¹⁶ when m = 1. Wherein R ¹⁰ represents an alkyl group, an alkenyl group, or an aryl group, R ¹¹ and R ¹² each independently represents an alkoxy group, an aryloxy group, an alkyl group, or an aryl group, and R ¹³ represents a nitro group Represents a phenyl group substituted with at least one group or a methoxy group, and each of R ^{14 to} R ¹⁶ independently represents an alkyl group or an aryl group. A represents —SO ₂ R ¹⁷ SO ₂ —, —CO—, —COCO—, —COR ¹⁷ CO—, —SO ₂ —, or —SO— when m = 2, wherein R ¹⁷ represents an alkylene. Represents a group, an alkenylene group, or an arylene group. R ^{1 to} R ⁹ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a halogen atom or —O—A, where A is as defined above for A. . ]

[In General Formulas (C-1) and (C-2), m represents 1 or 2. A is —SO ₂ R ¹ , —COR ¹ , —CO ₂ R ¹ , —CONHR ¹ , —POR ² R when m = 1 in General Formula (C-1) and in General Formula (C-2). ³ , —CH ₂ R ⁴ , or —SiR ⁵ R ⁶ R ⁷ , wherein R ¹ represents an alkyl group, an alkenyl group, or an aryl group, and R ² and R ³ are each independently an alkoxy group, Represents an aryloxy group, an alkyl group, or an aryl group, R ⁴ represents a phenyl group substituted with at least one of a nitro group or a methoxy group, and R ^{5 to} R ⁷ each independently represents an alkyl group, an alkenyl group, Or represents an aryl group. A represents —SO ₂ R ⁸ SO ₂ —, —CO—, —COCO—, —COR ⁸ CO—, —SO ₂ —, or —SO— when m = 2 in the general formula (C-1). Here, R ⁸ represents an alkylene group or an arylene group. Z ¹ and Z ³ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group or a halogen atom, Z ² represents the same as Z ¹ or represents —O—A, wherein A is the above Synonymous with A.
X and Y each independently represent a group represented by the following structural formula (3), an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylthio group, an alkylthio group, or —NR ⁹ R ¹⁰ , And R ⁹ represents a hydrogen atom or an alkyl group, and R ¹⁰ represents an alkyl group or an aryl group. ]

In [Formula ^(3), Z ¹ ~Z 3 has the same meaning as Z ¹ to Z ³ described above. W is -OR ⁸ O-, or -OCOR ⁸ CO ₂ - represents, wherein said R ⁸ has the same meaning as R ⁸ mentioned above. ]

<4> The compounds represented by the general formulas (A-1) to (A-4) and / or the general formula (B) and / or the general formulas (C-1) to (C-2) The protective coating composition as described in <3> above, which is encapsulated in a microcapsule.

<5> The protective coating composition according to any one of <1> to <4>, further comprising at least one polymer aqueous dispersion.

<6> The protective coating composition as described in <5> above, wherein the polymer aqueous dispersion contains at least one organosilicon resin.

<7> A coated article coated with the protective coating composition according to any one of <1> to <6> above.

  According to the present invention, there is provided a protective coating applied to a coating film of a coating capable of photochromic or optical recording, and the light resistance of the coating film against ultraviolet rays or the like without impairing the good light sensitivity of the coating film. It has become possible to provide a protective coating composition capable of improving the properties. Thereby, for example, by using only one type of coating composition and applying the protective coating of the present invention, a multicolor product having excellent light resistance and durability can be produced even with only one type of colorless coating. There are advantages, and a very useful protective coating composition can be provided. Moreover, the coated article using the same can be provided.

The protective coating composition of the present invention (hereinafter sometimes simply referred to as “protective coating”) is a substantially colorless pigment capable of adjusting the hue at least by the application of light energy. A protective coating applied to a coating film of a coating containing a forming precursor, wherein the light transmittance in the wavelength region of light used at the time of hue adjustment is at least 65% or more before the hue adjustment, and It is characterized by a decrease after the hue adjustment than before the hue adjustment.
In this way, by controlling the light transmittance in the wavelength region of the light used at the time of hue adjustment to be at least 65% or more before the hue adjustment and to decrease after the hue adjustment than before the hue adjustment. The protective coating of the present invention can improve the light resistance of the coated coating film, particularly the deterioration due to ultraviolet rays.

In particular, the protective coating composition of the present invention is preferably controlled so that the light transmittance at a wavelength of 360 nm is 65% or more before the hue adjustment and 50% or less after the hue adjustment. . In this way, by controlling the light transmittance at a wavelength of 360 nm before and after the hue adjustment process, it is possible to improve both the light sensitivity and the light resistance of the coating film of the paint containing the dye-forming precursor at a high level. it can.
The light transmittance at a wavelength of 360 nm after adjusting the hue is preferably 40% or less, more preferably 30% or less, and most preferably 20% or less from the viewpoint of further improving the light resistance of the coating film. preferable.
Hereinafter, although the main structure of the coating composition for protection of this invention is demonstrated in detail, this invention is not limited to these description matters.

(Compounds of general formulas (A-1) to (A-4))
The protective coating composition of the present invention is a compound represented by the following general formulas (A-1) to (A-4) from the viewpoint of maintaining good light sensitivity of the coated coating film and further improving light resistance. The form containing is preferable.

In the general formulas (A-1) to (A-4), m represents 1 or 2. When m = 1 in A is formula (A-1), and in the general formula (A-2) ~ (A -4), -SO 2 R, -COR, -CO 2 R, -CONHR, -POR ¹ R ² , —CH ₂ R ³ or —SiR ⁴ R ⁵ R ⁶ , wherein R represents an alkyl group or an aryl group, and R ¹ and R ² are each independently an alkoxy group, an aryloxy group, represents an alkyl group or an aryl group, wherein R ³ represents at least one substituted phenyl group by a nitro group or a methoxy group, an alkyl group or an aryl group, each said R ⁴ to R ⁶ independently. When m = 2 in the general formula (A-1), A represents —SO ₂ R ⁷ SO ₂ —, —CO—, —COCO—, —COR ⁷ CO—, —SO ₂ — or —SO—, Here, R ⁷ represents an alkylene group or an arylene group.

X represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a halogen atom in the general formulas (A-1), (A-3) and (A-4), and in the general formula (A-2) , An alkylene group, —OR ⁷ O— or —OCOR ⁷ CO ₂ —. W represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a halogen atom in the general formulas (A-1), (A-2) and (A-4), and in the general formula (A-3), , -OR ⁷ O-or -OCOR ⁷ CO ₂ - represents a. Y represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a halogen atom in the general formulas (A-1), (A-2) and (A-3), and in the general formula (A-4) , —OR ⁷ O—, —OCOR ⁷ CO ₂ —, —CH ₂ CH ₂ CO ₂ R ⁷ OCOCH ₂ CH ₂ —, —CH ₂ CH ₂ OCOR ⁷ CO ₂ CH ₂ CH ₂ —, or CH ₂ CH ₂ CON (R ⁸ ) R ⁷ N (R ⁸ ) COCH ₂ CH ₂ — is represented. Here, R ⁷ has the same meaning as R ⁷ in the description of A above, and R ⁸ represents a hydrogen atom or an alkyl group. Z represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.

  Of the above substituents, the alkyl group may be linear or branched, and may have an unsaturated bond. Further, these alkyl groups may be substituted with an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aryl group, a hydroxy group, or the like. The aryl group may be further substituted with an alkyl group, an alkoxy group or a halogen atom.

  Among the above substituents, the alkylene group may be linear or branched and may contain an unsaturated bond, an oxygen atom, a sulfur atom, or a nitrogen atom. The alkylene group may be further substituted with an alkoxy group, a hydroxy group, an aryloxy group, or an aryl group.

  Of the above substituents, the arylene group may be further substituted with an alkyl group, an alkoxy group, a halogen atom, or the like.

  Among the substituents represented by X, Y, and W, a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, a fluorine atom, A chlorine atom and a bromine atom are preferable, and among them, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or a chlorine atom is particularly preferable.

  Among the substituents represented by Z, a hydrogen atom, a chlorine atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms are preferable, and among them, a hydrogen atom and a chlorine atom are particularly preferable. An alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms are preferable.

  Among the substituents represented by R, an alkyl group having 1 to 18 carbon atoms and an aryl group having 6 to 18 carbon atoms are preferable, and among them, an alkyl group having 1 to 12 carbon atoms and 6 carbon atoms are particularly preferable. ~ 12 aryl groups are preferred.

Among the substituents represented by R ¹ and R ² , an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, and 6 to 6 carbon atoms. Twelve aryl groups are preferred.

Of the substituents represented by R ³ , 2-nitrophenyl group, 3,5-dimethoxyphenyl group, and 3,4,5-trimethoxyphenyl group are preferable.

Among the substituents represented by R ^{4 to} R ⁶ , an alkyl group having 1 to 12 carbon atoms and an aryl group having 6 to 12 carbon atoms are preferable, and among them, an alkyl group having 1 to 8 carbon atoms is particularly preferable. A phenyl group is preferred.

In the so-called bis body having two benzotriazole rings in the molecule, the substituent represented by R ⁷ is preferably an alkylene group having 1 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms, The substituent represented by R ⁸ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Of the substituents represented by A described above, —SO ₂ R is particularly preferable.

Specific examples of the substituents described above are given below, but the present invention is not limited thereto.
Among the substituents represented by X, Y, and W, monovalent ones include hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group. , T-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, allyl group, 2-butenyl group, benzyl group, α-dimethylbenzyl group, methoxy group, ethoxy group, propyloxy group, butyloxy group Octyloxy group, dodecyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxycarbonylethyl group, ethoxycarbonylethyl group, propyloxycarbonylethyl group, butyloxycarbonylethyl group, octyloxycarbonylethyl group, phenoxycarbonylethyl group, Phenyl group, tolyl group, chlorine atom, fluorine atom, bromine source And the like, those divalent, include the following.

  Specific examples of the substituent represented by Z include a hydrogen atom, a chlorine atom, a methyl group, an ethyl group, a propyl group, a hexyl group, a methoxy group, an ethoxy group, a propyloxy group, and an octyloxy group.

  Among the substituents represented by A, monovalent ones include methanesulfonyl group, ethanesulfonyl group, butanesulfonyl group, benzenesulfonyl group, 4-methylbenzenesulfonyl group, 2-mesitylenesulfonyl group, 4-methoxybenzene. Sulfonyl group, 4-octyloxybenzenesulfonyl group, 2,4,6-triisopropylbenzenesulfonyl group, β-styrenesulfonyl group, vinylbenzenesulfonyl group, 4-chlorobenzenesulfonyl group, 2,5-dichlorobenzenesulfonyl group, 2 , 4,5-trichlorobenzenesulfonyl group, 1-naphthalenesulfonyl group, 2-naphthalenesulfonyl group, quinolinesulfonyl group, thiophenesulfonyl group;

  Acetyl, propionyl, butyryl, pivaloyl, lauroyl, stearoyl, benzoyl, cinnamoyl, furoyl, nicotinoyl, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, hexylaminocarbonyl, phenylaminocarbonyl Group, diphenylphosphoryl group, diethylphosphoryl group, 2-nitrobenzyl group, 3,5-dimethoxybenzyl group, 3,4,5-trimethoxybenzyl group, trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, diethyl Examples include isopropylsilyl group, dimethylphenylsilyl group, diphenylmethylsilyl group, triphenylsilyl group and the like.

Examples of the divalent group include the following linking groups.

When A is —SiR ⁴ R ⁵ R ^6, a photoacid generator such as ammonium salt, diazonium salt, iodonium salt, sulfonium salt, phosphonium salt, onium salt may be used in combination for improving photoreactivity. Specific examples of these photoacid generators are detailed in “Organic Materials for Imaging” (1993) edited by the Organic Electronics Materials Research Group.

  Although the specific example of a compound represented by general formula (A-1)-(A-4) below is shown, this invention is not limited to these. These compounds can be used either alone or as a mixture of two or more.

When applying the protective coating containing the compounds represented by the general formulas (A-1) to (A-4), the solid content coating amount of the compound is preferably 0.05 to 3.0 g / m ^2. 0.1 to 2.0 g / m ² is more preferable. In this case, if the coating amount is less than 0.05 g / m ² , the light transmittance suppressing function, particularly the light transmittance in the ultraviolet region is reduced after the light irradiation in the wavelength region necessary for hue adjustment is completed. However, if the coating amount is more than 3.0 g / m ² , light having a wavelength in a region necessary for adjusting the light transmittance, particularly for hue adjustment, may be difficult. Lowering the transmittance of the optical recording medium sometimes hinders optical recording properties.

(Compound of general formula (B))
In addition, the protective coating composition of the present invention also preferably includes a compound represented by the following general formula (B) from the viewpoint of maintaining good light sensitivity of the coated coating film and further improving light resistance. .

In the general formula (B), m represents 1 or 2, and n represents 0 or 1. A represents —SO ₂ R ¹⁰ , —COR ¹⁰ , —CO ₂ R ¹⁰ , —CONHR ¹⁰ , —POR ¹¹ R ¹² , —CH ₂ R ¹³ , or —SiR ¹⁴ R ¹⁵ R ¹⁶ when m = 1. Wherein R ¹⁰ represents an alkyl group, an alkenyl group, or an aryl group, R ¹¹ and R ¹² each independently represents an alkoxy group, an aryloxy group, an alkyl group, or an aryl group, and R ¹³ represents a nitro group Represents a phenyl group substituted with at least one group or a methoxy group, and each of R ^{14 to} R ¹⁶ independently represents an alkyl group or an aryl group. A represents —SO ₂ R ¹⁷ SO ₂ —, —CO—, —COCO—, —COR ¹⁷ CO—, —SO ₂ —, or —SO— when m = 2, wherein R ¹⁷ represents an alkylene. Represents a group, an alkenylene group, or an arylene group. R ^{1 to} R ⁹ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a halogen atom or —O—A, where A is as defined above for A. .

  Of the above substituents, the alkyl group may be linear or branched, and may have an unsaturated bond. Furthermore, these alkyl groups may be substituted with an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aryl group, a hydroxy group, or the like. The aryl group may be further substituted with an alkyl group, an alkoxy group, a hydroxy group, or a halogen atom.

  Of the above substituents, the arylene group may be further substituted with an alkyl group, an alkoxy group, a halogen atom, or the like.

Among the substituents represented by R ^{1 to} R ⁹ , a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and the number of carbon atoms A 6-18 aryl group, a fluorine atom, a chlorine atom, and a bromine atom are preferable, and among them, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or a chlorine atom. Is preferred. Also, when the R ¹ to R ⁹ represents -O-A is preferably substituted at a position of R ^9.
Among the substituents represented by R ¹⁰ , an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 3 to 24 carbon atoms, and an aryl group having 6 to 18 carbon atoms are preferable, and among them, the number of carbon atoms is particularly preferable. An alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, and an aryl group having 6 to 12 carbon atoms are preferable.

Among the substituents represented by R ¹¹ and R ¹² , an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, and 6 to 6 carbon atoms Twelve aryl groups are preferred.

Of the substituents represented by R ¹³ , 2-nitrophenyl group, 3,5-dimethoxyphenyl group, and 3,4,5-trimethoxyphenyl group are preferable.

Of the substituents represented by R ^{14 to} R ¹⁶ , an alkyl group having 1 to 12 carbon atoms and an aryl group having 6 to 12 carbon atoms are preferable. Among these, an alkyl group having 1 to 8 carbon atoms and a phenyl group are particularly preferable.

In the case of m = 2, that is, in a so-called bis-form, the substituent represented by R ¹⁷ is preferably an alkylene group having 1 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms.
Of the substituents represented by A, —SO ₂ R ¹⁰ is particularly preferred.

Specific examples of the above-described substituents are shown below, but the present invention is not limited to these.
Among the substituents represented by R ^{1 to} R ⁹ , monovalent ones include hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group. , T-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, allyl group, 2-butenyl group, benzyl group, α-dimethylbenzyl group, methoxy group, ethoxy group, propyloxy group, butyloxy group Octyloxy group, dodecyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxycarbonylethyl group, ethoxycarbonylethyl group, propyloxycarbonylethyl group, butyloxycarbonylethyl group, octyloxycarbonylethyl group, phenoxycarbonylethyl group, Phenyl group, tolyl group, chlorine atom, fluorine atom, bromine atom Etc.

  Among the substituents represented by A, monovalent ones include methanesulfonyl group, ethanesulfonyl group, butanesulfonyl group, benzenesulfonyl group, 4-methylbenzenesulfonyl group, 2-mesitylenesulfonyl group, 4-methoxybenzene. Sulfonyl group, 4-octyloxybenzenesulfonyl group, 2,4,6-triisopropylbenzenesulfonyl group, β-styrenesulfonyl group, vinylbenzenesulfonyl group, 4-chlorobenzenesulfonyl group, 2,5-dichlorobenzenesulfonyl group, 2 , 4,5-trichlorobenzenesulfonyl group, 1-naphthalenesulfonyl group, 2-naphthalenesulfonyl group, quinolinesulfonyl group, thiophenesulfonyl group;

  Acetyl, propionyl, butyryl, pivaloyl, lauroyl, stearoyl, benzoyl, cinnamoyl, furoyl, nicotinoyl, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, hexylaminocarbonyl, phenylaminocarbonyl Group, diphenylphosphoryl group, diethylphosphoryl group, 2-nitrobenzyl group, 3,5-dimethoxybenzyl group, 3,4,5-trimethoxybenzyl group, trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, diethyl Isopropylsilyl group, dimethylphenylsilyl group, diphenylmethylsilyl group, triphenylsilyl group, o-hydroxycinnamoyl group, o-hydroxy-α-methylcinnamoyl group, o-hydroxy-β-methyl Examples include a rucinnamoyl group.

  Examples of the divalent group include the following linking groups.

When A is —SiR ¹⁴ R ¹⁵ R ^16, a photoacid generator such as an ammonium salt, a diazonium salt, an iodonium salt, a sulfonium salt, a phosphonium salt, or an onium salt may be used in combination for improving photoreactivity. Specific examples of the photoacid generator are described in detail in “Organic Materials for Imaging” (1993) edited by the Organic Electronics Materials Research Group.

  Specific examples of the compound represented by formula (B) are shown below, but the present invention is not limited thereto. These compounds can be used either alone or as a mixture of two or more.

When applying a protective coating containing the compound represented by the general formula (B), the solid content coating amount of the compound is preferably 0.05 to 3.0 g / m ² , preferably 0.1 to 2.0 g. / M ² is more preferable. In this case, if the coating amount is less than 0.05 g / m ² , the light transmittance suppressing function, particularly the light transmittance in the ultraviolet region is reduced after the light irradiation in the wavelength region necessary for hue adjustment is completed. However, if the coating amount is more than 3.0 g / m ² , the light transmittance adjustment function, particularly light having a wavelength in a region necessary for optical recording may be required. The optical recording performance may be hindered due to the tendency of the transmittance of the optical recording medium to decrease.

(Compounds of general formulas (C-1) and (C-2))
The protective coating composition of the present invention is represented by the following general formulas (C-1) and (C-2) from the viewpoint of maintaining good light sensitivity of the coated coating film and further improving light resistance. A form containing the compound is also preferred.

In the above general formulas (C-1) and (C-2), m represents 1 or 2. A is —SO ₂ R ¹ , —COR ¹ , —CO ₂ R ¹ , —CONHR ¹ , —POR ² R when m = 1 in General Formula (C-1) and in General Formula (C-2). ³ , —CH ₂ R ⁴ , —SiR ⁵ R ⁶ R ⁷ , wherein R ¹ represents an alkyl group, an alkenyl group, or an aryl group, and each of R ² and R ³ independently represents an alkoxy group, an aryloxy group, R ⁴ represents a phenyl group substituted with at least one nitro group or methoxy group, and R ^{5 to} R ⁷ each independently represents an alkyl group, an alkenyl group, or an aryl group. Represents a group. A represents —SO ₂ R ⁸ SO ₂ —, —CO—, —COCO—, —COR ⁸ CO—, —SO ₂ —, or —SO— when m = 2 in the general formula (C-1). Here, R ⁸ represents an alkylene group or an arylene group. Z ¹ and Z ³ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group or a halogen atom, Z ² represents the same as Z ¹ or represents —O—A, wherein A is the above Synonymous with A.
X and Y each independently represent a group represented by the following structural formula (3), an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylthio group, an alkylthio group, or —NR ⁹ R ¹⁰ , And R ⁹ represents a hydrogen atom or an alkyl group, and R ¹⁰ represents an alkyl group or an aryl group.

In the above structural formula ^(3), Z ¹ ~Z 3 has the same meaning as Z ¹ to Z ³ described above. W is -OR ⁸ O-, or -OCOR ⁸ CO ₂ - represents, wherein said R ⁸ has the same meaning as R ⁸ mentioned above.

  Of the above substituents, the alkyl group may be linear or branched, and may have an unsaturated bond. Further, these alkyl groups may be substituted with an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aryl group, a hydroxy group, or the like. The aryl group may be further substituted with an alkyl group, an alkoxy group, a hydroxy group, or a halogen atom.

  Of the above substituents, the arylene group may be further substituted with an alkyl group, an alkoxy group, a halogen atom, or the like.

Among the substituents represented by X and Y, a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and 6 to 6 carbon atoms 18 aryloxy groups, alkylthio groups having 1 to 18 carbon atoms, arylthio groups having 6 to 18 carbon atoms, —NR ⁹ R ¹⁰ having 1 to 18 carbon atoms, fluorine atoms, chlorine atoms, bromine atoms are preferable. Among these, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, and a carbon atom An alkylthio group having 1 to 12 carbon atoms, an arylthio group having 6 to 12 carbon atoms, —NR ⁹ R ¹⁰ having 4 to 18 carbon atoms, and a chlorine atom are preferable.
Moreover, when X and Y are groups represented by the structural formula (3), those having a total number of carbon atoms of 8 or more are preferable.

Among the substituents represented by Z ^{1 to} Z ³ , a hydrogen atom, a chlorine atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, and an alkyl group having 1 to 12 carbon atoms An alkoxy group and an aryl group having 6 to 18 carbon atoms are preferable, and among them, a hydrogen atom, a chlorine atom, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms are particularly preferable.

Among the substituents represented by R ¹ , an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, and an aryl group having 3 to 18 carbon atoms are preferable, and among these, the number of carbon atoms is particularly preferable. An alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 15 carbon atoms, and an aryl group having 6 to 12 carbon atoms are preferable.

Among the substituents represented by R ² and R ³ , an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, and 6 to 6 carbon atoms Twelve aryl groups are preferred.

Of the substituents represented by R ⁴ , 2-nitrophenyl group, 3,5-dimethoxyphenyl group, and 3,4,5-trimethoxyphenyl group are preferable.

Among the substituents represented by R ^{5 to} R ⁷ , an alkyl group having 1 to 12 carbon atoms and an aryl group having 6 to 12 carbon atoms are preferable, and among them, an alkyl group having 1 to 8 carbon atoms, A phenyl group is preferred.

In the case of m = 2 in the general formula (C-1) and in the case of the general formula (C-2), that is, in a so-called bis body, the substituent represented by R ⁸ has 1 to 12 carbon atoms. An alkylene group or an arylene group having 6 to 12 carbon atoms is preferred.
Of the substituents represented by A, —SO ₂ R ¹ is particularly preferable.

Specific examples of the above-described substituents are shown below, but the present invention is not limited to these.
Among the substituents represented by X and Y, monovalent ones include hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t -Butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, allyl group, 2-butenyl group, benzyl group, α-dimethylbenzyl group, methoxy group, ethoxy group, propyloxy group, butyloxy group, octyl group Oxy group, dodecyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxycarbonylethyl group, ethoxycarbonylethyl group, propyloxycarbonylethyl group, butyloxycarbonylethyl group, octyloxycarbonylethyl group, phenoxycarbonylethyl group, phenyl group , Tolyl group, chlorine atom, fluorine atom, bromine atom And the like.

  Among the substituents represented by X and Y, the divalent ones and the substituents represented by W include the following.

Specific examples of the substituent represented by Z ^{1 to} Z ³ include a hydrogen atom, a chlorine atom, a methyl group, an ethyl group, a propyl group, a hexyl group, a methoxy group, an ethoxy group, a propyloxy group, and an octyloxy group. Can be mentioned.

  Among the substituents represented by A, monovalent ones include methanesulfonyl group, ethanesulfonyl group, butanesulfonyl group, benzenesulfonyl group, 4-methylbenzenesulfonyl group, 2-mesitylenesulfonyl group, 4-methoxybenzene. Sulfonyl group, 4-octyloxybenzenesulfonyl group, 2,4,6-triisopropylbenzenesulfonyl group, β-styrenesulfonyl group, vinylbenzenesulfonyl group, 4-chlorobenzenesulfonyl group, 2,5-dichlorobenzenesulfonyl group, 2 , 4,5-trichlorobenzenesulfonyl group, 1-naphthalenesulfonyl group, 2-naphthalenesulfonyl group, quinolinesulfonyl group, thiophenesulfonyl group;

  Acetyl, propionyl, butyryl, pivaloyl, lauroyl, stearoyl, benzoyl, cinnamoyl, furoyl, nicotinoyl, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, hexylaminocarbonyl, phenylaminocarbonyl Group, diphenylphosphoryl group, diethylphosphoryl group, 2-nitrobenzyl group, 3,5-dimethoxybenzyl group, 3,4,5-trimethoxybenzyl group, trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, diethyl Isopropylsilyl group, dimethylphenylsilyl group, diphenylmethylsilyl group, triphenylsilyl group, o-hydroxycinnamoyl group, o-hydroxy-α-methylcinnamoyl group, o-hydroxy-β-methyl Examples include a rucinnamoyl group.

  The following are mentioned as a bivalent thing.

When A is -SiR ⁴ R ⁵ R ⁶ , a photoacid generator may be used in combination for improving photoreactivity, as in the general formula (B).

  Specific examples of the compounds represented by the general formulas (C-1) and (C-2) are shown below, but the present invention is not limited thereto. These compounds can be used either alone or as a mixture of two or more.

When a protective coating containing the compounds represented by the general formulas (C-1) and (C-2) is applied, the solid content coating amount of the compound is preferably 0.05 to 3.0 g / m ^2. 0.1 to 2.0 g / m ² is more preferable. In this case, if the coating amount is less than 0.05 g / m ² , the light transmittance suppressing function, particularly the light transmittance in the ultraviolet region is reduced after the light irradiation in the wavelength region necessary for hue adjustment is completed. However, if the coating amount is more than 3.0 g / m ² , the light transmittance adjustment function, particularly light having a wavelength in a region necessary for optical recording may be required. The optical recording performance may be hindered due to the tendency of the transmittance of the optical recording medium to decrease.

  The compounds represented by the general formulas (A-1) to (A-4), the general formula (B1), and the general formulas (C-1) to (C-2) described above have a hue by applying light energy. In the adjustment process, the irradiation light is hardly absorbed, and the light is irradiated after the color forming dye is formed, so that the ultraviolet light can be absorbed and the light stability of the color developing dye can be improved.

In the protective coating composition of this invention, each represented by general formula (A-1)-(A-4), general formula (B), and general formula (C-1)-(C-2). The compounds may be used alone or in any combination of two to three compounds.
In addition, the protective coating composition containing the compound represented by general formula (A-1)-(A-4), general formula (B1), and general formula (C-1)-(C-2). When preparing, (1) a method of using a solid dispersion, (2) a method of using an emulsion dispersion, (3) a method of using a polymer dispersion, (4) a method of using a latex dispersion, (5) There are methods for use in microcapsules. Among these, the protective coating of the present invention is preferably (5) a method for use in microcapsules.

(Microencapsulation)
As a method for emulsifying and dispersing the compounds represented by the general formulas (A-1) to (A-4), the general formula (B1), and the general formulas (C-1) to (C-2), first, The compound represented by the formula is dissolved in oil. Such oils include, for example, low boiling auxiliary solvents such as acetate ester, methylene chloride, cyclohexanone and / or phosphate ester, phthalate ester, acrylic ester, methacrylic ester, other carboxylic acid ethesul, fatty acid amide, alkyl Biphenyl, alkylated terphenyl, alkylated naphthalene, diarylethane, chlorinated paraffin, alcohol-based, phenol-based, ether-based, monoolefin-based, epoxy-based and the like. Specific examples of compounds include tricresyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, tricyclohexyl phosphate, dibutyl phthalate, dioctyl phthalate, dilaurate phthalate, dicyclohexyl phthalate, butyl olefinate, diethylene glycol benzoate, dioctyl sebacate, sebacin Dibutyl acid, dioctyl adipate, trioctyl trimellitic acid, acetyl triethyl citrate, octyl maleate, dibutyl maleate, isoamyl biphenyl, chlorinated paraffin, diisopropyl naphthalene, 1,1'-ditolyl ethane, 2,4-dita-shariamil Phenol, N, N-dibutyl-2-butoxy-5-tert-octylaniline, 2-ethylhexyl hydroxybenzoate, polyethylene glycol Include high boiling oils such Lumpur. Among these, alcohol-based, phosphoric ester-based, carboxylic acid-based ester, alkylated biphenyl, alkylated terphenyl, alkylated naphthalene, and diarylethane are particularly preferable. Furthermore, you may add antioxidants, such as a hindered phenol and a hindered amine, to the said high boiling point oil. The oil preferably has an unsaturated fatty acid, such as α-methylstyrene dimer. As the α-methylstyrene dimer, for example, there is a trade name “MSD100” manufactured by Mitsui Toatsu Chemicals.

An oil solution containing the compound represented by the above general formula is added to an aqueous solution of a water-soluble polymer and emulsified and dispersed by a colloid mill, a homogenizer, or ultrasonic waves. As the water-soluble polymer used at that time, a water-soluble polymer such as polyvinyl alcohol is used, but an emulsion or latex of a hydrophobic polymer may be used in combination.
Examples of the water-soluble polymer include polyvinyl alcohol, silanol-modified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, amino-modified polyvinyl alcohol, itaconic acid-modified polyvinyl alcohol, styrene-maleic anhydride copolymer, butadiene maleic anhydride copolymer, and ethylene anhydride. Examples include maleic acid copolymer, isobutylene maleic anhydride copolymer, polyacrylamide, polystyrene sulfonic acid, polyvinyl pyrrolidone, ethylene-acrylic acid copolymer, and gelatin. Among these, carboxy-modified polyvinyl alcohol is particularly preferable. Examples of the hydrophobic polymer emulsion or latex include styrene-butadiene copolymer, carboxy-modified styrene-butadiene copolymer, and acrylonitrile-butadiene copolymer. At this time, a conventionally known surfactant or the like may be added as necessary.

  As the microencapsulation method, a conventionally known microencapsulation method can be used. That is, the compound represented by the above general formula and the microcapsule wall precursor are dissolved in an organic solvent that is hardly soluble or insoluble in water, and is poured into an aqueous solution containing a water-soluble polymer, and a stirring means such as a homogenizer is provided. It can be prepared by emulsifying and dispersing, and raising the temperature to form a polymer substance that becomes a microcapsule wall at the oil / water phase interface. Specific examples of the polymer material that forms the wall film of such a microcapsule include, for example, polyurethane resin, polyurea resin, polyamide resin, polyester resin, polycarbonate resin, aminoaldehyde resin, melamine resin, polystyrene resin, and styrene-acrylate. Examples thereof include a polymer resin, a styrene-methacrylate copolymer resin, gelatin, and polyvinyl alcohol. Among these, a microcapsule having a wall film made of polyurethane-urea resin is particularly preferable.

  A microcapsule having a wall film made of polyurethane-urea resin is mixed in a core material to be encapsulated with a microcapsule wall precursor such as polyisocyanate and dissolved in an aqueous solution in which a water-soluble polymer such as polyvinyl alcohol is dissolved. It is produced by emulsifying and dispersing, and heating the emulsified dispersion to cause a polymer formation reaction at the oil droplet interface.

  Specific examples of the polyvalent isocyanate compound used in this case are shown below. For example, m-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, naphthalene-1,4-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'- Diphenylmethane-4,4′-diisocyanate, xylene-1,4-diisocyanate, 4,4′-diphenylpropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate, butylene-1,2-diisocyanate, Diisocyanates such as cyclohexylene-1,2-diisocyanate, cyclohexylene-1,4-diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, toluene Triisocyanates such as 2,4,6-triisocyanate, tetraisocyanates such as 4,4'-dimethyldiphenylmethane-2,2 ', 5,5'-tetraisocyanate, hexamethylene diisocyanate and trimethylolpropane Adducts of 2,4-tolylene diisocyanate and trimethylolpropane, adducts of xylylene diisocyanate and trimethylolpropane, isocyanate prepolymers such as adducts of tolylene diisocyanate and hexanetriol, etc. If necessary, two or more kinds of isocyanate compounds can be used together, and among these, polyisocyanates having three or more isocyanate groups in the molecule are particularly preferable.

In the microencapsulation method, as the organic solvent for dissolving the compound represented by the general formula, oil shown by emulsification dispersion can be used. The same applies to water-soluble polymers.
As a particle size of a microcapsule, 0.1-1.0 micrometer is preferable, More preferably, it is the range of 0.2-0.7 micrometer.

(Reducing agent)
In the present invention, in order to further reduce the coloration at the time of photo-fading, the compounds known as reducing agents are represented by the aforementioned general formulas (A-1) to (A-4), the general formula (B1), and the general formula. It can be used with the compounds represented by (C-1) to (C-2). This reducing agent may be inside or outside the microcapsule when the microcapsule is used. When the reducing agent is outside the microcapsule, the reducing agent enters the microcapsule when the color is developed under heat. Such additives include hydroquinone compounds, hydrazide compounds, hydroxy compounds, phenidone compounds, catechol compounds, resorcinol compounds, hydroxyhydroquinone compounds, pyrologricinol compounds, phenol compounds, phenyl hydrazide compounds, Examples thereof include gallic acid compounds, ascorbic acid compounds, and ethylene glycol compounds. Furthermore, these are described in JP-A-3-191341, JP-A-3-25434, JP-A-1-2529593, JP-A-2-302753, JP-A-1-129247, JP-A-1-227145. No. 1, JP-A-1-243048, JP-A-2-262649, and the like. Specific examples include the following compounds in addition to N-phenylacetohydrazide, N-phenylbutyrylhydrazide, pt-butylphenol, and 2-azidobenzoxazole.

(Dye-forming precursor)
The protective coating composition of the present invention is suitably applied to a coating film of a coating containing a substantially colorless pigment-forming precursor capable of adjusting the hue by applying light energy. As a paint containing such a dye-forming precursor, for example, by applying external light energy, a part of the dye-forming precursor is decomposed, and then a dye is formed by heating or the like. Any paint may be used as long as it is involved in hue adjustment such that the dye-forming precursor is decomposed, and conventionally known ones can be used. Among these, as the dye-forming precursor, those utilizing a reaction between a diazonium salt compound and a coupler are preferable, and those containing a basic substance that further promotes the reaction are more preferable.

The said diazonium salt compound is a compound shown below, and these can control the maximum absorption wavelength by the position and kind of substituent of Ar part.
Ar-N ₂ ⁺ · X ⁻
In the above formula, Ar represents an aryl group, and X ⁻ represents an acid anion.

  Specific examples of the diazonium salt compound include 4- (N- (2- (2,4-di-tert-amylphenoxy) butyryl) piperazino) benzenediazonium, 4-dioctylaminobenzenediazonium, 4- (N- ( 2-ethylhexanoyl) piperazino) benzenediazonium, 4-dihexylamino-2-hexyloxybenzenediazonium, 4-N-ethyl-N-hexadecylamino-2-ethoxybenzodiazonium, 3-chloro-4-dioctylamino- 2-octyloxyobenzenediazonium, 2,5-dibutoxy-4-morpholinobenzenediazonium, 2,5-octoxy-4-morpholinobenzenediazonium, 2,5-dibutoxy-4- (N- (2-ethylhexanoyl) Piperazino) benzenediazonium 2,5-diethoxy-4- (N- (2- (2,4-di-tert-amylphenoxy) butyryl) piperazino) benzenediazonium, 2,5-dibutoxy-4-tolylthiobenzenediazonium, 3- (2 -Octyloxyethoxy) -4-Morofolinobenzenediazonium and other acid anion salts and the following diazonium salt compounds (D-1 to 5) may be mentioned. In particular, hexafluorophosphate salt, tetrafluoroborate salt, and 1,5-naphthalene sulfonate salt are preferable.

Among these diazonium salt compounds, a particularly preferable compound in the present invention is 4- (N- (2- (2,4-di-tert-amylphenoxy) butyryl) piperazino) which is decomposed by light having a wavelength of 300 to 400 nm. Benzenediazonium, 4-dioctylaminobenzenediazonium, 4- (N- (2-ethylhexanoyl) piperazino) benzenediazonium, 4-dihexylamino-2-hexyloxybenzenediazonium, 4-N-ethyl-N-hexadecylamino 2-ethoxybenzodiazonium, 2,5-dibutoxy-4- (N- (2-ethylhexanoyl) piperazino) benzenediazonium, 2,5-diethoxy-4- (N- (2- (2,4-di) -Tert-amylphenoxy) butyryl) piperazino) benzenedia Compounds shown iodonium or above examples (D-3 to 5) and the like. Here, the maximum absorption wavelength of the diazonium salt compound was measured with a spectrophotometer (Shimazu “MPS-2000”) obtained by coating each compound with a coating thickness of 0.1 g / m ² to 1.0 g / m ^2. It is.

  Examples of couplers that react with the diazonium salt when heated include resorcin, flurglucin, sodium 2,3-dihydroxynaphthalene-6-sulfonate, 1-hydroxy-2-naphthoic acid morpholinopropylamide, 1,5-dihydroxy Naphthalene, 2,3-dihydroxynaphthalene, 2,3-dihydroxy-6-sulfanylnaphthalene, 2-hydroxy-3-naphthoic acid anilide, 2-hydroxy-3-naphthoic acid ethanolamide, 2-hydroxy-3-naphthoic acid octyl Amide, 2-hydroxy-3-naphthoic acid-N-dodecyloxypurpyramide, 2-hydroxy-3-naphthoic acid tetradecylamide, acetanilide, acetoacetanilide, benzoylacetanilide, 2-chloro-5-octylacetoaceto Lido, 1-phenyl-3-methyl-5-pyrazolone, 1- (2′-octylphenyl) -3-methyl-5-pyrazolone, 1- (2 ′, 4 ′, 6′-trichlorophenyl) -3- Benzamido-5-pyrazolone, 1- (2 ′, 4 ′, 6′-trichlorophenyl) -3-anilino-5-pyralone, 1-phenyl-3-phenylacetamido-5-pyrazolone, and the following (C -1-6) and the like. These couplers can be used in combination of two or more to obtain the desired color hue.

  In addition to the inorganic or organic basic compound, the basic substance includes a compound that decomposes upon heating and releases an alkaline substance. Typical examples include organic ammonium salts, organic amines, amides, ureas and thioureas and their derivatives, thiazoles, pyrroles, pyrimidines, piperazines, guanidines, indoles, imidazoles, imidazolines, triazoles. , Morpholines, piperidines, amidines, formazines, pyridines and the like nitrogen-containing compounds. Specific examples thereof include tricyclohexylamine, tribenzylamine, octadecylbenzylamine, stearylamine, allylurea, thiourea, methylthiourea, allylthiourea, ethylenethiourea, 2-benzylimidazole, 4-phenylimidazole, 2-phenyl- 4-methylimidazole, 2-undecylimidazoline, 2,4,5-trifuryl-2-imidazoline, 1,2-diphenyl-4,4-dimethyl-2-imidazoline, 2-phenyl-2-imidazoline, 1,2 , 3-triphenylguanidine, 1,2-dicyclohexylguanidine, 1,2,3-tricyclohexylguanidine, guanidine trichloroacetate, N, N′-dibenzylpiperazine, 4,4′-dithiomorpholine, morpholinium trichloro Acetate 2-amino-benzothiazole, and the like 2-benzoyl-hydrazino-benzothiazole. These can also use 2 or more types together.

(Polymer aqueous dispersion)
From the viewpoint of the working environment, the protective coating composition of the present invention preferably has at least one aqueous binder as its binder. Such an aqueous binder may be a mixture of various binders, and the ratio (solid content) of the binder in the protective coating composition is 3 to 3 based on the mass of the dry substance in the coating composition. 95 mass% is preferable and 5-75 mass% is more preferable.

  In order to improve the pot life as a protective coating, the coating composition can optionally contain an emulsifier or emulsifier mixture. As such emulsifiers, alkyl- and / or aryl ethoxylates are particularly suitable, in particular nonionic alkyl- and / or aryl ethoxylates, in particular polyaryl- and / or polyalkyl polyethylene glycol ethers. Yes. The total content of the emulsifier in the coating composition is preferably up to 10% by weight, more preferably up to 5% by weight, particularly preferably 0.5 to 3% by weight, based on the binder.

  The aqueous binder used in the protective coating of the present invention is advantageously a polymer aqueous dispersion based on homopolymer and / or copolymer, wherein the homopolymer and / or copolymer is at least one olefinic non-polymer. Those containing saturated monomers as constituent monomers are advantageous. Particularly preferred are 70 to 99% by weight of monoalcohols having 1 to 12 carbon atoms, especially monoalcohols having 1 to 8 carbon atoms, specifically methanol, ethanol, isopropanol, based on the total weight of monomers. Acrylic and methacrylic esters of isobutanol, n-butanol and 2-ethylhexyl alcohol, vinyl aromatic monomers, vinyl esters of alkane monocarboxylic acids having 1 to 12 carbon atoms, such as vinyl acetate, vinyl propionate, Vinyl-n-butyrate, vinyl laurate, “VeoVa® 9” and “VeoVa® 10” (Shell-Chemie, α, α-dialkyl-branched monocarboxylic acid vinyl ester), vinyl halides such as , Vinyl chloride and vinylidene chloride, α, A radical selected from the group consisting of monoolefinically unsaturated nitrites, such as acrylonitrile and methacrylonitrile, and alkyl esters of monoolefinically unsaturated dicarboxylic acids, such as maleic acid and fumaric acid-di-n-butyl ester It is a copolymer containing a polymerizable olefinically unsaturated compound.

  The copolymer further comprises 0.3 to 10% by weight, more preferably 0.5 to 5% by weight of α, β-monoolefinically unsaturated monomer, for example acrylic acid, based on the total weight of monomers. Contains methacrylic acid, itaconic acid, maleic acid and fumaric acid and optionally amides substituted at the nitrogen atom, for example acrylamide, methacrylamide, N-methylolacrylamide and N-butoxymethacrylamide Form is desirable.

  Furthermore, 0 to 20% by weight, preferably 0.5 to 5% by weight, based on the total weight of monomers, of hydroxyl-containing monomers, for example hydroxyalkyl acrylates and methacrylates, in particular hydroxyethyl methacrylate and hydroxypropyl methacrylate, and / or Acetylacetoxy group-containing monomers that improve wet adhesion, especially allyl acetoacetate, acetylacetoxy-ethyl methacrylate and acetylacetoxybutyl methacrylate, and / or monomers that crosslink, such as epoxy group-containing monomers and silane group-containing monomers, especially Glycidyl laurate, glycidyl methacrylate, vinylmethoxysilane and methacryloxypropyltrimethoxysilane, and / or amino group, ureido group or N-heterocyclic group Polymerizable monomer containing, for example, dimethylaminoethyl acrylate and methacrylate, N- (2-methacryloylethyl) -ethylene urea selected from the group consisting of ethylene urea and / or keto group-containing monomer, for example diacetone acrylamide Functional monomers such as diacetone methacrylamide, acrolein and 2-butanone methacrylate may be contained in the copolymer.

  In the above self-crosslinking polymer aqueous dispersion, the keto group-containing polymer contains a bifunctional or polyfunctional carboxylic acid hydrazide, for example, adipic acid hydrazide, up to 5% by mass based on the total mass of monomers. Also good.

Among the polymer aqueous dispersions used in the protective coating of the present invention, those containing at least one organosilicon resin are preferable from the viewpoint of having excellent coating film protecting ability.
As such an organosilicon resin, an organosilicon-containing monomer having at least one polymerizable unsaturated group and at least one siloxane bond in the molecule, and copolymerization with the monomer are possible. And a copolymer resin copolymerized from a polymerizable monomer.

  Examples of the organosilicon-containing monomer having at least one polymerizable unsaturated group and at least one siloxane bond in the molecule include, for example, vinyldimethylpolysiloxane and γ-methacryloxypropyldimethylpolysiloxane. Vinyldiethylpolysiloxane, γ-methacryloxypropyldiethylpolysiloxane, divinyldimethylpolysiloxane, bis (γ-methacryloxypropyl) dimethylpolysiloxane, and the like.

  Examples of polymerizable monomers that can be copolymerized with these monomers include unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, and fumaric acid, and salts thereof. Specific examples include methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and (meth) acrylic acid. The organosilicon resin can be obtained by a known method. it can.

  In the binder for protective coatings of the present invention, the blending amount of the organosilicon resin is preferably 50 to 90% by mass, and if the resin is less than 50% by mass, the coating film protecting ability is not sufficient, and after coating, There is a possibility that the coating film becomes brittle, and even if it exceeds 90% by mass, a protective effect proportional to the blending amount cannot be obtained, and the cost of the protective coating may be increased.

  The protective paint is preferably an emulsion paint. In that case, it is difficult to form a film as a coating film in a temperature range below the minimum film-forming temperature, so that a minimum film-forming aid is added to use as an emulsion paint. It is desirable to control the film temperature from room temperature to about 0 ° C. Examples of the film-forming aid that can be used for this purpose include various plasticizers such as DBP, higher glycerin, propylene ether, ethylene glycol, diethylene glycol, alkylene glycol, propylene glycol, and high-boiling organic solvents such as “butyl carbitol. , “Butyl cellosolve” (both trade names made by Union Carbide), “Texanol” (trade names made by Eastman Chemical), and the like.

  As a preferable film-forming auxiliary, propylene glycol and “texanol” which are effective for lowering the minimum film-forming temperature can be preferably used, particularly preferably propylene glycol-based, because they have good compatibility with the binder resin in the present invention. And methyl ether, n-butyl ether, acetate, and phenyl ether.

  Methods for improving the film-forming properties of emulsion-type paints include a method of drying at a high temperature by heating after coating, and a method of facilitating film formation by lowering the minimum film-forming temperature (MFT) of the paint. There is. The film-forming aid has the effect of lowering the MFT by blending this with the plasticization of the emulsion resin and facilitating the fusion of the emulsion particles. The blending amount of the film-forming auxiliary is preferably 1 to 5 parts by mass, and if it is less than 1 part by mass, the minimum film-forming temperature is not sufficiently lowered and it takes time to form a coating film. There is a problem that the coated film becomes too soft, the strength of the coated film decreases, and the water resistance of the coated film decreases.

  In addition, as additives that can be added to the protective coating, a dispersant, an antifoaming agent, an anti-settling agent, a stabilizer, an anti-aging agent, a thixotropy-imparting agent, and the like can be appropriately added as necessary.

  The protective coating according to the present invention can be produced by a conventionally known coating mixing and dispersing method. In particular, a method for producing an emulsion paint is recommended, but it is not limited to a specific method, and a ball mill, a roll mill, a paint shaker, a planetary mixer, a dissolver, a kneader, an attritor, a glen mill, and the like can be used.

  The protective coating according to the present invention can be applied by any coating method depending on the case, but considering that it is applied only to an arbitrary part, air spray coating, airless spray coating, and various electrostatic coatings have mist. Masking work is necessary because it scatters over a wide area, and equipment such as a dedicated painting booth may be necessary, and roll coaters and dipping are not realistic. For this reason, although various spray coatings are possible, brush coating or roller coating is the most efficient and cost-effective preferred coating method.

  The coating thickness of the protective coating can be applied to any thickness depending on the usage environment of the object to be coated, but generally 1 μm to 200 μm is preferable, and if it is less than 1 μm, sufficient coating film protective effect If the coating exceeds 200 μm, it takes a long time to form a film, and when it is applied to a vertical portion, problems such as sagging before film formation occur, which is not preferable.

  In the case of an emulsion type, the conditions for film formation depend on the minimum film formation temperature. However, if the minimum film formation temperature is around 0 ° C., the film is formed by simply leaving it after coating the protective coating. However, depending on the environmental conditions, it may take time to form a film, and it is possible to use a means of air drying with a fan or the like and forced air drying at about 40 to 80 ° C. It is necessary to form a film under conditions (temperature) that does not affect the temperature.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. In the following examples, “part” and “%” all represent “part by mass” and “mass%” unless otherwise specified.

[Example 1]
(Preparation of phthalated gelatin aqueous solution)
Phthalated gelatin (trade name “MGP gelatin” manufactured by Nippi Collagen Co., Ltd.) 32 parts, 1,2-benzothiazolin-3-one (manufactured by Daito Chemical Industry Co., Ltd., 3.5% methanol solution) 91 parts and 367 parts of water were mixed and dissolved by heating to 40 ° C. to obtain a phthalated gelatin aqueous solution.

(Preparation of alkali-treated gelatin aqueous solution)
25.5 parts of alkali-treated low ion gelatin (trade name “# 750 gelatin” manufactured by Nitta Gelatin Co., Ltd.), 1,2-benzothiazoline-3-one (manufactured by Daito Chemical Industry Co., Ltd., 3.5 % Methanol solution) 0.73 parts, 0.15 parts of calcium hydroxide and 144 parts of water were mixed and dissolved by heating to 50 ° C. to obtain an alkali-treated gelatin aqueous solution.

(Preparation of microcapsule solution (a) containing ultraviolet light-sensitive material)
To 10.6 parts of ethyl acetate, 3.2 parts of the following diazonium salt compound (A) (maximum absorption wavelength 420 nm), 5.3 parts of monoisopropylbiphenyl, 1.4 parts of tricresyl phosphate, lucillin “TPO-L” (BASF Japan Co., Ltd.) 0.64 parts, dibutyl sulfate 1.8 parts, and calcium dodecylbenzenesulfonate (trade name “Pionin A-41C” manufactured by Takemoto Yushi Co., Ltd., 70% methanol solution) 0.06 parts And heated to 40 ° C. to dissolve uniformly. To this mixed solution, 9.0 parts of xylylene diisocyanate / trimethylolpropane adduct (trade name “Takenate D110N”, 75% ethyl acetate solution manufactured by Mitsui Takeda Chemical Co., Ltd.) as a capsule wall material is added and stirred uniformly. Thus, an oil phase mixture was obtained.

Separately, 49.5 parts of the phthalated gelatin aqueous solution were mixed with 18.9 parts of water and 0.43 part of sodium dodecylbenzenesulfonate aqueous solution (trade name “Neopelex G-15” manufactured by Kao Corporation, 15% aqueous solution). The mixture was added and mixed to obtain an aqueous phase mixture.
The above oil phase mixture was added to this aqueous phase mixture, and emulsified and dispersed at a temperature of 40 ° C. and a rotation speed of 10,000 rpm for 10 minutes using a homogenizer manufactured by Nippon Seiki Seisakusho. After 24 parts of water was added to the resulting emulsion and homogenized, the mixture was stirred at a temperature of 40 ° C. for 3 hours to carry out an encapsulation reaction while removing ethyl acetate. Thereafter, 3.2 parts of an ion exchange resin “Amberlite IRA68” manufactured by Organo Corp. and 6.4 parts of “Amberlite IRC50” manufactured by Organo Corp. were added, and the mixture was further stirred for 1 hour. Thereafter, the ion exchange resin was removed by filtration, and the concentration was adjusted so that the solid content of the capsule solution was 23%, thereby obtaining a microcapsule solution (a) containing an ultraviolet range photosensitive material.

(Preparation of microcapsule solution (b) containing ultraviolet photosensitive material)
In the preparation of the microcapsule liquid (a) containing the ultraviolet photosensitive material, the same as the preparation of the microcapsule liquid (a) except that the following diazonium salt compound (B) was used instead of the diazonium salt compound (A). In this manner, a microcapsule liquid (b) containing an ultraviolet photosensitive material was prepared.

(Preparation of coupler compound emulsion (c))
36.7 parts of ethyl acetate, 11.0 parts of the following coupler compound (C), 11.5 parts of triphenylguanidine (manufactured by Hodogaya Chemical Co., Ltd.), 4,4 '-(m-phenylenediisopropylidene) diphenol (Trade name “Bisphenol M” manufactured by Mitsui Petrochemical Co., Ltd.) 23.1 parts, 3,3,3 ′, 3′-tetramethyl-5,5 ′, 6,6′-tetra (1-propyloxy) -1,1'-spirobisindane 3.7 parts, 4- (2-ethylhexyloxy) benzenesulfonic acid amide (manac Co., Ltd.) 15.1 parts, 4-n-pentyloxybenzenesulfonic acid amide (manac 7.6 parts) and calcium dodecylbenzenesulfonate (trade name “Pionin A-41-C” manufactured by Takemoto Yushi Co., Ltd., 70% methanol solution) 4.7 parts are dissolved in an oil phase. Liquid mixture Obtained.

Separately, 229 parts of water was added to 113 parts of the alkali-treated gelatin aqueous solution to obtain an aqueous phase mixture.
The above oil phase mixture was put into this aqueous phase mixture and emulsified and dispersed at a temperature of 40 ° C. and a rotation speed of 10,000 rpm for 5 minutes using a homogenizer manufactured by Nippon Seiki Seisakusho. The obtained emulsion was heated to remove ethyl acetate, and then the concentration was adjusted so that the solid content concentration of the emulsion was 23% to obtain a coupler compound emulsion (c).

(Preparation of acrylic resin emulsion)
A mixture of 10 parts of 2-hydroxyethyl acrylate, 48 parts of styrene, 28 parts of ethyl acrylate, 5 parts of methacrylic acid, 60 parts of n-butanol and 2 parts of benzoyl peroxide was used in a flask in which 1/4 of the mixture was replaced with nitrogen. The temperature was heated to 80 ° C., and the remaining 3/4 amount was gradually dropped into the flask over 3 hours. Next, a mixture of 0.2 parts of benzoyl peroxide and 5 parts of n-butanol was added dropwise over 30 minutes. After the completion, the mixture was stirred at the same temperature for 1 hour, and then a mixture of 5 parts of dimethylaminoethanol and 150 parts of water was gradually added. In addition, a desired acrylic resin emulsion was obtained.

(Preparation of resol type phenol resin solution)
15 parts of pt-butylphenol, 30 parts of 35% formalin, and 30 parts of 25% aqueous calcium hydroxide solution were mixed and reacted at a temperature of 50 ° C. for 3 hours. Thereafter, the solution was neutralized with hydrochloric acid and extracted with a mixed solvent of ethyl acetate / n-butanol = 1/1 to obtain a desired resol type phenol resin solution.

(Preparation of UV recording paint)
5.0 parts of the above-mentioned ultraviolet region-encapsulated microcapsule liquid (a), 5.0 parts of the above-mentioned ultraviolet region-encapsulated microcapsule liquid (b), 15.4 parts of the coupler compound emulsion (a), the above acrylic resin 20.2 parts of the emulsion, 1.0 part of the above-mentioned resol type phenol resin solution, and 1.2 parts of water were uniformly mixed to obtain an ultraviolet recording paint.

(Preparation of microcapsule liquid (d) encapsulated in UV absorber precursor)
To 6.0 parts of ethyl acetate, 1.5 parts of the following compound (D) as an ultraviolet absorber precursor, 0.5 parts of the following compound (E) as a reducing agent, and 0.8 parts of tricresyl phosphate are sufficiently added. Dissolved in. To this mixed solution, 3.0 parts of xylylene diisocyanate / trimethylolpropane adduct (trade name “Takenate D110N”, 75% ethyl acetate solution, manufactured by Mitsui Takeda Chemical Co., Ltd.) as a capsule wall material is added and stirred uniformly. Thus, an oil phase mixture was obtained. Next, 29.7 parts of an aqueous solution of 8% carboxy-modified polyvinyl alcohol (trade name “KL-318” manufactured by Kuraray Co., Ltd.) was added and emulsified and dispersed using a homogenizer. The obtained emulsified liquid was dropped into 40 parts of water and stirred at a temperature of 40 ° C. for 3 hours to carry out an encapsulation reaction, thereby preparing an ultraviolet absorber precursor-encapsulated microcapsule liquid (d).

(Preparation of protective coating composition)
20 parts of an aqueous dispersion (concentration 20%) of a copolymer resin obtained by emulsion polymerization of vinyldimethylpolysiloxane and methyl methacrylate at a ratio of 45/55 (mass ratio), and the ultraviolet absorber precursor adjusted to a concentration of 30% The protective microcapsule solution (d) (8.7 parts) and water (0.3 parts) were mixed uniformly to obtain the protective coating composition (1) of the present invention.

[Example 2]
In Example 1, the protective coating composition (2) of the present invention was used in the same manner as in Example 1 except that the following compound (F) was added instead of the compound (D) used as the ultraviolet absorber precursor. Got.

[Example 3]
In Example 1, the protective coating composition (3) of the present invention was used in the same manner as in Example 1 except that the following compound (G) was added instead of the compound (D) used as the ultraviolet absorber precursor. Got.

[Comparative Example 1]
In Example 1, the protective coating composition (4) of the comparative example was used in the same manner as in Example 1 except that the following compound (H) was added instead of the compound (D) used as the ultraviolet absorber precursor. Got.

[Comparative Example 2]
In Example 1, a protective coating composition (5) of Comparative Example was obtained in the same manner as in Example 1 except that the compound (D) as the ultraviolet absorber precursor was not used.

(Sample preparation and evaluation test)
The ultraviolet recording type coating material obtained above was applied onto a 198 μm thick WP support using a coating bar so that the dry film thickness was 30 μm and dried. On this coating film, each of the protective coatings obtained above was applied and dried using a coating bar so that the dry film thickness was 20 μm. The ultraviolet recording type coating film coated with each protective coating film thus obtained was exposed with light having an emission center wavelength of 365 nm and an irradiation energy of 4.00 mW / cm ² for 1 to 60 seconds. When heated for 10 seconds with a roller at a temperature of 105 ° C., the color developed from red to yellow. Further, the colored coating film was fixed by irradiating with a light having an emission center wavelength of 365 nm and an irradiation energy of 4.00 mW / cm ² for 1 minute, and then the colored density of the magenta component was measured by a reflection densitometer “X-rite” (X-rite). The results are shown in Table 9.

(Light resistance evaluation test)
Next, for each colored coating film having a magenta reflection density of about 1.0, a light cycle (at a temperature of 25 ° C. and a humidity of 32% RH) using an intermittent Xenon Weather-ometer “Ci65A” manufactured by ATLAS. 3.8 hours) and dark cycle (temperature 20 ° C, humidity 91% RH for 1 hour), repeated exposure tests over 3 days, and calculated the reflection density ratio after exposure to the reflection density before exposure The results are shown in Table 10 below.

(Measurement of light transmittance of protective film)
Separately, only the above protective coating is applied to the TAC base with a coating bar so that the dry film thickness becomes 20 μm, and the hue adjustment condition of the UV recording coating is applied to the dried coating. Exposure was conducted in the same manner, and the light transmittance of the protective coating film before and after the exposure was measured using a spectrophotometer “MP-200” manufactured by Shimadzu Corporation. The results are shown in Table 10.

  The samples coated with the protective coating according to the present invention (Examples 1 to 3) had a light transmittance in the wavelength region (360 nm) for adjusting the hue, 65% or more before the hue adjustment, as compared with the sample of Comparative Example 1. As a result, it was found that the photosensitivity was excellent. In addition, the samples coated with the protective coating of the present invention (Examples 1 to 3) have a light transmittance at a wavelength of 360 nm after hue adjustment reduced to 20% or less compared to the sample of Comparative Example 2. It was also found that it has excellent light resistance to ultraviolet rays and the like.

Claims (7)

  At least a protective coating applied to a coating film of a coating containing a substantially colorless dye-forming precursor capable of adjusting the hue by the application of light energy, the wavelength of light used at the time of adjusting the hue A protective coating composition, wherein the light transmittance in the region is at least 65% or more before the hue adjustment, and decreases after the hue adjustment than before the hue adjustment.   The protective coating composition according to claim 1, wherein the light transmittance at a wavelength of 360 nm is 65% or more before the hue adjustment and 50% or less after the hue adjustment. Compounds represented by the following general formulas (A-1) to (A-4) and / or compounds represented by the general formula (B) and / or general formulas (C-1) to (C-2) The protective coating composition according to claim 1, comprising a compound represented by the formula:

[In General Formulas (A-1) to (A-4), m represents 1 or 2. When m = 1 in A is formula (A-1), and in the general formula (A-2) ~ (A -4), -SO 2 R, -COR, -CO 2 R, -CONHR, -POR ¹ R ² , —CH ₂ R ³ or —SiR ⁴ R ⁵ R ⁶ , wherein R represents an alkyl group or an aryl group, and R ¹ and R ² are each independently an alkoxy group, an aryloxy group, represents an alkyl group or an aryl group, wherein R ³ represents at least one substituted phenyl group by a nitro group or a methoxy group, an alkyl group or an aryl group, each said R ⁴ to R ⁶ independently. When m = 2 in the general formula (A-1), A represents —SO ₂ R ⁷ SO ₂ —, —CO—, —COCO—, —COR ⁷ CO—, —SO ₂ — or —SO—, Here, R ⁷ represents an alkylene group or an arylene group. ]

[In General Formula (B), m represents 1 or 2, and n represents 0 or 1. A represents —SO ₂ R ¹⁰ , —COR ¹⁰ , —CO ₂ R ¹⁰ , —CONHR ¹⁰ , —POR ¹¹ R ¹² , —CH ₂ R ¹³ , or —SiR ¹⁴ R ¹⁵ R ¹⁶ when m = 1. Wherein R ¹⁰ represents an alkyl group, an alkenyl group, or an aryl group, R ¹¹ and R ¹² each independently represents an alkoxy group, an aryloxy group, an alkyl group, or an aryl group, and R ¹³ represents a nitro group Represents a phenyl group substituted with at least one group or a methoxy group, and each of R ^{14 to} R ¹⁶ independently represents an alkyl group or an aryl group. A represents —SO ₂ R ¹⁷ SO ₂ —, —CO—, —COCO—, —COR ¹⁷ CO—, —SO ₂ —, or —SO— when m = 2, wherein R ¹⁷ represents an alkylene. Represents a group, an alkenylene group, or an arylene group. R ^{1 to} R ⁹ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a halogen atom or —O—A, where A is as defined above for A. . ]

[In General Formulas (C-1) and (C-2), m represents 1 or 2. A is —SO ₂ R ¹ , —COR ¹ , —CO ₂ R ¹ , —CONHR ¹ , —POR ² R when m = 1 in General Formula (C-1) and in General Formula (C-2). ³ , —CH ₂ R ⁴ , or —SiR ⁵ R ⁶ R ⁷ , wherein R ¹ represents an alkyl group, an alkenyl group, or an aryl group, and R ² and R ³ are each independently an alkoxy group, Represents an aryloxy group, an alkyl group, or an aryl group, R ⁴ represents a phenyl group substituted with at least one of a nitro group or a methoxy group, and R ^{5 to} R ⁷ each independently represents an alkyl group, an alkenyl group, Represents an aryl group. A represents —SO ₂ R ⁸ SO ₂ —, —CO—, —COCO—, —COR ⁸ CO—, —SO ₂ —, or —SO— when m = 2 in the general formula (C-1). Here, R ⁸ represents an alkylene group or an arylene group. Z ¹ and Z ³ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group or a halogen atom, Z ² represents the same as Z ¹ or represents —O—A, wherein A is the above Synonymous with A.
X and Y each independently represent a group represented by the following structural formula (3), an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylthio group, an alkylthio group, or —NR ⁹ R ¹⁰ , And R ⁹ represents a hydrogen atom or an alkyl group, and R ¹⁰ represents an alkyl group or an aryl group. ]

In [Formula ^(3), Z ¹ ~Z 3 has the same meaning as Z ¹ to Z ³ described above. W is -OR ⁸ O-, or -OCOR ⁸ CO ₂ - represents, wherein said R ⁸ has the same meaning as R ⁸ mentioned above. ]   The compounds represented by the general formulas (A-1) to (A-4) and / or the general formula (B) and / or the general formulas (C-1) to (C-2) are contained in the microcapsules. The protective coating composition according to claim 3, wherein the protective coating composition is contained.   Furthermore, at least 1 or more types of polymer aqueous dispersion is contained, The protective coating composition in any one of Claims 1-4 characterized by the above-mentioned.   The protective coating composition according to claim 5, wherein the polymer aqueous dispersion contains at least one organosilicon resin.   A coated article coated with the protective coating composition according to any one of claims 1 to 6.