JP6874522B2 - Composition for laser marking and its use - Google Patents

Description

The present invention relates to a composition for laser marking, which comprises a specific near-infrared absorbing dye, and its use.

In recent years, the inkjet method has been the mainstream for printing and printing on the surfaces of various containers such as sheets, packaging sheets, egg packs, cards, foods, cosmetics, toiletries, pharmaceuticals, and caps of containers, but ink stains and characters There are many problems in terms of lack of ink or equipment maintenance. On the other hand, in the movement to automate and unmanned the marking process, a non-contact marking method using a laser beam, which has a high marking speed, is becoming widespread.

Patent Document 1 and Patent Document 2 propose a non-contact recording method using laser light having a wavelength in the near infrared region. Generally, a laser marking ink is composed of a color former, a color developer, and a near-infrared absorbing dye. When the coated object of this ink is irradiated with a laser beam, the near-infrared absorbing dye absorbs the laser beam and generates heat, so that the color-developing agent and the color-developing agent in the irradiated portion react to develop a color.

In order to obtain good color development ability, it is important to select a near-infrared absorbing dye that is colorless before laser irradiation, strongly absorbs light in the near-infrared region during laser irradiation, and efficiently converts heat. , Phthalocyanine (Patent Document 3), Cyanin (Patent Document 4), and Squalylium (Patent Document 5) have been proposed. However, the phthalocyanine-based material has a structure-derived absorption band in the visible light region and is colored by itself, so that there is a problem in invisibility. Further, although cyanine-based and squarylium-based materials have good invisibility, they generally have a structure with strong cohesiveness and are difficult to disperse and dissolve, so that there is a problem in viscosity and storage stability as an ink.

JP-A-58-209594 JP-A-58-094494 JP-A-2005-119262 JP-A-11-254830 Japanese Unexamined Patent Publication No. 7-25153

The problem to be solved by the present invention is a composition for laser marking, which has extremely high invisibility and near-infrared absorbing ability, excellent viscosity and storage stability, and excellent color development when irradiated with a laser, and a recording method thereof. To provide.

That is, the present invention is a composition for laser marking containing a near-infrared absorbing dye [A], a coloring agent [B], a developing agent [C], and a resin [D].
The near-infrared absorbing dye [A] is selected from the group consisting of a compound represented by the following general formula (1), a compound represented by the following general formula (2), and a compound represented by the following general formula (3). The present invention relates to a composition for laser marking containing at least one compound.

［一般式（１）中、
Ｒ_１〜Ｒ_５は、それぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリールオキシ基、スルホ基、ＳＯ_３ ⁻Ｍ_ａ ^＋、−ＳＯ_２ＮＲ_６Ｒ_７、−ＣＯＯＲ_８、−ＣＯＮＲ_９Ｒ_１０、ニトロ基、シアノ基又はハロゲン原子を表す。
Ｘ_１〜Ｘ_１０は、それぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基、置換基を有してもよいアリール基、置換基を有してもよいアラルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリールオキシ基、アミノ基、置換アミノ基、スルホ基、−ＳＯ_２ＮＲ_１１Ｒ_１２、−ＣＯＯＲ_１３、−ＣＯＮＲ_１４Ｒ_１５、ニトロ基、シアノ基又はハロゲン原子を表す。Ｘ_１〜Ｘ_１０は、置換基同士が結合して環を形成してもよい。
Ｍ_ａ ^＋は、無機又は有機のカチオンを表し、Ｒ_６〜Ｒ_１５は、それぞれ独立に、水素原子又は置換基を有してもよいアルキル基を表す。］ General formula (1)

[In general formula (1),
R _{1 to} R ₅ independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. an aryloxy group which may have a sulfo ^{_{group, SO 3 - M a +,}} -SO 2 NR 6 R 7, -COOR 8, -CONR 9 R 10, a nitro group, a cyano group or a halogen atom.
X _{1 to} X ₁₀ independently have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, and a substituent. Aralkyl group which may have, alkoxy group which may have substituent, aryloxy group which may have substituent, amino group, substituted amino group, sulfo group, -SO ₂ NR ₁₁ R ₁₂ ,- Represents COOR ₁₃ , -CONR ₁₄ R ₁₅ , nitro group, cyano group or halogen atom. In X _{1 to} X ₁₀ , the substituents may be bonded to each other to form a ring.
M _a ⁺ denotes an inorganic or organic cation, R ₆ to R ₁₅ each independently represent an alkyl group which may have a hydrogen atom or a substituent. ]

［一般式（２）中、
Ｙは、置換基を有してもよい複素環を表す。
Ｒ_１６〜Ｒ_２０は、それぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリールオキシ基、スルホ基、ＳＯ_３ ⁻Ｍ_ｂ ^＋、−ＳＯ_２ＮＲ_２１Ｒ_２２、−ＣＯＯＲ_２３、−ＣＯＮＲ_２４Ｒ_２５、ニトロ基、シアノ基又はハロゲン原子を表す。
Ｍ_ｂ ^＋は、無機又は有機のカチオンを表し、Ｒ_２１〜Ｒ_２５は、それぞれ独立に、水素原子又は置換基を有してもよいアルキル基を表す。］ General formula (2)

[In general formula (2),
Y represents a heterocycle which may have a substituent.
R _{16 to} R ₂₀ independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. an aryloxy group which may have a sulfo ^{_{group, SO 3 - M b +,}} -SO 2 NR 21 R 22, -COOR 23, -CONR 24 R 25, a nitro group, a cyano group or a halogen atom.
M _b ⁺ represents an inorganic or organic cation, and R _{21 to} R ₂₅ each independently represent an alkyl group which may have a hydrogen atom or a substituent. ]

［一般式（３）中、
Ｑ_１、Ｑ_４、Ｑ_５及びＱ_８は、それぞれ独立に、炭素原子又は窒素原子を表す。Ｑ_１、Ｑ_４、Ｑ_５又はＱ_８が窒素原子の場合、それぞれに結合するＸ_１１、Ｘ_１４、Ｘ_１５又はＸ_１８はないものとする。
Ｒ_２６〜Ｒ_３０は、それぞれ独立に、水素原子、スルホ基、−ＳＯ_３ ⁻Ｍ_ｃ ^＋又はハロゲン原子を表す。Ｍ_ｃ ^＋は、無機又は有機のカチオンを表す。
Ｘ_１１〜Ｘ_１８は、それぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基、置換基を有してもよいアリール基、置換基を有してもよいアラルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリールオキシ基、ヒドロキシル基、アミノ基、−ＮＲ_３１Ｒ_３２、スルホ基、−ＳＯ_２ＮＲ_３３Ｒ_３４、−ＣＯＯＲ_３５、−ＣＯＮＲ_３６Ｒ_３７、ニトロ基、シアノ基又はハロゲン原子を表す。Ｘ_１１〜Ｘ_１８は、置換基同士が結合して環を形成してもよい。
Ｒ_３１〜Ｒ_３７は、それぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアシル基又は置換基を有してもよいピリジニル基を表す。Ｒ_３１とＲ_３２、Ｒ_３３とＲ_３４、Ｒ_３６とＲ_３７は、置換基同士が結合して環を形成してもよい。］ General formula (3)

[In general formula (3),
Q ₁ , Q ₄ , Q ₅ and Q ₈ each independently represent a carbon atom or a nitrogen atom. If Q ₁ , Q ₄ , Q ₅ or Q ₈ are nitrogen atoms, it is assumed that there are no _{X 11} , X ₁₄ , X ₁₅ or X _{18 bonded to each.}
R _{26 to} R ₃₀ independently represent a hydrogen atom, a sulfo group, -SO ₃ ^- M _c ⁺ or a halogen atom. _Mc ⁺ represents an inorganic or organic cation.
X _{11 to} X ₁₈ independently have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, and a substituent. Aralkyl group which may have, alkoxy group which may have substituent, aryloxy group which may have substituent, hydroxyl group, amino group, -NR ₃₁ R ₃₂ , sulfo group, -SO ₂ NR _{Represents 33} R ₃₄ , -COOR ₃₅ , -CONR ₃₆ R ₃₇ , nitro group, cyano group or halogen atom. In X _{11 to} X ₁₈ , substituents may be bonded to each other to form a ring.
R _{31 to} R ₃₇ each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, and an acyl group or a substituent which may have a substituent. Represents a pyridinyl group that may have. In R ₃₁ and R ₃₂ , R ₃₃ and R _{34, and} R ₃₆ and R ₃₇ , the substituents may be bonded to each other to form a ring. ]

The present invention also relates to the above-mentioned laser marking composition in which the near-infrared absorbing dye [A] contains a compound represented by the general formula (1).

Further, in the present invention, _{at least one or more of R 1 to} R ₅ in the general formula (1) has an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent. also alkoxy group, an optionally substituted aryloxy group, a sulfo ^{_{group, SO 3 - M a +,}} -SO 2 NR 6 R 7, -COOR 8, -CONR 9 R 10, a nitro group, a cyano The present invention relates to the above-mentioned composition for laser marking which is a group or a halogen atom.

The present invention also relates to the above-mentioned laser marking composition in which _{at least one or more of R 1 to} R ₅ in the general formula (1) is a sulfo group or SO ₃ ^- M _a ^+.

The present invention also relates to the above-mentioned laser marking composition in which the near-infrared absorbing dye [A] contains a compound represented by the general formula (2).

The present invention also relates to the above-mentioned laser marking composition in which Y in the general formula (2) is a saturated or unsaturated heterocycle having a 4-membered ring to a 7-membered ring which may have a substituent.

The present invention also relates to the above-mentioned laser marking composition in which the near-infrared absorbing dye [A] contains a compound represented by the general formula (3).

The present invention also relates to the above-mentioned laser marking composition _{in which Q 1} , Q ₄ , Q ₅ and Q ₈ in the general formula (3) are carbon atoms.

The present invention also relates to the above-mentioned laser marking composition in which the content of the near-infrared absorbing dye [A] in the total solid content of the laser marking composition is 0.05 to 5% by mass.

The present invention also relates to a coated product obtained by coating the above-mentioned laser marking composition.

The present invention also relates to a recording material obtained by irradiating the coated object with a laser beam for recording.

Further, the present invention relates to a recording method in which the coated object is irradiated with a laser beam and recorded.

The composition for laser marking of the present invention has excellent invisibility and near-infrared absorbing ability, and has extremely high viscosity and storage stability by using a specific near-infrared absorbing dye which has good optical characteristics and is hard to aggregate and precipitate. It has excellent properties and is very excellent in color development when irradiated with a laser.

<Laser marking composition>
The composition for laser marking of the present invention will be described in detail. The composition for laser marking of the present invention contains, in addition to the specific near-infrared absorbing dye [A], a color former [B], a color developer [C], and a resin [D] as essential components, and other known additives. Etc. The near-infrared absorbing dye can be used in both the dispersed state and the dissolved state.

<Near infrared absorbing pigment [A]>
The near-infrared absorbing dye [A] of the present invention is selected from the group consisting of a compound represented by the general formula (1), a compound represented by the general formula (2), and a compound represented by the general formula (3). It is characterized by containing at least one compound. It may be used alone or in combination of two or more.

(Compound represented by the general formula (1))
General formula (1)

[In general formula (1),
R _{1 to} R ₅ independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. an aryloxy group which may have a sulfo ^{_{group, SO 3 - M a +,}} -SO 2 NR 6 R 7, -COOR 8, -CONR 9 R 10, a nitro group, a cyano group or a halogen atom.
X _{1 to} X ₁₀ independently have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, and a substituent. Aralkyl group which may have, alkoxy group which may have substituent, aryloxy group which may have substituent, amino group, substituted amino group, sulfo group, -SO ₂ NR ₁₁ R ₁₂ ,- Represents COOR ₁₃ , -CONR ₁₄ R ₁₅ , nitro group, cyano group or halogen atom. In X _{1 to} X ₁₀ , the substituents may be bonded to each other to form a ring.
M _a ⁺ denotes an inorganic or organic cation, R ₆ to R ₁₅ each independently represent an alkyl group which may have a hydrogen atom or a substituent. ]

In R _{1 to} R ₅ , the "alkyl group which may have a substituent" includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, a tert-amyl group and a 2-ethylhexyl group. Examples thereof include stearyl group, chloromethyl group, trichloromethyl group, trifluoromethyl group, 2-methoxyethyl group, 2-chloroethyl group, 2-nitroethyl group, cyclopentyl group, cyclohexyl group, dimethylcyclohexyl group and the like. Of these, a methyl group, an ethyl group and an n-propyl group are preferable from the viewpoint of synthetic difficulty and invisibility.

In R _{1 to} R ₅ , the "aryl group which may have a substituent" includes a phenyl group, a naphthyl group, a 4-methylphenyl group, a 3,5-dimethylphenyl group, a pentafluorophenyl group, and a 4-bromophenyl group. Groups, 2-methoxyphenyl group, 4-diethylaminophenyl group, 3-nitrophenyl group, 4-cyanophenyl group and the like can be mentioned, and among these, the phenyl group and the 4-methylphenyl group have the difficulty of synthesis and the degree of synthesis. Preferred from the viewpoint of invisibility.

In R _{1 to} R ₅ , "alkoxy groups even if they have a substituent" include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, n-octyloxy group and 2-ethylhexyloxy. Examples thereof include a group, a trifluoromethoxy group, a cyclohexyloxy group, a stearyloxy group and the like, and among these, a methoxy group, an ethoxy group and a trifluoromethoxy group are preferable from the viewpoint of synthesis difficulty and invisibility.

In R _{1 to} R ₅ , the "aryloxy group which may have a substituent" includes a phenoxy group, a naphthyloxy group, a 4-methylphenyloxy group, a 3,5-chlorophenyloxy group and a 4-chloro-2-. Methylphenyloxy group, 4-tert-butylphenyloxy group, 4-methoxyphenyloxy group, 4-diethylaminophenyloxy group, 4-nitrophenyloxy group and the like can be mentioned, and among these, phenoxy group and 4-methyl A phenyloxy group and a naphthyloxy group are preferable from the viewpoint of synthetic difficulty and invisibility.

As "organic or inorganic cation" M _a ⁺ of the R ₁ to R ₅ may be employed without any known limitation, specifically, a metal atom, an ammonium compound, a pyridinium compound, imidazolium compound, a phosphonium compound, Examples include sulfonium compounds. Among these, trivalent metal atoms and ammonium compounds are preferable from the viewpoint of synthesis difficulty and invisibility.

Examples of the "halogen atom" in R _{1 to} R ₅ include fluorine, bromine, chlorine and iodine.

From the viewpoint of invisibility, it is preferable that at least one or more of R _{1 to} R ₅ is substituted with a non-hydrogen atom, and among them, at least one or more of _{R 1 to} R _{5 is a sulfo group or SO 3} ^−. More preferably, it is _Ma ^+.

In R _{6 to} R ₁₅ , the "alkyl group which may have a substituent" is synonymous with _{R 1 to} R _5. In R ₆ and R ₇ , R ₉ and R _10, R ₁₁ and R ₁₂ , and R ₁₄ and R ₁₅ , substituents may be bonded to each other to form a ring.

In X _{1 to} X ₁₀ , the "alkyl group which may have a substituent" includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, a tert-amyl group and a 2-ethylhexyl group. Examples thereof include stearyl group, chloromethyl group, trichloromethyl group, trifluoromethyl group, 2-methoxyethyl group, 2-chloroethyl group, 2-nitroethyl group, cyclopentyl group, cyclohexyl group, dimethylcyclohexyl group and the like. Of these, a methyl group, an ethyl group and an n-propyl group are preferable from the viewpoint of synthesis difficulty, storage stability and invisibility, and a methyl group is particularly preferable.

In X _{1 to} X ₁₀ , the "alkenyl group which may have a substituent" includes a vinyl group, a 1-propenyl group, an allyl group, a 2-butenyl group, a 3-butenyl group, an isopropenyl group, an isobutenyl group and 1 -Pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group and the like can be mentioned. Among these, a vinyl group and an allyl group are preferable from the viewpoint of synthesis difficulty, storage stability, and invisibility.

In X _{1 to} X ₁₀ , the "aryl group which may have a substituent" includes a phenyl group, a naphthyl group, a 4-methylphenyl group, a 3,5-dimethylphenyl group, a pentafluorophenyl group, and a 4-bromophenyl group. Groups, 2-methoxyphenyl group, 4-diethylaminophenyl group, 3-nitrophenyl group, 4-cyanophenyl group and the like can be mentioned. Among these, phenyl group and 4-methylphenyl group are difficult to synthesize and stable in storage. It is preferable from the viewpoint of sex and invisibility.

Examples of the "aralkyl group which may have a substituent" in X _{1 to X 10} include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group and the like, and among these, the benzyl group is difficult to synthesize. It is preferable from the viewpoint of degree, storage stability, and invisibility.

In X _{1 to} X ₁₀ , "alkoxy groups even if they have a substituent" include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, n-octyloxy group and 2-ethylhexyloxy. Examples include a group, a trifluoromethoxy group, a cyclohexyloxy group, a stearyloxy group, etc. Among these, a methoxy group, an ethoxy group, and a trifluoromethoxy group are selected from the viewpoint of synthesis difficulty, storage stability, and invisibility. preferable.

In X _{1 to} X ₁₀ , the "aryloxy group which may have a substituent" includes a phenoxy group, a naphthyloxy group, a 4-methylphenyloxy group, a 3,5-chlorophenyloxy group and a 4-chloro-2-. Examples thereof include a methylphenyloxy group, a 4-tert-butylphenyloxy group, a 4-methoxyphenyloxy group, a 4-diethylaminophenyloxy group, a 4-nitrophenyloxy group, and among these, a phenoxy group and a naphthyloxy group. However, it is preferable from the viewpoint of synthesis difficulty, storage stability, and invisibility.

In X _{1 to} X ₁₀ , the "substituted amino group" includes a methylamino group, an ethylamino group, an isopropylamino group, an n-butylamino group, a cyclohexylamino group, a stearylamino group, a dimethylamino group, a diethylamino group and a dibutylamino group. , N, N-di (2-hydroxyethyl) amino group, phenylamino group, naphthylamino group, 4-tert-butylphenylamino group, diphenylamino group, N-phenyl-N-ethylamino group and the like. Of these, dimethylamino groups and diethylamino groups are preferable from the viewpoints of difficulty in synthesis, storage stability, and invisibility.

Examples of the "halogen atom" in X _{1 to} X ₁₀ include fluorine, bromine, chlorine and iodine.

In X _{1 to} X ₁₀ , substituents may be bonded to each other to form a ring, and examples thereof include, but are not limited to, the following structures.

X _{1 to} X ₁₀ preferably contain an unsubstituted alkyl group, particularly from the viewpoint of near-infrared absorbing ability, _{and at least one of X 3} , X ₄ , X ₇ and X ₈ is an unsubstituted alkyl group. Is more preferable, and it is particularly preferable that _{X 3} and X _{7 are unsubstituted alkyl groups.} The unsubstituted alkyl group is preferably a methyl group.

(Compound represented by the general formula (2))
General formula (2)

[In general formula (2),
Y represents a heterocycle which may have a substituent.
R _{16 to} R ₂₀ independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. an aryloxy group which may have a sulfo ^{_{group, SO 3 - M b +,}} -SO 2 NR 21 R 22, -COOR 23, -CONR 24 R 25, a nitro group, a cyano group or a halogen atom.
M _b ⁺ represents an inorganic or organic cation, and R _{21 to} R ₂₅ each independently represent an alkyl group which may have a hydrogen atom or a substituent. ]

The heterocycle in Y refers to an atom containing one or more atoms (heteroatoms) other than carbon atoms among the atoms constituting the ring system. Typical heteroatoms include nitrogen atoms, oxygen atoms, and sulfur atoms, and one heterocycle may contain a plurality of heteroatoms. Those containing an oxygen atom and / or a sulfur atom as the heteroatom of the heterocycle are preferable from the viewpoint of spectral characteristics, durability imparting and synthesis difficulty. Examples of the heterocycle include saturated or unsaturated heterocycles of 3 to 10 membered rings, and saturated or unsaturated heterocycles of 4 to 7 membered rings have difficulty in synthesis and absorption of near infrared rays. From the viewpoint of ability and invisibility, a 6-membered saturated or unsaturated heterocycle is preferable, and an unsubstituted tetrahydropyran ring or an unsubstituted tetrahydrothiopyran ring is more preferable.

Examples of the "substituent" in Y include the "alkyl group which may have a substituent" and the "aryl group which may have a substituent" in _{R 1 to} R ₅ and X _{1 to} X _{10 described above.} "Halkyl group having a substituent", "aryloxy group having a substituent", "halogen atom", "alkenyl group having a substituent", "having a substituent" In addition to the "aralkyl group" and the "substituted amino group", a hydroxyl group, an amino group, an oxo group and the like may be mentioned, and the substituents may be bonded to each other to form a ring. Moreover, one heterocycle may have a plurality of substituents.

Specific examples of the "heterocycle which may have a substituent" in Y include, but are not limited to, the following structures.

In R _{16 to} R ₂₀ , the "alkyl group which may have a substituent" includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, a tert-amyl group and a 2-ethylhexyl group. Examples thereof include stearyl group, chloromethyl group, trichloromethyl group, trifluoromethyl group, 2-methoxyethyl group, 2-chloroethyl group, 2-nitroethyl group, cyclopentyl group, cyclohexyl group, dimethylcyclohexyl group and the like. Of these, a methyl group, an ethyl group and an n-propyl group are preferable from the viewpoint of synthetic difficulty and invisibility.

In R _{16 to} R ₂₀ , the "aryl group which may have a substituent" includes a phenyl group, a naphthyl group, a 4-methylphenyl group, a 3,5-dimethylphenyl group, a pentafluorophenyl group, and a 4-bromophenyl group. Groups, 2-methoxyphenyl group, 4-diethylaminophenyl group, 3-nitrophenyl group, 4-cyanophenyl group and the like can be mentioned. Among these, the phenyl group and the 4-methylphenyl group have the difficulty of synthesis and the synthesis difficulty. Preferred from the viewpoint of invisibility.

In R _{16 to} R ₂₀ , "alkoxy groups even if they have a substituent" include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, n-octyloxy group and 2-ethylhexyloxy. Examples thereof include a group, a trifluoromethoxy group, a cyclohexyloxy group, a stearyloxy group and the like, and among these, a methoxy group, an ethoxy group and a trifluoromethoxy group are preferable from the viewpoint of synthesis difficulty and invisibility.

In R _{16 to} R ₂₀ , the "aryloxy group which may have a substituent" includes a phenoxy group, a naphthyloxy group, a 4-methylphenyloxy group, a 3,5-chlorophenyloxy group and a 4-chloro-2-. Methylphenyloxy group, 4-tert-butylphenyloxy group, 4-methoxyphenyloxy group, 4-diethylaminophenyloxy group, 4-nitrophenyloxy group and the like can be mentioned, and among these, phenoxy group and 4-methyl A phenyloxy group and a naphthyloxy group are preferable from the viewpoint of synthetic difficulty and invisibility.

As the "inorganic or organic cation" of M _b ⁺ _{in R 16 to} R ₂₀ , known ones can be adopted without limitation, and in the case of an organic cation, either a low molecular weight type or a high molecular weight type may be used. Specific examples thereof include metal atoms, ammonium compounds, pyridinium compounds, imidazolium compounds, phosphonium compounds, and sulfonium compounds. In the case of the polymer type, for example, "resin having a quaternary ammonium base" and the like can be mentioned, but the present invention is not limited thereto.
Among these, a resin having a trivalent metal atom, an ammonium compound, and a quaternary ammonium base is preferable from the viewpoint of synthesis difficulty and invisibility.

Examples of the "halogen atom" in R _{16 to} R ₂₀ include fluorine, bromine, chlorine and iodine.

From the viewpoint of invisibility, R _{16 to} R _{20 are all hydrogen atoms, or four of R 16 to} R ₂₀ are hydrogen atoms and one is a sulfo group or -SO ₃ ^- M _b ^+. Is particularly preferable.

In R _{21 to} R ₂₅ , the "alkyl group which may have a substituent" is synonymous with _{R 16 to} R _20.

(Compound represented by the general formula (3))
General formula (3)

[In general formula (3),
Q ₁ , Q ₄ , Q ₅ and Q ₈ each independently represent a carbon atom or a nitrogen atom. If Q ₁ , Q ₄ , Q ₅ or Q ₈ are nitrogen atoms, it is assumed that there are no _{X 11} , X ₁₄ , X ₁₅ or X _{18 bonded to each.}
R _{26 to} R ₃₀ independently represent a hydrogen atom, a sulfo group, -SO ₃ ^- M _c ⁺ or a halogen atom. _Mc ⁺ represents an inorganic or organic cation.
X _{11 to} X ₁₈ independently have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, and a substituent. Aralkyl group which may have, alkoxy group which may have substituent, aryloxy group which may have substituent, hydroxyl group, amino group, -NR ₃₁ R ₃₂ , sulfo group, -SO ₂ NR _{Represents 33} R ₃₄ , -COOR ₃₅ , -CONR ₃₆ R ₃₇ , nitro group, cyano group or halogen atom. In X _{11 to} X ₁₈ , substituents may be bonded to each other to form a ring.
R _{31 to} R ₃₇ each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, and an acyl group or a substituent which may have a substituent. Represents a pyridinyl group that may have. In R ₃₁ and R ₃₂ , R ₃₃ and R _{34, and} R ₃₆ and R ₃₇ , the substituents may be bonded to each other to form a ring. ]

As Q ₁ , Q ₄ , Q ₅ and Q ₈ , carbon atoms are more preferable.

Examples of the "halogen atom" in R _{26 to} R ₃₀ include fluorine, bromine, chlorine and iodine.

As "organic or inorganic cation" M _c ⁺ of the R ₂₆ to R ₃₀ may be employed without a known limitations, the organic cation may be either a low molecular type and a polymer type. Specific examples thereof include metal atoms, ammonium compounds, pyridinium compounds, imidazolium compounds, phosphonium compounds, and sulfonium compounds. In the case of the polymer type, for example, "resin having a quaternary ammonium base" and the like can be mentioned, but the present invention is not limited thereto. Among these, a resin having a trivalent metal atom, an ammonium compound, and a quaternary ammonium base is preferable from the viewpoint of synthesis difficulty and invisibility.

It is _M ^{c +} - R ₂₆ ~R _30, from the viewpoint of invisibility, or all hydrogen atom, or a four are hydrogen atom of _R 26 _{to R 30,} 1 single sulfo group or _-SO ³ Is particularly preferable.

In X _{11 to} X ₁₈ , the "alkyl group which may have a substituent" includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, an isobutyl group, a tert-amyl group and 2-. Ethylhexyl group, stearyl group, chloromethyl group, trichloromethyl group, trifluoromethyl group, 2-methoxyethyl group, 2-chloroethyl group, 2-nitroethyl group, cyclopentyl group, cyclohexyl group, dimethylcyclohexyl group and the like can be mentioned. Of these, a methyl group and an ethyl group are preferable from the viewpoint of difficulty in synthesis.

In X _{11 to} X ₁₈ , the "alkenyl group which may have a substituent" includes a vinyl group, a 1-propenyl group, an allyl group, a 2-butenyl group, a 3-butenyl group, an isopropenyl group, an isobutenyl group and 1 -Pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group and the like can be mentioned. Of these, a vinyl group and an allyl group are preferable from the viewpoint of difficulty in synthesis.

In X _{11 to} X ₁₈ , the "aryl group which may have a substituent" includes a phenyl group, a naphthyl group, a 4-methylphenyl group, a 3,5-dimethylphenyl group, a pentafluorophenyl group, and a 4-bromophenyl group. Groups, 2-methoxyphenyl group, 4-diethylaminophenyl group, 3-nitrophenyl group, 4-cyanophenyl group and the like can be mentioned, and among these, the phenyl group and 4-methylphenyl group are considered from the viewpoint of difficulty in synthesis. Is preferable.

As the "optionally substituted aralkyl group" in X ₁₁ to X _18, a benzyl group, phenethyl group, phenylpropyl group, and a naphthylmethyl group, a benzyl group Among these, synthetic difficulty Preferred from the viewpoint of degree.

In X _{11 to} X ₁₈ , "alkoxy groups even if they have a substituent" include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, n-octyloxy group and 2-ethylhexyloxy. Examples thereof include a group, a trifluoromethoxy group, a cyclohexyloxy group, a stearyloxy group, a 2- (diethylamino) ethoxy group, and among these, a methoxy group, an ethoxy group, a trifluoromethoxy group, and a 2- (diethylamino) ethoxy group. , Preferred from the viewpoint of synthesis difficulty.

In X _{11 to} X ₁₈ , the "aryloxy group which may have a substituent" includes a phenoxy group, a naphthyloxy group, a 4-methylphenyloxy group, a 3,5-chlorophenyloxy group and a 4-chloro-2-. Examples thereof include a methylphenyloxy group, a 4-tert-butylphenyloxy group, a 4-methoxyphenyloxy group, a 4-diethylaminophenyloxy group, a 4-nitrophenyloxy group, and among these, a phenoxy group and a naphthyloxy group. However, it is preferable from the viewpoint of the difficulty of synthesis.

Examples of the "halogen atom" in X _{11 to} X ₁₈ include fluorine, bromine, chlorine and iodine.

In X _{11 to} X ₁₈ , substituents may be bonded to each other to form a ring, and examples thereof include, but are not limited to, the following structures.

It is particularly preferable that all of X _{11 to} X ₁₈ are hydrogen atoms, particularly from the viewpoint of near-infrared absorbing ability.

In R _{31 to} R ₃₇ , the "alkyl group which may have a substituent" includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, an isobutyl group, a sec-butyl group and a tert-. Amil group, 2-ethylhexyl group, stearyl group, chloromethyl group, trichloromethyl group, trifluoromethyl group, 2-methoxyethyl group, 2-chloroethyl group, 2-nitroethyl group, cyclopentyl group, cyclohexyl group, dimethylcyclohexyl group, etc. Among these, a methyl group and an ethyl group are preferable from the viewpoint of the difficulty of synthesis.

In R _{31 to} R ₃₇ , the "aryl group which may have a substituent" includes a phenyl group, a naphthyl group, a 4-methylphenyl group, a 3,5-dimethylphenyl group, a pentafluorophenyl group, and a 4-bromophenyl group. Groups, 2-methoxyphenyl group, 4-diethylaminophenyl group, 3-nitrophenyl group, 4-cyanophenyl group and the like can be mentioned, and among these, the phenyl group and 4-methylphenyl group are considered from the viewpoint of difficulty in synthesis. Is preferable.

Examples of the "acyl group which may have a substituent" in R _{31 to} R ₃₇ include an acetyl group, a propioil group, a benzoyl group, an acryloyl group, a trifluoroacetyl group and the like, and among these, the acetyl group is used. , Preferred from the viewpoint of synthesis difficulty.

Examples of the "pyridinyl group which may have a substituent" in R _{31 to R 37} include 2-pyridinyl group, 3-pyridinyl group, 4-pyridinyl group, 2-methyl-4-pyridinyl group and the like. Of these, the 4-pyridinyl group is preferable from the viewpoint of the difficulty of synthesis.

In R ₃₁ and R ₃₂ , R ₃₃ and R _{34, and} R ₃₆ and R ₃₇ , the substituents may be bonded to each other to form a ring.

(Manufacturing method of near-infrared absorbing dye [A])
As a method for producing the near-infrared absorbing dye [A] represented by the general formula (1), 1,8-diaminonaphthalene represented by the following general formula (4) and a ketone represented by the following general formula (5) are used. After heating and refluxing in a solvent together with a catalyst to condense the species, 3,4-dihydroxy-3-cyclobutene-1,2-dione represented by the following formula (6) is added and further heated to reflux to condense. Then, a production method for obtaining the squarylium dye represented by the general formula (1) can be considered. When at least one of _{R 1 to} R _{5 is SO 3} ^- M ⁺ , SO is obtained by counter-exchange the hydrogen ion of the sulfo group of the dye substituted with the sulfo group with the compound having the desired cation. _A ^{production method for obtaining a dye substituted with 3-} M _a ⁺ can be considered, and the counter can be replaced by a known method.
The near-infrared absorbing dye [A] represented by the general formula (2) and the general formula (3) can also be produced by changing the corresponding ketones in the same manner as described above, but is used in the present invention. The near-infrared absorbing dye [A] is not limited by these production methods.

<Color former [B]>
Examples of the color former [B] include electron-donating leuco dyes, and various known compounds can be used. These can be used alone or in combination of two or more, and are appropriately selected depending on the application and required quality characteristics. Specific examples include, but are not limited to, the following compounds.

(1) Triarylmethane compound 3,3'-bis (4-dimethylaminophenyl) -6-dimethylaminophthalide <trade name: crystal violet lactone, CVL>, 3- (4-dimethylamino-2-methylphenyl) ) -3- (4-Dimethylaminophenyl) phthalide, 3,3'-bis (2- (4-dimethylaminophenyl) -2- (4-methoxyphenyl) ethenyl) -4,5,6,7-tetra Chlorophthalide <NIR-Black>, 3,3'-bis (4-dimethylaminophenyl) phthalide <MGL>, 3- (4-dimethylaminophenyl) -3- (1,2-dimethylindole-3-yl) ) Phtalide, 3- (4-dimethylaminophenyl) -3- (2-phenylindole-3-yl) phthalide, 3,3'-bis (4-ethylcarbazole-3-yl) -3-dimethylaminophthalide , 3,3'-bis (1-ethyl-methylindole-3-yl) phthalide <Indrill Red>, 3,3'-bis (2-phenylindole-3-yl) -5-dimethylaminophthalide , Tris (4-dimethylaminophenyl) methane <LCV>, etc.

(2) Diphenylmethane-based compounds 4,4-bis (dimethylamino) benzhydrinbenzyl ether, N-halophenyl-leuco auramine, N-2,4,5-trichlorophenyl leucooramine and the like.

(3) Xanthene compounds Rhodamine B-anilinolactam, 3-diethylamino-7-dibenzylaminofluorane, 3-diethylamino-7-butylaminofluorane, 3-diethylamino-7-anilinofluorane <Green-2 >, 3-Diethylamino-7- (2-chloroanilino) fluorane, 3-dibutylamino-7- (2-chloroanilino) fluorane <TH-107>, 3-diethylamino-7- (3-trifluoromethylanilino) fluorane <Black-100>, 3-diethylamino-6-methyl-7-anilinofluorane <ODB>, 3-dibutylamino-6-methyl-7-anilinofluorane <ODB-2>, 3-piperidino-6 -Methyl-7-anilinofluorane, 3- (N-isoamyl-N-ethylamino) -6-methyl-7-anilinofluorane <S-205>, 3- (N-ethyl-N-tolylamino) -6-Methyl-7-anilinofluorane, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilinofluorane <PSD-150>, 3-diethylamino-6-chloro-7 -(Β-ethoxyethylamino) fluorane, 3-diethylamino-6-chloro-7- (γ-chloropropylamino) fluorane, 3-cyclohexylamino-6-chlorofluorane <OR-55>, 3-diethylamino-6 -Chloro-7-anilinofluorane, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilinofluorane, 3-diethylamino-7-phenylfluorane, etc.

(4) Thiazine compounds Benzoyl leucomethylene blue, p-nitrobenzoyl leucomethylene blue and the like.

(5) Spiro-based compounds Examples thereof include 3-methylspirodinaphthopyran, 3-ethylspirinaftopyran, 3-benzylspirodinaphthopyran, 3-methylnaphtho- (6'-methoxybenzo) spiropyran and the like.

(6) Pentadiene compound 1,1,5,5-tetrakis (4-dimethylaminophenyl) -3-methoxy-1,4-pentadiene, 1,1,5,5-tetrakis (4-dimethylaminophenyl) -1 , 4-Pentadiene, etc.

<Color developer [C]>
Examples of the color developer [C] include electron-accepting compounds, and various known compounds can be used. These can be used alone or in combination of two or more, and are appropriately selected according to the intended use and required quality. Specific examples include, but are not limited to, the following compounds.

Inorganic acidic substances such as active white clay, atapargite, colloidal silica, aluminum silicate, benzyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, normal propyl 4-hydroxybenzoate, isopropyl 4-hydroxybenzoate, 4-hydroxybenzoic acid 4-Hydroxybenzoic acid esters such as butyl, 4-hydroxyphthalic acid diesters such as dimethyl 4-hydroxyphthalate, diisopropyl 4-hydroxyphthalate, dibenzyl 4-hydroxyphthalate, dihexyl 4-hydroxyphthalate, and phthalic acid Phyrate monoesters such as monobenzyl ester, phthalic acid monocyclohexyl ester, phthalic acid monophenyl ester, phthalic acid monomethylphenyl ester, bis (4-hydroxy-3-tert-butyl-6-methylphenyl) sulfide, bis ( Bishydroxyphenyl sulfides such as 4-hydroxy-2,5-dimethylphenyl) sulfide, bis (4-hydroxy-5-ethyl-2-methylphenyl) sulfide, 3,4-bisphenol A, 1,1-bis ( 4-Hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane <bisphenol A>, bis (4-hydroxyphenyl) methane <bisphenol F>, 2,2-bis (4-hydroxyphenyl) hexane, Tetramethylbisphenol A, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,4-bis (2- (4-hydroxyphenyl) propyl) benzene.

1,3-bis (2- (4-hydroxyphenyl) propyl) benzene, 1,4-bis (4-hydroxyphenyl) cyclohexane, 2,2'-bis- (4-hydroxy-3-isopropylphenyl) propane, Bisphenols such as 1,4-bis (1- (4- (2- (4-hydroxyphenyl) -2-propyl) phenyl) ethyl) benzene, 4-hydroxy-4'-isopropoxydiphenyl sulfone, 4-hydroxy 4-Hydroxyphenylaryl sulfones such as -4'-methoxydiphenyl sulfone and 4-hydroxy-4'-normal propoxydiphenyl sulfone, bis (4-hydroxyphenyl) sulfone <bisphenol S>, tetramethylbisphenol S, bis (3) -Ethyl-4-hydroxyphenyl) sulfone, bis (3-propyl-4-hydroxyphenyl) sulfone, bis (3-isopropyl-4-hydroxyphenyl) sulfone, bis (3-tert-butyl-4-hydroxy-6- Bishydroxyphenyl sulfones such as methylphenyl) sulfone, bis (3-chloro-4-hydroxyphenyl) sulfone, bis (3-bromo-4-hydroxyphenyl) sulfone, 2-hydroxyphenyl-4'-hydroxyphenyl sulfone, 4-Hydroxyphenylaryl sulfonates such as 4-hydroxybenzene sulphonate, 4-hydroxyphenyl-p-tolyl sulphonate, 4-hydroxyphenyl-p-chlorobenzene sulphonate, benzyl 4-hydroxybenzoyloxybenzoate, 4-. 4-Hydroxybenzoyloxy benzoate esters such as ethyl hydroxybenzoyloxy benzoate, normal propyl 4-hydroxybenzoyloxy benzoate, isopropyl 4-hydroxybenzoyloxy benzoate, butyl 4-hydroxybenzoyloxy benzoate, 2,4- Dihydroxybenzophenone, α, α'-bis- (3-methyl-4-hydroxyphenyl) -m-diisopropylbenzophenone, benzophenones such as 2,3,4,4'-tetrahydroxybenzophenone, N-stearyl-p-amino Phenol, 4-hydroxysalitylanilide, 4,4'-dihydroxydiphenyl ether, n-butylbis (hydroxyphenyl) acetate, α, α', α "-tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene , Sulfone Allyl.

4,4'-thiobis (6-t-butyl-m-cresol), 2,2-bis (3-allyl-4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxy- 3-Methylphenyl) Sulfide, p-tert-butylphenol, p-phenylphenol, p-benzylphenol, 1-naphthol, 2-naphthol and other phenolic compounds, N, N'-di-m-chlorophenylthiourea and the like. Urea compound, benzoic acid, p-tert-butyl benzoic acid, trichlorobenzoic acid, 3-sec-butyl-4-hydroxybenzoic acid, 3-cyclohexyl-4-hydroxybenzoic acid, 3,5-dimethyl-4-hydroxybenzoic acid Acids, terephthalic acid, salicylic acid, 3-isopropylsalicylic acid, 3-tert-butylsalicylic acid, 4- (2- (p-methoxyphenoxy) ethyloxy) salicylic acid, 4- (3- (p-tolylsulfonyl) propyloxy) salicylic acid, Aromatic carboxylic acids such as 5- (p- (2- (p-methoxyphenoxy) ethoxy) cumyl) salicylic acid, and zinc, magnesium, aluminum, calcium, titanium, manganese, tin, nickel and the like of these aromatic carboxylic acids. Salts with polyvalent metals, as well as organic acidic substances such as antipyrine complexes of zinc thiocyanate and complex zinc salts of terephthalaldehyde acid and other aromatic carboxylic acids.

<Resin [D]>
As the resin [D], as a water-soluble resin, cellulose, methyl cellulose, methoxy cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, polyacrylamide, polyacrylic acid, casein, gelatin, styrene / maleic anhydride copolymer salt, isobutylene. / Maleic anhydride copolymer salt, polyacrylic acid ester, polyurethane resin, acrylic / styrene resin and the like. As the solvent type resin, styrene / maleic acid, acrylic / styrene resin, polystyrene, polyester, polycarbonate, epoxy resin, polyurethane resin, polybutyral resin, polyacrylic acid ester, styrene / butadiene copolymer, styrene / butadiene / Acrylic acid copolymers, polyvinyl acetate, fluororesins, phenol resins, acrylic silicon / modified silicon resins, aminoalkyd resins, phthalic acid resins and the like can be mentioned, and water-soluble resins are preferable.
When used as a composition, a curing agent can be used in combination for the purpose of improving the film strength, heat resistance, water resistance, solvent resistance, etc. of the surface protective layer.
The content of the resin [D] is preferably 5 to 50% by mass, more preferably 5 to 30% by mass, based on the total solid content of the laser marking composition. As the resin [D], at least one selected from the group consisting of polyvinyl alcohol, polyacrylamide, polyacrylic acid, polyacrylic acid ester, polyurethane resin and acrylic / styrene resin is more preferable.

<Other known additives>
Other known additives include sensitizers, storage stabilizers, fillers, dispersants, surfactants, defoamers, optical brighteners, water resistant agents, lubricants, UV absorbers, antioxidants, etc. And can be used according to the required quality.

<Manufacturing method of laser marking composition>
The composition for laser marking of the present invention can be produced by a conventionally known method. The method for preparing various coating liquids for the laser marking composition is not particularly limited, and generally, water is used as a dispersion medium, and the near-infrared absorbing dye [A], the coloring agent [B], and the coloring agent [C] of the present invention are used. ], Resin [D] and, if necessary, other known additives can be mixed and stirred. The near-infrared absorbing dye [A], the coloring agent [B], and the coloring agent [C] of the present invention are separately crushed and dispersed in an aqueous system with a sand grinder, an attritor, a ball mill, etc., and then mixed to form an aqueous system. A method of obtaining a coating liquid and a method of obtaining an aqueous coating liquid after microencapsulating any one of the near-infrared absorbing dye [A], the coloring agent [B] and the coloring agent [C] of the present invention are known. ing.

The ratio of the color-developing agent [B] and the color-developing agent [C] to be used is appropriately selected according to the type of the color-developing agent [B] and the color-developing agent [C] to be used, and is not particularly limited. ] A color developer [C] of about 0.1 to 50 parts by mass, preferably about 0.1 to 10 parts by mass is used with respect to 1 part by mass.

The near-infrared absorbing dye [A] of the present invention is used in the range of 0.1 parts by mass or less, preferably 0.001 to 0.08 parts by mass, with respect to 1 part by mass of the color former [B]. The laser marking composition is preferably used in the range of 0.05 to 5% by mass, more preferably 0.05 to 3% by mass, based on the total solid content.

It is more preferable that the near-infrared absorbing dye [A], the coloring agent [B], and the coloring agent [C] of the present invention are atomized so as not to exceed the average particle size of 3 μm. As described above, the near-infrared absorbing dye [A] of the present invention can be used even in a dissolved state. Therefore, in that case, the average particle size of the near-infrared absorbing dye [A] of the present invention must be taken into consideration. May be good. The reason for atomization is that the more the material is atomized, the more the dot diameter of the colored printing part is almost the same as the spot diameter of the laser beam that is the light source, and the uniform dot diameter is obtained, resulting in high-quality and clear printing. This is because it is thought that a line drawing can be obtained.

<Coated material>
The composition for laser marking of the present invention can be coated on a known base material to obtain a coated product. The known base material may be made of a plastic film, paper, metal leaf, glass, ceramic, wood, or the like, and the shape and size of the base material may be arbitrary. The type of synthetic resin constituting the plastic film is not particularly limited, and may be a thermoplastic resin, a thermosetting resin, or a UV / EB curable resin. Examples of thermoplastic resins include polyolefin, polyvinylidene chloride, polyvinylidene chloride, polystyrene, polyvinylacetate, polytetrafluoroethylene, acrylonitrile butadiene styrene, polyacrylic methacrylate, polyamide, nylon, polyacetal, polycarbonate, polybutylene terephthalate, and polyethylene. Examples thereof include terephthalate, polyvinylidene chloride, polysulfone, polyimide, polyamide, mixtures thereof, and copolymers based on these. Examples of thermosetting resins include phenol resins, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, polyurethanes, thermosetting polyimides, and mixtures thereof.

(Coating method)
Examples of the coating method include, but are not limited to, spray coating, spin coating, slit coating, roll coating, inkjet, screen, gravure, offset, flexo and other printing methods.

<Recording material, laser>
The coated material can be used as a recording material by irradiating it with a laser beam. The laser beam used for laser marking is not particularly limited as long as it is a near-infrared laser beam, and examples thereof include laser beams such as semiconductor lasers, dye (pulse) lasers, and Alexandrite lasers. Since the near-infrared absorbing dye of the present invention has an absorption band in the region of 750 to 950 nm, the wavelength of the laser used is preferably in the range of 750 to 950 nm. The laser irradiation conditions are appropriately selected depending on the coating method, coating conditions, type of base material, and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded. In the examples and comparative examples, "parts" and "%" mean "parts by mass" and "% by mass", respectively.

(Method for identifying near-infrared absorbing dye [A])
The MALDITF-MS spectrum was used to identify the near-infrared absorbing dye [A] used in the present invention. For the MALDIOF-MS spectrum, the obtained compound was identified by matching the molecular ion peak of the obtained mass spectrum with the mass number obtained by calculation using the MALDI mass spectrometer autoflex III manufactured by Bruker Daltonics. ..

(Weight average molecular weight (Mw) of a resin having a quaternary ammonium base in the side chain)
The weight average molecular weight (Mw) of the resin having a quaternary ammonium base in the side chain used in the present invention is a GPC equipped with an RI detector using a TSKgel column (manufactured by Tosoh Corporation) (HLC-8120 GPC manufactured by Tosoh Corporation). It is a polystyrene-equivalent weight average molecular weight (Mw) measured using THF as a developing solvent.

(Quaternary ammonium salt value of a resin having a quaternary ammonium base in the side chain)
The quaternary ammonium salt value of the resin having a quaternary ammonium base in the side chain used in the present invention was determined by titrating with a 0.1 N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator, and then potassium hydroxide. Converted to the equivalent of. The quaternary ammonium salt value indicates the quaternary ammonium salt value of the solid content.

<Manufacturing method of near-infrared absorbing dye [A]>
[Method for producing compound [A] represented by general formula (1)]
(Manufacturing of near-infrared absorbing dye [A-1])
To 400 parts of toluene, 40.0 parts of 1,8-diaminonaphthalene, 25.1 parts of cyclohexanone, and 0.087 parts of p-toluenesulfonic acid monohydrate are mixed, heated and stirred in an atmosphere of nitrogen gas, and 3 It was refluxed for hours. The water produced during the reaction was removed from the system by azeotropic distillation. After completion of the reaction, the dark brown solid obtained by distilling toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The obtained brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, and 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added to create an atmosphere of nitrogen gas. The mixture was heated and stirred inside, and the mixture was refluxed for 8 hours. The water produced during the reaction was removed from the system by azeotropic distillation. After completion of the reaction, the solvent was distilled and 200 parts of hexane was added while stirring the obtained reaction mixture. The obtained black-brown precipitate was filtered off, washed successively with hexane, ethanol and acetone, dried under reduced pressure, and 61.9 parts of the near-infrared absorbing dye [A-1] (yield: 92%). Got As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-1].

Near-infrared absorbing dye [A-1]

(Manufacturing of near-infrared absorbing dye [A-2])
Production of near-infrared absorbing dye [A-1] except that 32.2 parts of 2,6-dimethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of near-infrared absorbing dye [A-1]. The same operation as in the above was carried out to obtain 71.9 parts (yield: 97%) of the near-infrared absorbing dye [A-2]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-2].

Near-infrared absorbing dye [A-2]

(Manufacture of near-infrared absorbing dye [A-3])
Production of near-infrared absorbing dye [A-1] except that 32.2 parts of 3,5-dimethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of near-infrared absorbing dye [A-1]. The same operation as in the above was carried out to obtain 72.6 parts (yield: 98%) of the near-infrared absorbing dye [A-3]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-3].

Near-infrared absorbing dye [A-3]

(Manufacturing of near-infrared absorbing dye [A-4])
Similar to the production of the near-infrared absorbing dye [A-1], except that 28.6 parts of 4-methylcyclohexanone was used instead of 25.1 parts of the cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. To obtain 67.2 parts (yield: 95%) of the near-infrared absorbing dye [A-4]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-4].

Near-infrared absorbing dye [A-4]

(Manufacturing of near-infrared absorbing dye [A-5])
Near-infrared absorbing dye [A-1], except that 35.8 parts of 3,3,5-trimethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. The same operation as in the production of the above was carried out to obtain 71.3 parts (yield: 92%) of the near-infrared absorbing dye [A-5]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-5].

Near infrared absorbing dye [A-5]

(Manufacturing of near-infrared absorbing dye [A-6])
Production of near-infrared absorbing dye [A-1] except that 39.4 parts of 3,5-diethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of near-infrared absorbing dye [A-1]. The same operation as in the above was carried out to obtain 76.9 parts (yield: 95%) of the near-infrared absorbing dye [A-6]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-6].

Near infrared absorbing dye [A-6]

(Manufacturing of near-infrared absorbing dye [A-7])
Near-infrared absorbing dye [A-1], except that 39.4 parts of 5-isopropyl-2-methylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. The same operation as in the production of the above was carried out to obtain 76.9 parts (yield: 95%) of the near-infrared absorbing dye [A-7]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-7].

Near-infrared absorbing dye [A-7]

(Manufacturing of near-infrared absorbing dye [A-8])
Similar to the production of the near-infrared absorbing dye [A-1], except that 46.0 parts of 2-cyclohexylcyclohexanone was used instead of 25.1 parts of the cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. To obtain 79.4 parts (yield: 91%) of the near-infrared absorbing dye [A-8]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-8].

Near infrared absorbing dye [A-8]

(Manufacturing of near-infrared absorbing dye [A-9])
Similar to the production of the near-infrared absorbing dye [A-1], except that 28.1 parts of 2-norbornenanone was used instead of 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. The operation was carried out to obtain 64.6 parts (yield: 92%) of the near-infrared absorbing dye [A-9]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-9].

Near-infrared absorbing dye [A-9]

(Manufacturing of near-infrared absorbing dye [A-10])
Near-infrared absorbing dye [A-1] except that 42.5 parts of spiro [5.5] undecane-1-one was used instead of 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. The same operation as in the production of -1] was carried out to obtain 78.8 parts (yield: 94%) of the near-infrared absorbing dye [A-10]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-10].

Near infrared absorbing dye [A-10]

(Manufacturing of near-infrared absorbing dye [A-11])
Instead of 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-1], 3-methyl-3,4,4a, 5,8,8a-hexahydronaphthalen-1 (2H) -one 41 The same operation as in the production of the near-infrared absorbing dye [A-1] was carried out except that 9 parts were used, and 76.7 parts (yield: 92%) of the near-infrared absorbing dye [A-11] was obtained. .. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-11].

Near-infrared absorbing dye [A-11]

(Manufacturing of near-infrared absorbing dye [A-12])
Near-infrared absorbing dye [A-1], except that 41.0 parts of 3- (2-chloroethyl) cyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. The same operation as in the production of the above was carried out to obtain 77.5 parts (yield: 94%) of the near-infrared absorbing dye [A-12]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-12].

Near infrared absorbing dye [A-12]

(Manufacturing of near-infrared absorbing dye [A-13])
Near-infrared absorbing dye [A-1] except that 59.8 parts of 3,5-di (trifluoromethyl) cyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. The same operation as in the production of -1] was carried out to obtain 93.3 parts (yield: 93%) of the near-infrared absorbing dye [A-13]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-13].

Near-infrared absorbing dye [A-13]

(Manufacturing of near-infrared absorbing dye [A-14])
Similar to the production of the near-infrared absorbing dye [A-1], except that 44.5 parts of 2-phenylcyclohexanone was used instead of 25.1 parts of the cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. To obtain 78.9 parts (yield: 92%) of a near-infrared absorbing dye [A-14]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-14].

Near-infrared absorbing dye [A-14]

(Manufacturing of near-infrared absorbing dye [A-15])
Production of near-infrared absorbing dye [A-1] except that 48.1 parts of 4-p-tolylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of near-infrared absorbing dye [A-1]. The same operation as in the above was carried out to obtain 84.7 parts (yield: 95%) of the near-infrared absorbing dye [A-15]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-15].

Near-infrared absorbing dye [A-15]

(Manufacturing of near-infrared absorbing dye [A-16])
Similar to the production of the near-infrared absorbing dye [A-1], except that 48.1 parts of 4-benzylcyclohexanone was used instead of 25.1 parts of the cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. 85.6 parts (yield: 96%) of the near-infrared absorbing dye [A-16] was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-16].

Near infrared absorbing dye [A-16]

(Manufacturing of near-infrared absorbing dye [A-17])
Similar to the production of the near-infrared absorbing dye [A-1], except that 36.3 parts of 4-ethoxycyclohexanone was used instead of 25.1 parts of the cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. 71.0 parts (yield: 91%) of the near-infrared absorbing dye [A-17] was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-17].

Near-infrared absorbing dye [A-17]

(Manufacturing of near-infrared absorbing dye [A-18])
Near-infrared absorbing dye [A-1] except that 68.0 parts of 2,6-di (trifluoromethoxy) cyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. The same operation as in the production of -1] was carried out to obtain 100.5 parts (yield: 93%) of the near-infrared absorbing dye [A-18]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-18].

Near-infrared absorbing dye [A-18]

(Manufacturing of near-infrared absorbing dye [A-19])
Similar to the production of the near-infrared absorbing dye [A-1], except that 48.6 parts of 4-phenoxycyclohexanone was used instead of 25.1 parts of the cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. 82.5 parts (yield: 92%) of the near-infrared absorbing dye [A-19] was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-19].

Near-infrared absorbing dye [A-19]

(Manufacturing of near-infrared absorbing dye [A-20])
Near-infrared absorbing dye [A-1] except that 51.1 parts of 3-oxo-cyclohexanesulfonic acid sodium salt was used instead of 25.1 parts of cyclohexanone used in the production of near-infrared absorbing dye [A-1]. ] Was carried out in the same manner as in the production of the near-infrared absorbing dye [A-20] to obtain 83.3 parts (yield: 96%). As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-20].

Near infrared absorbing dye [A-20]

(Manufacturing of near-infrared absorbing dye [A-21])
Near-infrared absorbing dye [A-1] except that 52.4 parts of N-ethyl-3-oxocyclohexane-1-sulfoamide was used instead of 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. The same operation as in the production of A-1] was carried out to obtain 87.7 parts (yield: 94%) of the near-infrared absorbing dye [A-21]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-21].

Near-infrared absorbing dye [A-21]

(Manufacturing of near-infrared absorbing dye [A-22])
Production of near-infrared absorbing dye [A-1] except that 36.3 parts of 4-oxocyclohexanecarboxylic acid was used instead of 25.1 parts of cyclohexanone used in the production of near-infrared absorbing dye [A-1]. The same operation as in the above was carried out to obtain 71.0 parts (yield: 91%) of the near-infrared absorbing dye [A-22]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-22].

Near-infrared absorbing dye [A-22]

(Manufacturing of near-infrared absorbing dye [A-23])
Of the near-infrared absorbing dye [A-1], except that 43.5 parts of ethyl 2-oxocyclohexanecarboxylic acid was used instead of 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. The same operation as in the production was carried out to obtain 78.9 parts (yield: 93%) of the near-infrared absorbing dye [A-23]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-23].

Near-infrared absorbing dye [A-23]

(Manufacturing of near-infrared absorbing dye [A-24])
Near-infrared absorbing dye [A-] except that 46.8 parts of 4-oxo-N-propylcyclohexanecarboxamide was used instead of 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. The same operation as in the production of 1] was carried out to obtain 87.1 parts (yield: 99%) of the near-infrared absorbing dye [A-24]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-24].

Near infrared absorbing dye [A-24]

(Manufacturing of near-infrared absorbing dye [A-25])
Similar to the production of the near-infrared absorbing dye [A-1], except that 28.9 parts of 4-aminocyclohexanone was used instead of 25.1 parts of the cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. To obtain 68.1 parts (yield: 96%) of the near-infrared absorbing dye [A-25]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-25].

Near infrared absorbing dye [A-25]

(Manufacturing of near-infrared absorbing dye [A-26])
Of the near-infrared absorbing dye [A-1], except that 36.1 parts of 4- (dimethylamino) cyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. The same operation as in the production was carried out to obtain 73.9 parts (yield: 95%) of the near-infrared absorbing dye [A-26]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-26].

Near infrared absorbing dye [A-26]

(Manufacturing of near-infrared absorbing dye [A-27])
Production of near-infrared absorbing dye [A-1] except that 31.4 parts of 4-oxocyclohexanecarbonitrile was used instead of 25.1 parts of cyclohexanone used in the production of near-infrared absorbing dye [A-1]. The same operation as in the above was carried out to obtain 67.5 parts (yield: 92%) of the near-infrared absorbing dye [A-27]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-27].

Near-infrared absorbing dye [A-27]

(Manufacturing of near-infrared absorbing dye [A-28])
Similar to the production of the near-infrared absorbing dye [A-1], except that 36.6 parts of 4-nitrocyclohexanone was used instead of 25.1 parts of the cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. 72.0 parts (yield: 92%) of the near-infrared absorbing dye [A-28] was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-28].

Near-infrared absorbing dye [A-28]

(Manufacturing of near-infrared absorbing dye [A-29])
Production of near-infrared absorbing dye [A-1] except that 34.3 parts of 3,5-difluorocyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of near-infrared absorbing dye [A-1]. The same operation as in the above was carried out to obtain 70.7 parts (yield: 93%) of the near-infrared absorbing dye [A-29]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-29].

Near infrared absorbing dye [A-29]

(Manufacturing of near-infrared absorbing dye [A-30])
Similar to the production of the near-infrared absorbing dye [A-1], except that 33.9 parts of 2-chlorocyclohexanone was used instead of 25.1 parts of the cyclohexanone used in the production of the near-infrared absorbing dye [A-1]. To obtain 71.1 parts (yield: 94%) of the near-infrared absorbing dye [A-30]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-30].

Near infrared absorbing dye [A-30]

(Manufacturing of near-infrared absorbing dye [A-31])
Production of near-infrared absorbing dye [A-1] except that 65.4 parts of 3,3-dibromocyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of near-infrared absorbing dye [A-1]. The same operation as in the above was carried out to obtain 99.3 parts (yield: 94%) of the near-infrared absorbing dye [A-31]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-31].

Near-infrared absorbing dye [A-31]

(Manufacturing of near-infrared absorbing dye [A-32])
400 parts of toluene is mixed with 43.5 parts of 1,8-diamino-3-methylnaphthalene, 25.1 parts of cyclohexanone, and 0.087 parts of p-toluenesulfonic acid monohydrate, and heated in an atmosphere of nitrogen gas. The mixture was stirred and refluxed for 3 hours. The water produced during the reaction was removed from the system by azeotropic distillation. After completion of the reaction, the dark brown solid obtained by distilling toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The obtained brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, and 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added to create an atmosphere of nitrogen gas. The mixture was heated and stirred inside, and the mixture was refluxed for 8 hours. The water produced during the reaction was removed from the system by azeotropic distillation. After completion of the reaction, the solvent was distilled and 200 parts of hexane was added while stirring the obtained reaction mixture. The obtained black-brown precipitate was filtered off, washed successively with hexane, ethanol and acetone, dried under reduced pressure, and 64.4 parts of the near-infrared absorbing dye [A-32] (yield: 91%). Got As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-32].

Near infrared absorbing dye [A-32]

(Manufacturing of near-infrared absorbing dye [A-33])
Instead of 43.5 parts of 1,8-diamino-3-methylnaphthalene and 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-32], 1,8-diamino-4-trifluoromethylnaphthalene The same operation as in the production of the near-infrared absorbing dye [A-32] was performed except that 57.2 parts and 32.2 parts of 2,6-dimethylcyclohexanone were used, and the near-infrared absorbing dye [A-33] 84. Three parts (yield: 93%) were obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-33].

Near-infrared absorbing dye [A-33]

(Manufacturing of near-infrared absorbing dye [A-34])
Instead of 43.5 parts of 1,8-diamino-3-methylnaphthalene and 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-32], 1,8-diamino-3-phenylnaphthalene 59. The same operation as in the production of the near-infrared absorbing dye [A-32] was performed except that 2 parts and 32.2 parts of 3,5-dimethylcyclohexanone were used, and 88.9 parts of the near-infrared absorbing dye [A-34] were used. (Yield: 96%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-34].

Near-infrared absorbing dye [A-34]

(Manufacturing of near-infrared absorbing dye [A-35])
Instead of 43.5 parts of 1,8-diamino-3-methylnaphthalene and 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-32], 1,8-diamino-3-p-tolylnaphthalene Except for the use of 62.8 parts and 28.6 parts of 4-methylcyclohexanone, the same operation as in the production of the near-infrared absorbing dye [A-32] was carried out, and 85.2 parts of the near-infrared absorbing dye [A-35] was performed. (Yield: 92%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-35].

Near-infrared absorbing dye [A-35]

(Manufacturing of near-infrared absorbing dye [A-36])
Instead of 43.5 parts of 1,8-diamino-3-methylnaphthalene and 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-32], 1,8-diamino-3-methoxynaphthalene 47. Except for the use of 6 parts and 35.8 parts of 3,3,5-trimethylcyclohexanone, the same operation as in the production of the near-infrared absorbing dye [A-32] was carried out, and the near-infrared absorbing dye [A-36] 79. 7 parts (yield: 94%) were obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-36].

Near infrared absorbing dye [A-36]

(Manufacture of near-infrared absorbing dye [A-37])
Instead of 43.5 parts of 1,8-diamino-3-methylnaphthalene and 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-32], 1,8-diamino-2-trifluoromethoxynaphthalene Except for the use of 61.2 parts and 39.4 parts of 3,5-diethylcyclohexanone, the same operation as in the production of the near-infrared absorbing dye [A-32] was carried out, and the near-infrared absorbing dye [A-37] 92. Two parts (yield: 90%) were obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-37].

Near infrared absorbing dye [A-37]

(Manufacturing of near-infrared absorbing dye [A-38])
Instead of 43.5 parts of 1,8-diamino-3-methylnaphthalene and 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-32], 1,8-diamino-2-phenoxynaphthalene 63. The same operation as in the production of the near-infrared absorbing dye [A-32] was carried out except that 3 parts and 39.4 parts of 5-isopropyl-2-methylcyclohexanone were used, and the near-infrared absorbing dye [A-38] 95. 0 parts (yield: 92%) were obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-38].

Near-infrared absorbing dye [A-38]

(Manufacturing of near-infrared absorbing dye [A-39])
Instead of 43.5 parts of 1,8-diamino-3-methylnaphthalene and 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-32], 1,8-diamino-3-p-tolyloxy Except for the use of 66.8 parts of naphthalene and 46.0 parts of 2-cyclohexylcyclohexanone, the same operation as in the production of the near-infrared absorbing dye [A-32] was carried out, and the near-infrared absorbing dye [A-39] 104.0 was performed. Part (yield: 92%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-39].

Near-infrared absorbing dye [A-39]

(Manufacturing of near-infrared absorbing dye [A-40])
Instead of 43.5 parts of 1,8-diamino-3-methylnaphthalene used in the production of the near-infrared absorbing dye [A-32], 60.2 parts of 4,5-diaminonaphthalene-1-sulfonic acid was used. Except for the above, the same operation as in the production of the near-infrared absorbing dye [A-32] was carried out to obtain 80.7 parts (yield: 93%) of the near-infrared absorbing dye [A-40]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-40].

Near infrared absorbing dye [A-40]

(Manufacturing of near-infrared absorbing dye [A-41])
Production of near-infrared absorbing dye [A-40], except that 32.2 parts of 2,6-dimethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of near-infrared absorbing dye [A-40]. The same operation as in the above was carried out to obtain 87.0 parts (yield: 93%) of the near-infrared absorbing dye [A-41]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-41].

Near-infrared absorbing dye [A-41]

(Manufacturing of near-infrared absorbing dye [A-42])
Production of near-infrared absorbing dye [A-40], except that 32.2 parts of 3,5-dimethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of near-infrared absorbing dye [A-40]. The same operation as in the above was carried out to obtain 87.0 parts (yield: 93%) of the near-infrared absorbing dye [A-42]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-42].

Near-infrared absorbing dye [A-42]

(Manufacturing of near-infrared absorbing dye [A-43])
Similar to the production of the near-infrared absorbing dye [A-40], except that 28.6 parts of 4-methylcyclohexanone was used instead of 25.1 parts of the cyclohexanone used in the production of the near-infrared absorbing dye [A-40]. 83.8 parts (yield: 93%) of the near-infrared absorbing dye [A-43] was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-43].

Near-infrared absorbing dye [A-43]

(Manufacturing of near-infrared absorbing dye [A-44])
Instead of 43.5 parts of 1,8-diamino-3-methylnaphthalene and 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-32], 4,5-diamino-N-ethylnaphthalene-1 The same operation as in the production of the near-infrared absorbing dye [A-32] was carried out except that 67.1 parts of −sulfoamide and 28.1 parts of 2-norbornenanone were used, and the near-infrared absorbing dye [A-44] 90.5 was performed. Part (yield: 94%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-44].

Near-infrared absorbing dye [A-44]

(Manufacturing of near-infrared absorbing dye [A-45])
Instead of 43.5 parts of 1,8-diamino-3-methylnaphthalene and 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-32], 4,5-diamino-1-naphthoic acid 51. The same operation as in the production of the near-infrared absorbing dye [A-32] was performed except that 1 part and 42.5 parts of the spiro [5.5] undecane-1-one were used, and the near-infrared absorbing dye [A-45] was used. ] 86.0 parts (yield: 91%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-45].

Near-infrared absorbing dye [A-45]

(Manufacturing of near-infrared absorbing dye [A-46])
Methyl 4,5-diamino-1-naphthoate 54 instead of 43.5 parts of 1,8-diamino-3-methylnaphthalene and 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-32] .. 7 parts and 3-methyl-3,4,4a, 5,8,8a-hexahydronaphthalene-1 (2H) -one 41.9 parts are used, but the near-infrared absorbing dye [A-32] The same operation as in the production was carried out to obtain 89.7 parts (yield: 92%) of the near-infrared absorbing dye [A-46]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-46].

Near infrared absorbing dye [A-46]

(Manufacturing of near-infrared absorbing dye [A-47])
Instead of 43.5 parts of 1,8-diamino-3-methylnaphthalene and 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-32], 4,5-diamino-N-ethylnaphthamide 58 The same operation as in the production of the near-infrared absorbing dye [A-32] was performed except that 0 part and 41.0 parts of 3- (2-chloroethyl) cyclohexanone were used, and the near-infrared absorbing dye [A-47] 90 was performed. 8. 8 parts (yield: 91%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-47].

Near-infrared absorbing dye [A-47]

(Manufacturing of near-infrared absorbing dye [A-48])
Instead of 43.5 parts of 1,8-diamino-3-methylnaphthalene and 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-32], 1,8-diamino-3-nitrophthalene 51.4 The same operation as in the production of the near-infrared absorbing dye [A-32] was performed except that 59.8 parts of the part and 3,5-di (trifluoromethyl) cyclohexanone were used, and the near-infrared absorbing dye [A-48] was used. 103.5 parts (yield: 93%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-48].

Near-infrared absorbing dye [A-48]

(Manufacturing of near-infrared absorbing dye [A-49])
Instead of 43.5 parts of 1,8-diamino-3-methylnaphthalene and 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-32], 1,8-diamino-4-chloronaphthalene 48. The same operation as in the production of the near-infrared absorbing dye [A-32] was performed except that 7 parts and 32.2 parts of 3,5-dimethylcyclohexanone were used, and 75.9 parts of the near-infrared absorbing dye [A-49] were used. (Yield: 92%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-49].

Near-infrared absorbing dye [A-49]

(Manufacturing of near-infrared absorbing dye [A-50])
Instead of 43.5 parts of 1,8-diamino-3-methylnaphthalene and 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-32], 1,8-diamino-4-chloronaphthalene 48. The same operation as in the production of the near-infrared absorbing dye [A-32] was performed except that 7 parts and 44.5 parts of 2-phenylcyclohexanone were used, and 90.4 parts of the near-infrared absorbing dye [A-50] (collected). Rate: 96%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-50].

Near infrared absorbing dye [A-50]

(Manufacturing of near-infrared absorbing dye [A-51])
Instead of 43.5 parts of 1,8-diamino-3-methylnaphthalene and 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-32], 1,8-diamino-4-chloronaphthalene 48. The same operation as in the production of the near-infrared absorbing dye [A-32] was performed except that 7 parts and 48.1 parts of 4-p-tolylcyclohexanone were used, and 92.7 parts of the near-infrared absorbing dye [A-51] were used. (Yield: 95%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-51].

Near-infrared absorbing dye [A-51]

(Manufacturing of near-infrared absorbing dye [A-52])
Instead of 43.5 parts of 1,8-diamino-3-methylnaphthalene and 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-32], 1,8-diamino-4-chloronaphthalene 48. The same operation as in the production of the near-infrared absorbing dye [A-32] was performed except that 7 parts and 48.1 parts of 4-benzylcyclohexanone were used, and 88.8 parts of the near-infrared absorbing dye [A-52] (collected). Rate: 91%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-52].

Near-infrared absorbing dye [A-52]

(Manufacturing of near-infrared absorbing dye [A-53])
Instead of 43.5 parts of 1,8-diamino-3-methylnaphthalene and 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-32], 1,8-diamino-4-chloronaphthalene 48. The same operation as in the production of the near-infrared absorbing dye [A-32] was performed except that 7 parts and 36.3 parts of 4-ethoxycyclohexanone were used, and 80.3 parts of the near-infrared absorbing dye [A-53] (collected). Rate: 93%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-53].

Near infrared absorbing dye [A-53]

(Manufacturing of near-infrared absorbing dye [A-54])
Instead of 43.5 parts of 1,8-diamino-3-methylnaphthalene and 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-32], 1,8-diamino-4-chloronaphthalene 48. The same operation as in the production of the near-infrared absorbing dye [A-32] was performed except that 7 parts and 68.0 parts of 2,6-di (trifluoromethoxy) cyclohexanone were used, and the near-infrared absorbing dye [A-54] was used. ] 109.5 parts (yield: 94%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-54].

Near-infrared absorbing dye [A-54]

(Manufacturing of near-infrared absorbing dye [A-55])
Instead of 43.5 parts of 1,8-diamino-3-methylnaphthalene and 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-32], 1,8-diamino-4-chloronaphthalene 48. Except for the use of 7 parts and 48.6 parts of 4-phenoxycyclohexanone, the same operation as in the production of the near-infrared absorbing dye [A-32] was performed, and 91.2 parts of the near-infrared absorbing dye [A-55] (collected). Rate: 93%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-55].

Near-infrared absorbing dye [A-55]

(Manufacturing of near-infrared absorbing dye [A-56])
Instead of 43.5 parts of 1,8-diamino-3-methylnaphthalene and 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-32], 1,8-diamino-4-chloronaphthalene 48. The same operation as in the production of the near-infrared absorbing dye [A-32] was carried out except that 7 parts and 51.1 parts of 3-oxo-cyclohexanesulfonic acid sodium salt were used, and the near-infrared absorbing dye [A-56] 88 was performed. .5 parts (yield: 93%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-56].

Near infrared absorbing dye [A-56]

(Manufacturing of near-infrared absorbing dye [A-57])
Instead of 43.5 parts of 1,8-diamino-3-methylnaphthalene and 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-32], 1,8-diamino-4-chloronaphthalene 48. The same operation as in the production of the near-infrared absorbing dye [A-32] was performed except that 7 parts and 52.4 parts of N-ethyl-3-oxocyclohexane-1-sulfoamide were used, and the near-infrared absorbing dye [A-57] was used. ] 92.5 parts (yield: 91%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-57].

Near-infrared absorbing dye [A-57]

(Manufacturing of near-infrared absorbing dye [A-58])
Instead of 43.5 parts of 1,8-diamino-3-methylnaphthalene and 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-32], 1,8-diamino-4-chloronaphthalene 48. The same operation as in the production of the near-infrared absorbing dye [A-32] was performed except that 7 parts and 36.3 parts of 4-oxocyclohexanecarboxylic acid were used, and 79.5 parts of the near-infrared absorbing dye [A-58] was used. (Yield: 92%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-58].

Near infrared absorbing dye [A-58]

(Manufacturing of near-infrared absorbing dye [A-59])
Instead of 43.5 parts of 1,8-diamino-3-methylnaphthalene and 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-32], 1,8-diamino-4-chloronaphthalene 48. The same operation as in the production of the near-infrared absorbing dye [A-32] was performed except that 7 parts and 43.5 parts of ethyl 2-oxocyclohexanecarboxylate were used, and the near-infrared absorbing dye [A-59] 88.5 was performed. Parts (yield: 95%) were obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-59].

Near-infrared absorbing dye [A-59]

(Manufacturing of near-infrared absorbing dye [A-60])
Instead of 43.5 parts of 1,8-diamino-3-methylnaphthalene and 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-32], 1,8-diamino-4-chloronaphthalene 48. The same operation as in the production of the near-infrared absorbing dye [A-32] was performed except that 7 parts and 46.8 parts of 4-oxo-N-propylcyclohexanecarboxamide were used, and the near-infrared absorbing dye [A-60] 89 was performed. .6 parts (yield: 93%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-60].

Near infrared absorbing dye [A-60]

(Manufacturing of near-infrared absorbing dye [A-61])
Instead of 43.5 parts of 1,8-diamino-3-methylnaphthalene and 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-32], 1,8-diamino-4-chloronaphthalene 48. Except for the use of 7 parts and 28.9 parts of 4-aminocyclohexanone, the same operation as in the production of the near-infrared absorbing dye [A-32] was carried out, and 73.0 parts of the near-infrared absorbing dye [A-61] (collected). Rate: 92%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-61].

Near-infrared absorbing dye [A-61]

(Manufacturing of near-infrared absorbing dye [A-62])
Instead of 43.5 parts of 1,8-diamino-3-methylnaphthalene and 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-32], 1,8-diamino-4-chloronaphthalene 48. The same operation as in the production of the near-infrared absorbing dye [A-32] was performed except that 7 parts and 36.1 parts of 4- (dimethylamino) cyclohexanone were used, and the near-infrared absorbing dye [A-62] 81.0 was performed. Parts (yield: 94%) were obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-62].

Near infrared absorbing dye [A-62]

(Manufacturing of near-infrared absorbing dye [A-63])
Instead of 43.5 parts of 1,8-diamino-3-methylnaphthalene and 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-32], 1,8-diamino-4-chloronaphthalene 48. The same operation as in the production of the near-infrared absorbing dye [A-32] was performed except that 7 parts and 31.4 parts of 4-oxocyclohexanecarbonitrile were used, and 77.7 parts of the near-infrared absorbing dye [A-63] was used. (Yield: 95%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-63].

Near-infrared absorbing dye [A-63]

(Manufacturing of near-infrared absorbing dye [A-64])
Instead of 43.5 parts of 1,8-diamino-3-methylnaphthalene and 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-32], 1,8-diamino-4-chloronaphthalene 48. Except for the use of 7 parts and 36.6 parts of 4-nitrocyclohexanone, the same operation as in the production of the near-infrared absorbing dye [A-32] was carried out, and 78.8 parts of the near-infrared absorbing dye [A-64] (yield). Rate: 91%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-64].

Near infrared absorbing dye [A-64]

(Manufacturing of near-infrared absorbing dye [A-65])
Instead of 43.5 parts of 1,8-diamino-3-methylnaphthalene and 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-32], 1,8-diamino-4,5-dichloronaphthalene Except for the use of 57.4 parts and 34.3 parts of 3,5-difluorocyclohexanone, the same operation as in the production of the near-infrared absorbing dye [A-32] was carried out, and the near-infrared absorbing dye [A-65] 88. One part (yield: 95%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-65].

Near infrared absorbing dye [A-65]

(Manufacturing of near-infrared absorbing dye [A-66])
Instead of 43.5 parts of 1,8-diamino-3-methylnaphthalene and 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-32], 1,8-diamino-4,5-dibromonaphthalene Except for the use of 79.9 parts and 33.9 parts of 2-chlorocyclohexanone, the same operation as in the production of the near-infrared absorbing dye [A-32] was carried out, and 102.6 parts of the near-infrared absorbing dye [A-66] was performed. (Yield: 90%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-66].

Near-infrared absorbing dye [A-66]

(Manufacturing of near-infrared absorbing dye [A-67])
Instead of 43.5 parts of 1,8-diamino-3-methylnaphthalene and 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye [A-32], 1,8-diamino-2-naphthonitrile 46. Except for the use of 3 parts and 65.4 parts of 3,3-dibromocyclohexanone, the same operation as in the production of the near-infrared absorbing dye [A-32] was carried out, and 102.8 parts of the near-infrared absorbing dye [A-67] was performed. (Yield: 92%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-67].

Near infrared absorbing dye [A-67]

(Manufacturing of near-infrared absorbing dye [A-68])
20.0 parts of the near-infrared absorbing dye [A-42] was added to 300 parts of water, stirred and redispersed, and then the pH was adjusted to 9.0 with 26% aqueous ammonia and dissolved. 179.7 parts of an 8% dodecyltrimethylammonium chloride aqueous solution was gradually added to this solution. Precipitates appeared one after another from the dropped portion, and the pH gradually decreased with the addition. No bleeding was observed after the addition was completed. The precipitate was separated from the slurry by filtration, washed with water, and dried at 80 ° C. to obtain 31.5 parts (yield: 99%) of the near-infrared absorbing dye [A-68].

(Manufacturing of near-infrared absorbing dye [A-69])
Near-infrared absorbing dye except that 219.5 parts of 8% tetrabutylammonium bromide aqueous solution was used instead of 179.7 parts of the 8% dodecyltrimethylammonium chloride aqueous solution used in the production of the near-infrared absorbing dye [A-68]. The same operation as in the production of [A-68] was carried out to obtain 32.2 parts (yield: 99%) of the near-infrared absorbing dye [A-69].

(Manufacturing of near-infrared absorbing dye [A-70])
Instead of 179.7 parts of the 8% dodecyltrimethylammonium chloride aqueous solution used in the production of the near-infrared absorbing dye [A-68], 181.2 parts of the 8% 1,2-dimethyl-3-propylimidazolium iodide aqueous solution was used. Except for the use, the same operation as in the production of the near-infrared absorbing dye [A-68] was carried out to obtain 26.6 parts (yield: 98%) of the near-infrared absorbing dye [A-70].

(Manufacturing of near-infrared absorbing dye [A-71])
Near-infrared absorption except that 116.9 parts of 8% 1-butylpyridinium chloride aqueous solution was used instead of 179.7 parts of the 8% dodecyltrimethylammonium chloride aqueous solution used in the production of the near-infrared absorbing dye [A-68]. The same operation as in the production of the dye [A-68] was carried out to obtain 26.7 parts (yield: 99%) of the near-infrared absorbing dye [A-71].

(Manufacturing of near-infrared absorbing dye [A-72])
Near-infrared absorption except that 252.8 parts of an 8% ethyltriphenylphosphonium bromide aqueous solution was used instead of 179.7 parts of the 8% dodecyltrimethylammonium chloride aqueous solution used in the production of the near-infrared absorbing dye [A-68]. The same operation as in the production of the dye [A-68] was carried out to obtain 34.7 parts (yield: 99%) of the near-infrared absorbing dye [A-72].

(Manufacturing of near-infrared absorbing dye [A-73])
Near-infrared absorbing dye [A-68], except that 107.0 parts of 8% trimethylsulfonium bromide aqueous solution was used instead of 179.7 parts of the 8% dodecyltrimethylammonium chloride aqueous solution used in the production of the near-infrared absorbing dye [A-68]. The same operation as in the production of A-68] was carried out to obtain 23.5 parts (yield: 98%) of the near-infrared absorbing dye [A-73].

(Manufacturing of near-infrared absorbing dye [A-74])
Near-infrared absorbing dye [A], except that 71.5 parts of 8% aluminum sulfate aqueous solution was used instead of 179.7 parts of the 8% dodecyltrimethylammonium chloride aqueous solution used in the production of the near-infrared absorbing dye [A-68]. The same operation as in the production of −68] was carried out to obtain 20.2 parts (yield: 99%) of the near-infrared absorbing dye [A-74].

[Manufacturing method of near-infrared absorbing dye [A] represented by the general formula (2)]
(Manufacturing of near-infrared absorbing dye [A-75])
To 400 parts of toluene, 40.0 parts of 1,8-diaminonaphthalene, 25.6 parts of tetrahydro-4H-pyran-4-one, and 0.087 parts of p-toluenesulfonic acid monohydrate are mixed and mixed with nitrogen gas. The mixture was heated and stirred in an atmosphere and refluxed for 3 hours. The water produced during the reaction was removed from the system by azeotropic distillation. After completion of the reaction, the dark brown solid obtained by distilling toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The obtained brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, and 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added to create an atmosphere of nitrogen gas. The mixture was heated and stirred inside, and the mixture was refluxed for 8 hours. The water produced during the reaction was removed from the system by azeotropic distillation. After completion of the reaction, the solvent was distilled and 200 parts of hexane was added while stirring the obtained reaction mixture. The obtained black-brown precipitate was filtered off, washed successively with hexane, ethanol and acetone, dried under reduced pressure, and 65.8 parts of a near-infrared absorbing dye [A-75] (yield: 97%). Got As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-75].

Near infrared absorbing dye [A-75]

(Manufacturing of near-infrared absorbing dye [A-76])
Instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-75], 32.7 parts of 2,6-dimethyl-dihydro-4H-pyran-4-one The same operation as in the production of the near-infrared absorbing dye [A-75] was carried out except that 70.9 parts (yield: 95%) of the near-infrared absorbing dye [A-76] was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-76].

Near-infrared absorbing dye [A-76]

(Manufacturing of near-infrared absorbing dye [A-77])
Near-infrared rays, except that 1-ethyl-4-piperidinone was used in place of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-75]. The same operation as in the production of the absorbing dye [A-75] was carried out to obtain 70.6 parts (yield: 95%) of the near-infrared absorbing dye [A-77]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-77].

Near infrared absorbing dye [A-77]

(Manufacturing of near-infrared absorbing dye [A-78])
Instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-75], 39.6 parts of 2,2,6,6-tetramethyl-4-piperidin The same operation as in the production of the near-infrared absorbing dye [A-75] was carried out except that the above was used to obtain 76.3 parts (yield: 94%) of the near-infrared absorbing dye [A-78]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-78].

Near infrared absorbing dye [A-78]

(Manufacturing of near-infrared absorbing dye [A-79])
Near-infrared absorbing dye [A], except that 29.7 parts of 4-oxotian was used instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-75]. The same operation as in the production of −75] was carried out to obtain 68.8 parts (yield: 96%) of the near-infrared absorbing dye [A-79]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-79].

Near infrared absorbing dye [A-79]

(Manufacturing of near-infrared absorbing dye [A-80])
Instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-75], 53.7 parts of 2-phenyl-1,3-dithian-5-on was used. The same operation as in the production of the near-infrared absorbing dye [A-75] was carried out except that 88.9 parts (yield: 94%) of the near-infrared absorbing dye [A-80] was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-80].

Near infrared absorbing dye [A-80]

(Manufacturing of near-infrared absorbing dye [A-81])
Near-infrared absorbing dye [A-75], except that 36.3 parts of alloxan was used instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of near-infrared absorbing dye [A-75]. ] Was carried out in the same manner as in the production of the near-infrared absorbing dye [A-81] to obtain 74.9 parts (yield: 96%). As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-81].

Near-infrared absorbing dye [A-81]

(Manufacturing of near-infrared absorbing dye [A-82])
Near-infrared absorbing dye [A], except that 18.4 parts of 3-oxetanone was used instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-75]. The same operation as in the production of −75] was carried out to obtain 56.1 parts (yield: 92%) of the near-infrared absorbing dye [A-82]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-82].

Near-infrared absorbing dye [A-82]

(Manufacturing of near-infrared absorbing dye [A-83])
Near-infrared absorbing dye except that 22.0 parts of tetrahydrofuran-3-on was used instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-75]. The same operation as in the production of [A-75] was carried out to obtain 59.9 parts (yield: 93%) of the near-infrared absorbing dye [A-83]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-83].

Near-infrared absorbing dye [A-83]

(Manufacturing of near-infrared absorbing dye [A-84])
Instead of the 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-75], 1-azabicyclo [3,2,1] octane-3-one 32.0 parts The same operation as in the production of the near-infrared absorbing dye [A-75] was carried out except that 69.4 parts (yield: 94%) of the near-infrared absorbing dye [A-84] was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-84].

Near infrared absorbing dye [A-84]

(Manufacturing of near-infrared absorbing dye [A-85])
Instead of 40.0 parts of 1,8-diaminonaphthalene and 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-75], 1,8-diamino-3-3 The same operation as the production of the near-infrared absorbing dye [A-75] was performed except that 43.5 parts of methylnaphthalene and 68.0 parts of 2-benzyl-6-phenyl-dihydro-4H-pyran-4-one were used. This was carried out to obtain 101.5 parts (yield: 91%) of the near-infrared absorbing dye [A-85]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-85].

Near-infrared absorbing dye [A-85]

(Manufacturing of near-infrared absorbing dye [A-86])
Instead of 40.0 parts of 1,8-diaminonaphthalene and 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-75], 1,8-diamino-4-one Production of near-infrared absorbing dye [A-75], except that 57.2 parts of trifluoromethylnaphthalene and 35.5 parts of 2-methyl-2-azabicyclo [2,2,2] octane-5-one were used. The same operation was carried out to obtain 87.2 parts (yield: 93%) of the near-infrared absorbing dye [A-86]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-86].

Near infrared absorbing dye [A-86]

(Manufacturing of near-infrared absorbing dye [A-87])
Instead of 40.0 parts of 1,8-diaminonaphthalene and 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-75], 1,8-diamino-3-3 Except for the use of 59.2 parts of phenylnaphthalene and 49.9 parts of 1-isopropyloctahydroquinoline-4 (1H) -on, the same operation as for the production of the near-infrared absorbing dye [A-75] was performed to carry out near-infrared rays. 103.9 parts (yield: 95%) of the absorbent dye [A-87] was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-87].

Near-infrared absorbing dye [A-87]

(Manufacturing of near-infrared absorbing dye [A-88])
Instead of 40.0 parts of 1,8-diaminonaphthalene and 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-75], 1,8-diamino-3-3 Except for the use of 62.8 parts of p-tolylnaphthalene and 35.5 parts of hexahydroindolizine-7 (1H) -on, the same operation as for the production of the near-infrared absorbing dye [A-75] was performed to carry out near-infrared rays. 91.2 parts (yield: 92%) of the absorbent dye [A-88] was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-88].

Near infrared absorbing dye [A-88]

(Manufacturing of near-infrared absorbing dye [A-89])
Instead of 40.0 parts of 1,8-diaminonaphthalene and 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-75], 1,8-diamino-3-3 Similar to the production of near-infrared absorbing dye [A-75], except that 47.6 parts of methoxynaphthalene and 70.9 parts of 2- (4-chlorophenyl) -6- (trifluoromethyl) piperidine-4-one were used. To obtain 102.4 parts (yield: 94%) of the near-infrared absorbing dye [A-89]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-89].

Near-infrared absorbing dye [A-89]

(Manufacturing of near-infrared absorbing dye [A-90])
Instead of 40.0 parts of 1,8-diaminonaphthalene and 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-75], 1,8-diamino-2- Except for the use of 61.2 parts of trifluoromethoxynaphthalene and 41.9 parts of thiochroman-4-one, the same operation as in the production of the near-infrared absorbing dye [A-75] was carried out, and the near-infrared absorbing dye [A-90] was used. ] 94.9 parts (yield: 90%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-90].

Near-infrared absorbing dye [A-90]

(Manufacturing of near-infrared absorbing dye [A-91])
Instead of 40.0 parts of 1,8-diaminonaphthalene and 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-75], 1,8-diamino-2- Except for the use of 63.3 parts of phenoxynaphthalene and 35.8 parts of 2,6-dimethyl-4H-thiopyran-4-one, the same operation as in the production of the near-infrared absorbing dye [A-75] was performed to carry out near-infrared rays. 85.6 parts (yield: 92%) of the absorbent dye [A-91] was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-91].

Near infrared absorbing dye [A-91]

(Manufacturing of near-infrared absorbing dye [A-92])
Instead of 40.0 parts of 1,8-diaminonaphthalene and 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-75], 1,8-diamino-3-3 Similar to the production of near-infrared absorbing dye [A-75], except that 66.8 parts of p-tolyloxynaphthalene and 33.2 parts of 6- (hydroxymethyl) dihydro-2H-pyran-3 (4H) -one were used. 92.8 parts (yield: 92%) of the near-infrared absorbing dye [A-92] was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-92].

Near-infrared absorbing dye [A-92]

(Manufacturing of near-infrared absorbing dye [A-93])
Near-infrared absorbing dye [A-75], except that 40.0 parts of 4,5-diaminonaphthalene-1-sulfonic acid was used instead of 40.0 parts of 1,8-diaminonaphthalene used in the production. The same operation as in the production of the infrared absorbing dye [A-75] was carried out to obtain 81.1 parts (yield: 93%) of the near infrared absorbing dye [A-93]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-93].

Near-infrared absorbing dye [A-93]

(Manufacturing of near-infrared absorbing dye [A-94])
Instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-93], 32.7 parts of 2,6-dimethyl-dihydro-4H-pyran-4-one The same operation as in the production of the near-infrared absorbing dye [A-93] was carried out except that 86.5 parts (yield: 92%) of the near-infrared absorbing dye [A-94] was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-94].

Near-infrared absorbing dye [A-94]

(Manufacturing of near-infrared absorbing dye [A-95])
Near-infrared rays, except that 1-ethyl-4-piperidinone was used in place of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-93]. The same operation as in the production of the absorbing dye [A-93] was carried out to obtain 87.2 parts (yield: 93%) of the near-infrared absorbing dye [A-95]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-95].

Near infrared absorbing dye [A-95]

(Manufacturing of near-infrared absorbing dye [A-96])
Instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-93], 39.6 parts of 2,2,6,6-tetramethyl-4-piperidin was used. Except for the use, the same operation as in the production of the near-infrared absorbing dye [A-93] was carried out to obtain 94.6 parts (yield: 94%) of the near-infrared absorbing dye [A-96]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-96].

Near infrared absorbing dye [A-96]

(Manufacturing of near-infrared absorbing dye [A-97])
Near-infrared absorbing dye [A-93] except that 29.7 parts of 4-oxotian was used instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-93]. The same operation as in the production of −93] was carried out to obtain 82.9 parts (yield: 91%) of the near-infrared absorbing dye [A-97]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-97].

Near-infrared absorbing dye [A-97]

(Manufacturing of near-infrared absorbing dye [A-98])
Instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-93], 53.7 parts of 2-phenyl-1,3-dithian-5-on was used. The same operation as in the production of the near-infrared absorbing dye [A-93] was carried out except for the above, and 103.7 parts (yield: 91%) of the near-infrared absorbing dye [A-98] was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-98].

Near-infrared absorbing dye [A-98]

(Manufacturing of near-infrared absorbing dye [A-99])
Near-infrared absorbing dye [A-93], except that 36.3 parts of alloxan was used instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of near-infrared absorbing dye [A-93]. ] Was carried out in the same manner as in the production of the near-infrared absorbing dye [A-99] to obtain 90.6 parts (yield: 93%). As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-99].

Near-infrared absorbing dye [A-99]

(Manufacturing of near-infrared absorbing dye [A-100])
Instead of 40.0 parts of 1,8-diaminonaphthalene and 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-75], 4,5-diamino-N- Of the near-infrared absorbing dye [A-75], except that 67.1 parts of ethylnaphthalene-1-sulfoamide and 39.9 parts of hexahydropyrano [3,2-b] pyran-3 (2H) -one were used. The same operation as in the production was carried out to obtain 101.1 parts (yield: 94%) of the near-infrared absorbing dye [A-100]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-100].

Near infrared absorbing dye [A-100]

(Manufacturing of near-infrared absorbing dye [A-101])
Instead of 40.0 parts of 1,8-diaminonaphthalene and 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-75], 4,5-diamino-1- The same operation as in the production of the near-infrared absorbing dye [A-75] was performed except that 51.1 parts of naphthoic acid and 29.1 parts of 1-azabicyclo [2.2.1] heptane-3-one were used. 73.9 parts (yield: 91%) of the near-infrared absorbing dye [A-101] was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-101].

Near-infrared absorbing dye [A-101]

(Manufacturing of near-infrared absorbing dye [A-102])
Instead of 40.0 parts of 1,8-diaminonaphthalene and 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-75], 4,5-diamino-1- Except for the use of 54.7 parts of methyl naphthoate and 48.3 parts of 1-methyl-4-phenylpiperidine-3-one, the same operation as in the production of the near-infrared absorbing dye [A-75] was performed to carry out near-infrared rays. 95.2 parts (yield: 92%) of the absorbing dye [A-102] was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-102].

Near-infrared absorbing dye [A-102]

(Manufacturing of near-infrared absorbing dye [A-103])
Instead of 40.0 parts of 1,8-diaminonaphthalene and 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-75], 4,5-diamino-N- The same operation as the production of the near-infrared absorbing dye [A-75] except that 58.0 parts of ethylnaphthamide and 36.8 parts of 5,5-dimethyldihydro-2H-thiopyran-3 (4H) -one were used. To obtain 87.1 parts (yield: 91%) of the near-infrared absorbing dye [A-103]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-103].

Near-infrared absorbing dye [A-103]

(Manufacturing of near-infrared absorbing dye [A-104])
Instead of 40.0 parts of 1,8-diaminonaphthalene and 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-75], 1,8-diamino-3-3 Except for the use of 51.4 parts of nitrophthalene and 41.9 parts of isothiochroman-4-one, the same operation as in the production of the near-infrared absorbing dye [A-75] was carried out, and the near-infrared absorbing dye [A-104] was performed. 87.7 parts (yield: 93%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-104].

Near infrared absorbing dye [A-104]

(Manufacturing of near-infrared absorbing dye [A-105])
Near-infrared rays, except that 48.7 parts of 1,8-diamino-4-chloronaphthalene was used instead of 40.0 parts of 1,8-diaminonaphthalene used in the production of the near-infrared absorbing dye [A-75]. The same operation as in the production of the absorbing dye [A-75] was carried out to obtain 70.1 parts (yield: 92%) of the near-infrared absorbing dye [A-105]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-105].

Near-infrared absorbing dye [A-105]

(Manufacturing of near-infrared absorbing dye [A-106])
Instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-105], 32.7 parts of 2,6-dimethyl-dihydro-4H-pyran-4-one The same operation as in the production of the near-infrared absorbing dye [A-105] was carried out except that 79.6 parts (yield: 96%) of the near-infrared absorbing dye [A-106] was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-106].

Near-infrared absorbing dye [A-106]

(Manufacturing of near-infrared absorbing dye [A-107])
Near-infrared rays, except that 1-ethyl-4-piperidinone was used in place of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-105]. The same operation as in the production of the absorbing dye [A-105] was carried out to obtain 78.6 parts (yield: 95%) of the near-infrared absorbing dye [A-107]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-107].

Near-infrared absorbing dye [A-107]

(Manufacturing of near-infrared absorbing dye [A-108])
Instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-105], 39.6 parts of 2,2,6,6-tetramethyl-4-piperidin was used. Except for the use, the same operation as in the production of the near-infrared absorbing dye [A-105] was carried out to obtain 81.5 parts (yield: 91%) of the near-infrared absorbing dye [A-108]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-108].

Near-infrared absorbing dye [A-108]

(Manufacturing of near-infrared absorbing dye [A-109])
Near-infrared absorbing dye [A-105] except that 29.7 parts of 4-oxotian was used instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-105]. The same operation as in the production of −105] was carried out to obtain 74.5 parts (yield: 93%) of the near-infrared absorbing dye [A-109]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-109].

Near infrared absorbing dye [A-109]

(Manufacturing of near-infrared absorbing dye [A-110])
Instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-105], 53.7 parts of 2-phenyl-1,3-dithian-5-on was used. The same operation as in the production of the near-infrared absorbing dye [A-105] was carried out except that 96.7 parts (yield: 94%) of the near-infrared absorbing dye [A-110] was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-110].

Near infrared absorbing dye [A-110]

(Manufacturing of near-infrared absorbing dye [A-111])
Near-infrared absorbing dye [A-105] except that 36.3 parts of alloxan was used instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of near-infrared absorbing dye [A-105]. ] Was carried out in the same manner as in the production of the near-infrared absorbing dye [A-111] to obtain 80.3 parts (yield: 93%). As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-111].

Near-infrared absorbing dye [A-111]

(Manufacturing of near-infrared absorbing dye [A-112])
Instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-105], 33.2 parts of 2,2-dimethyl-1,3-dioxane-5-one The same operation as in the production of the near-infrared absorbing dye [A-105] was carried out except that 79.3 parts (yield: 95%) of the near-infrared absorbing dye [A-112] was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-112].

Near-infrared absorbing dye [A-112]

(Manufacturing of near-infrared absorbing dye [A-113])
Instead of 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-105], 1,5-dithiaspiro [5.5] undecane-3-on 51.7 parts The same operation as in the production of the near-infrared absorbing dye [A-105] was carried out except that 91.9 parts (yield: 91%) of the near-infrared absorbing dye [A-113] was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-113].

Near-infrared absorbing dye [A-113]

(Manufacturing of near-infrared absorbing dye [A-114])
Instead of 4,0.0 parts of 1,8-diaminonaphthalene and 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-75], 1,8-diamino-4, The same operation as in the production of the near-infrared absorbing dye [A-75] was performed except that 57.4 parts of 5-dichloronaphthalene and 33.8 parts of 2-methyl-1,3-oxatian-5-one were used. 87.7 parts (yield: 95%) of the near-infrared absorbing dye [A-114] was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-114].

Near-infrared absorbing dye [A-114]

(Manufacturing of near-infrared absorbing dye [A-115])
Instead of 4,0.0 parts of 1,8-diaminonaphthalene and 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-75], 1,8-diamino-4, Near-infrared absorbing dye [A-75] except that 79.9 parts of 5-dibromonaphthalene and 35.3 parts of 5H-pyrazolo [5,1-b] [1,3] oxazine-6 (7H) -on were used. ] Was carried out in the same manner as in the production of the near-infrared absorbing dye [A-115] to obtain 103.8 parts (yield: 90%). As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-115].

Near-infrared absorbing dye [A-115]

(Manufacturing of near-infrared absorbing dye [A-116])
Instead of 40.0 parts of 1,8-diaminonaphthalene and 25.6 parts of tetrahydro-4H-pyran-4-one used in the production of the near-infrared absorbing dye [A-75], 1,8-diamino-2- The same operation as in the production of the near-infrared absorbing dye [A-75] was performed except that 46.3 parts of naphthonitrile and 37.9 parts of 1,4-dithiepan-6-one were used, and the near-infrared absorbing dye [A] was performed. −116] 78.7 parts (yield: 92%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-116].

Near-infrared absorbing dye [A-116]

(Manufacturing of near-infrared absorbing dye [A-117])
20.0 parts of the near-infrared absorbing dye [A-93] was added to 300 parts of water, stirred and redispersed, and then adjusted to pH 9.0 with 26% aqueous ammonia and dissolved. 235.5 parts of an 8% tetrabutylammonium bromide aqueous solution was gradually added to this solution. Precipitates appeared one after another from the dropped portion, and the pH gradually decreased with the addition. No bleeding was observed after the addition was completed. The precipitate was separated from the slurry by filtration, washed with water, and dried at 80 ° C. to obtain 33.1 parts (yield: 99%) of a near-infrared absorbing dye [A-117].

(Manufacturing of near-infrared absorbing dye [A-118])
Instead of 235.5 parts of the 8% tetrabutylammonium bromide aqueous solution used in the production of the near-infrared absorbing dye [A-117], 194.4 parts of the 8% 1,2-dimethyl-3-propylimidazolium iodide aqueous solution was used. Except for the use, the same operation as in the production of the near-infrared absorbing dye [A-117] was carried out to obtain 27.1 parts (yield: 98%) of the near-infrared absorbing dye [A-118].

(Manufacturing of near-infrared absorbing dye [A-119])
Near-infrared absorption except that 125.4 parts of 8% 1-butylpyridinium chloride aqueous solution was used instead of 235.5 parts of the 8% tetrabutylammonium bromide aqueous solution used in the production of the near-infrared absorbing dye [A-117]. The same operation as in the production of the dye [A-117] was carried out to obtain 27.2 parts (yield: 99%) of the near-infrared absorbing dye [A-119].

(Manufacturing of near-infrared absorbing dye [A-120])
Near-infrared absorption except that 271.2 parts of an 8% ethyltriphenylphosphonium bromide aqueous solution was used instead of 235.5 parts of the 8% tetrabutylammonium bromide aqueous solution used in the production of the near-infrared absorbing dye [A-117]. The same operation as in the production of the dye [A-117] was carried out to obtain 35.8 parts (yield: 99%) of the near-infrared absorbing dye [A-120].

(Manufacturing of near-infrared absorbing dye [A-121])
Near-infrared absorbing dye [A-117] except that 114.7 parts of 8% trimethylsulfonium bromide aqueous solution was used instead of 235.5 parts of the 8% tetrabutylammonium bromide aqueous solution used in the production of the near-infrared absorbing dye [A-117]. The same operation as in the production of A-117] was carried out to obtain 23.8 parts (yield: 98%) of the near-infrared absorbing dye [A-121].

(Manufacturing of near-infrared absorbing dye [A-122])
Near-infrared absorbing dye [A-117] except that 76.7 parts of 8% aluminum sulfate aqueous solution was used instead of 235.5 parts of the 8% tetrabutylammonium bromide aqueous solution used in the production of the near-infrared absorbing dye [A-117]. The same operation as in the production of -117] was carried out to obtain 20.2 parts (yield: 99%) of the near-infrared absorbing dye [A-122].

[Method for producing compound represented by general formula (3)]
(Manufacturing of near-infrared absorbing dye [A-123])
400 parts of toluene is mixed with 40.0 parts of 1,8-diaminonaphthalene, 46.0 parts of 9-fluorenone, and 0.087 parts of p-toluenesulfonic acid monohydrate, and the mixture is heated and stirred in an atmosphere of nitrogen gas. It was refluxed for 3 hours. The water produced during the reaction was removed from the system by azeotropic distillation. After completion of the reaction, the dark brown solid obtained by distilling toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The obtained brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, and 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added to create an atmosphere of nitrogen gas. The mixture was heated and stirred inside, and the mixture was refluxed for 8 hours. The water produced during the reaction was removed from the system by azeotropic distillation. After completion of the reaction, the solvent was distilled and 200 parts of hexane was added while stirring the obtained reaction mixture. The obtained black-brown precipitate was filtered off, washed successively with hexane, ethanol and acetone, dried under reduced pressure, and 84.6 parts of a near-infrared absorbing dye [A-123] (yield: 97%). Got As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-123].

Near-infrared absorbing dye [A-123]

(Manufacturing of near-infrared absorbing dye [A-124])
Near-infrared absorbing dye [A-123], except that 49.6 parts of 2-methyl-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. ] Was carried out in the same manner as in the production of the near-infrared absorbing dye [A-124] to obtain 86.7 parts (yield: 96%). As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-124].

Near infrared absorbing dye [A-124]

(Manufacturing of near-infrared absorbing dye [A-125])
Near-infrared absorbing dye [A], except that 53.2 parts of 1,8-dimethyl-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. The same operation as in the production of −123] was carried out to obtain 88.2 parts (yield: 94%) of the near-infrared absorbing dye [A-125]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-125].

Near-infrared absorbing dye [A-125]

(Manufacturing of near-infrared absorbing dye [A-126])
Near-infrared absorbing dye [A], except that 3,6-diethyl-9-fluorenone 60.3 parts was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. The same operation as in the production of −123] was carried out to obtain 95.0 parts (yield: 94%) of the near-infrared absorbing dye [A-126]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-126].

Near infrared absorbing dye [A-126]

(Manufacturing of near-infrared absorbing dye [A-127])
Near-infrared absorbing dye [A], except that 44.7 parts of 4,5-diisopropyl-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. The same operation as in the production of −123] was carried out to obtain 106.6 parts (yield: 93%) of the near-infrared absorbing dye [A-127]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-127].

Near-infrared absorbing dye [A-127]

(Manufacturing of near-infrared absorbing dye [A-128])
Near-infrared absorbing dye [A-123], except that 2,7-bis (trifluoromethyl) -9-fluorenone 80.7 parts was used instead of 9-fluorenone 46.0 parts used in the production. The same operation as in the production of the infrared absorbing dye [A-123] was carried out to obtain 109.8 parts (yield: 91%) of the near infrared absorbing dye [A-128]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-128].

Near infrared absorbing dye [A-128]

(Manufacture of near-infrared absorbing dye [A-129])
Near-infrared absorbing dye [A], except that 59.3 parts of 2,3-divinyl-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. The same operation as in the production of −123] was carried out to obtain 95.0 parts (yield: 95%) of the near-infrared absorbing dye [A-129]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-129].

Near-infrared absorbing dye [A-129]

(Manufacturing of near-infrared absorbing dye [A-130])
Near-infrared absorbing dye [A-123], except that 65.5 parts of 2-phenyl-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. ] Was carried out in the same manner as in the production of 96.6 parts (yield: 91%) of the near-infrared absorbing dye [A-130]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-130].

Near infrared absorbing dye [A-130]

(Manufacturing of near-infrared absorbing dye [A-131])
Near-infrared absorbing dye [A], except that 69.0 parts of 2-p-tolyl-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. The same operation as in the production of −123] was carried out to obtain 100.1 parts (yield: 92%) of the near-infrared absorbing dye [A-131]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-131].

Near-infrared absorbing dye [A-131]

(Manufacturing of near-infrared absorbing dye [A-132])
Near-infrared absorbing dye [A-123], except that 69.0 parts of 3-benzyl-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. ] Was carried out in the same manner as in the production of [A-132] to obtain 101.4 parts (yield: 93%) of the near-infrared absorbing dye [A-132]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-132].

Near-infrared absorbing dye [A-132]

(Manufacturing of near-infrared absorbing dye [A-133])
Near-infrared absorbing dye [A], except that 2,3-dimethoxy-9-fluorenone 61.4 parts was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. The same operation as in the production of −123] was carried out to obtain 93.4 parts (yield: 92%) of the near-infrared absorbing dye [A-133]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-133].

Near-infrared absorbing dye [A-133]

(Manufacturing of near-infrared absorbing dye [A-134])
Near-infrared absorbing dye except that 67.5 parts of 3- (trifluoromethoxy) -9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. The same operation as in the production of [A-123] was carried out to obtain 100.4 parts (yield: 93%) of the near-infrared absorbing dye [A-134]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-134].

Near infrared absorbing dye [A-134]

(Manufacturing of near-infrared absorbing dye [A-135])
Other than using 2,7-bis (2- (diethylamino) ethoxy) -9-fluorenone 104.8 parts instead of 9-fluorenone 46.0 parts used in the production of the near-infrared absorbing dye [A-123]. The same operation as in the production of the near-infrared absorbing dye [A-123] was carried out to obtain 136.9 parts (yield: 96%) of the near-infrared absorbing dye [A-135]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-135].

Near infrared absorbing dye [A-135]

(Manufacturing of near-infrared absorbing dye [A-136])
Near-infrared absorbing dye [A-123], except that 69.5 parts of 3-phenoxy-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. ], The same operation as in the production of [A-136] was carried out to obtain 100.3 parts (yield: 92%) of the near-infrared absorbing dye [A-136]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-136].

Near infrared absorbing dye [A-136]

(Manufacturing of near-infrared absorbing dye [A-137])
Near-infrared absorbing dye [A-123], except that 50.1 parts of 1-hydroxy-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. ] Was carried out in the same manner as in the production of the near-infrared absorbing dye [A-137] to obtain 83.0 parts (yield: 91%). As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-137].

Near-infrared absorbing dye [A-137]

(Manufacturing of near-infrared absorbing dye [A-138])
Near-infrared absorbing dye [A-123], except that 50.1 parts of 2-hydroxy-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. ] Was carried out in the same manner as in the production of the near-infrared absorbing dye [A-138] to obtain 83.9 parts (yield: 92%). As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-138].

Near-infrared absorbing dye [A-138]

(Manufacturing of near-infrared absorbing dye [A-139])
Near-infrared absorbing dye [A], except that 54.2 parts of 2,7-dihydroxy-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. The same operation as in the production of −123] was carried out to obtain 91.1 parts (yield: 96%) of the near-infrared absorbing dye [A-139]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-139].

Near-infrared absorbing dye [A-139]

(Manufacturing of near-infrared absorbing dye [A-140])
Near-infrared absorbing dye [A-123], except that 49.9 parts of 2-amino-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. ] Was carried out in the same manner as in the production of the near-infrared absorbing dye [A-140] to obtain 86.8 parts (yield: 96%). As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-140].

Near infrared absorbing dye [A-140]

(Manufacturing of near-infrared absorbing dye [A-141])
Near-infrared absorbing dye [A], except that 53.7 parts of 4,5-diamino-9-fluorenone were used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. The same operation as in the production of −123] was carried out to obtain 90.1 parts (yield: 95%) of the near-infrared absorbing dye [A-141]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-141].

Near-infrared absorbing dye [A-141]

(Manufacturing of near-infrared absorbing dye [A-142])
Near-infrared absorbing dye except that 70.0 parts of 2-amino-3-bromo-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. The same operation as in the production of [A-123] was carried out to obtain 100.4 parts (yield: 91%) of the near-infrared absorbing dye [A-142]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-142].

Near-infrared absorbing dye [A-142]

(Manufacturing of near-infrared absorbing dye [A-143])
Near-infrared absorbing dye except that 70.0 parts of 2-amino-7-bromo-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. The same operation as in the production of [A-123] was carried out to obtain 102.4 parts (yield: 93%) of the near-infrared absorbing dye [A-143]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-143].

Near-infrared absorbing dye [A-143]

(Manufacturing of near-infrared absorbing dye [A-144])
Near-infrared absorbing dye [A-123], except that 57.0 parts of 2- (dimethylamino) -9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. The same operation as in the production of A-123] was carried out to obtain 92.1 parts (yield: 94%) of the near-infrared absorbing dye [A-144]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-144].

Near-infrared absorbing dye [A-144]

(Manufacturing of near-infrared absorbing dye [A-145])
Except for the use of 60.6 parts of N- (9-oxo-9H-fluorene-4-yl) acetamide instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. , The same operation as in the production of the near-infrared absorbing dye [A-123] was carried out to obtain 96.0 parts (yield: 95%) of the near-infrared absorbing dye [A-145]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-145].

Near infrared absorbing dye [A-145]

(Manufacturing of near-infrared absorbing dye [A-146])
Except for the use of 60.6 parts of N- (9-oxo-9H-fluorene-3-yl) acetamide instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. , The same operation as in the production of the near-infrared absorbing dye [A-123] was carried out to obtain 93.7 parts (yield: 93%) of the near-infrared absorbing dye [A-146]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-146].

Near-infrared absorbing dye [A-146]

(Manufacturing of near-infrared absorbing dye [A-147])
Near-infrared absorption except that 66.5 parts of 9-oxo-9H-fluorene-2-sulfonic acid was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. The same operation as in the production of the dye [A-123] was carried out to obtain 97.3 parts (yield: 91%) of the near-infrared absorbing dye [A-147]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-147].

Near-infrared absorbing dye [A-147]

(Manufacturing of near-infrared absorbing dye [A-148])
Near infrared except that 86.9 parts of 9-oxo-9H-fluorene-2,7-disulfonic acid was used instead of 46.0 parts of 9-fluorenone used in the production of the near infrared absorbing dye [A-123]. The same operation as in the production of the infrared absorbing dye [A-123] was carried out to obtain 118.1 parts (yield: 94%) of the near infrared absorbing dye [A-148]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-148].

Near-infrared absorbing dye [A-148]

(Manufacturing of near-infrared absorbing dye [A-149])
Instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123], N ² , N ⁷ -di-sec-butyl-9-oxo-9H-fluorene-2,7-disulfone The same operation as in the production of the near-infrared absorbing dye [A-123] was performed except that 115.1 parts of the amide was used, and 145.4 parts (yield: 95%) of the near-infrared absorbing dye [A-149] was obtained. Obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-149].

Near-infrared absorbing dye [A-149]

(Manufacturing of near-infrared absorbing dye [A-150])
Instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123], N ² , N ⁷ -bis (2,4-dimethylphenyl) -9-oxo-9H-fluorene-2 , 7-Disulfonamide 139.6 parts were used, but the same operation as in the production of the near-infrared absorbing dye [A-123] was carried out, and 163.6 parts of the near-infrared absorbing dye [A-150] (yield: 93%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-150].

Near infrared absorbing dye [A-150]

(Manufacturing of near-infrared absorbing dye [A-151])
Instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123], N ² , N ⁷ -bis (4-chlorophenyl) -9-oxo-9H-fluorene-2,7- The same operation as in the production of the near-infrared absorbing dye [A-123] was performed except that 142.9 parts of the disulfonamide was used, and 166.0 parts of the near-infrared absorbing dye [A-151] (yield: 93%). Got As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-151].

Near-infrared absorbing dye [A-151]

(Manufacturing of near-infrared absorbing dye [A-152])
Instead of 9-fluorenone 46.0 parts used in the manufacture of near infrared absorbing dye ^{[A-123], N 2} , N 7 - diacetyl-9-oxo -9H- 2,7-di sulfonamide 107.9 The same operation as in the production of the near-infrared absorbing dye [A-123] was carried out except that the part was used, and 135.2 parts (yield: 93%) of the near-infrared absorbing dye [A-152] was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-152].

Near-infrared absorbing dye [A-152]

(Manufacturing of near-infrared absorbing dye [A-153])
Instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123], 9-oxo-N ² , N ⁷ -di (pyridin-4-yl) -9H-fluorene-2, The same operation as in the production of the near-infrared absorbing dye [A-123] was performed except that 125.8 parts of the 7-disulfonamide was used, and 148.6 parts of the near-infrared absorbing dye [A-153] (yield: 91). %) Was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-153].

Near-infrared absorbing dye [A-153]

(Manufacturing of near-infrared absorbing dye [A-154])
Instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123], N ² , N ⁷ -bis (3,5-dimethylpiperidine-1-ylsulfonyl) -9H-fluorene- The same operation as in the production of the near-infrared absorbing dye [A-123] was performed except that 135.5 parts of 9-on was used, and 161.2 parts of the near-infrared absorbing dye [A-154] (yield: 94%). ) Was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-154].

Near-infrared absorbing dye [A-154]

(Manufacturing of near-infrared absorbing dye [A-155])
Near-infrared absorption except that 57.3 parts of 9-oxo-9H-fluorene-1-carboxylic acid was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. The same operation as in the production of the dye [A-123] was carried out to obtain 93.5 parts (yield: 95%) of the near-infrared absorbing dye [A-155]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-155].

Near infrared absorbing dye [A-155]

(Manufacturing of near-infrared absorbing dye [A-156])
Near-infrared absorption except that 57.3 parts of 9-oxo-9H-fluorene-4-carboxylic acid was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. The same operation as in the production of the dye [A-123] was carried out to obtain 91.3 parts (yield: 93%) of the near-infrared absorbing dye [A-156]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-156].

Near-infrared absorbing dye [A-156]

(Manufacturing of near-infrared absorbing dye [A-157])
Near-infrared rays, except that 60.8 parts of methyl 9-oxo-9H-fluorene-1-carboxylate was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. The same operation as in the production of the absorbing dye [A-123] was carried out to obtain 96.3 parts (yield: 95%) of the near infrared absorbing dye [A-157]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-157].

Near-infrared absorbing dye [A-157]

(Manufacturing of near-infrared absorbing dye [A-158])
Near-infrared rays, except that 64.4 parts of ethyl 9-oxo-9H-fluorene-4-carboxylate were used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. The same operation as in the production of the absorbing dye [A-123] was carried out to obtain 98.8 parts (yield: 94%) of the near infrared absorbing dye [A-158]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-158].

Near-infrared absorbing dye [A-158]

(Manufacturing of near-infrared absorbing dye [A-159])
Near-infrared absorbing dye except that 57.0 parts of 9-oxo-9H-fluorene-2-carboxamide was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. The same operation as in the production of [A-123] was carried out to obtain 92.3 parts (yield: 94%) of the near-infrared absorbing dye [A-159]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-159].

Near-infrared absorbing dye [A-159]

(Manufacturing of near-infrared absorbing dye [A-160])
Near-infrared absorbing dye [A-123], except that 57.5 parts of 2-nitro-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. ] Was carried out in the same manner as in the production of [A-160] to obtain 91.4 parts (yield: 93%) of the near-infrared absorbing dye [A-160]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-160].

Near infrared absorbing dye [A-160]

(Manufacturing of near-infrared absorbing dye [A-161])
Near-infrared absorbing dye [A], except that 69.0 parts of 2,7-dinitro-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. The same operation as in the production of −123] was carried out to obtain 103.6 parts (yield: 95%) of the near-infrared absorbing dye [A-161]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-161].

Near-infrared absorbing dye [A-161]

(Manufacturing of near-infrared absorbing dye [A-162])
Near-infrared absorption except that 52.4 parts of 9-oxo-9H-fluorene-3-carbonitrile were used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. The same operation as in the production of the dye [A-123] was carried out to obtain 88.7 parts (yield: 95%) of the near-infrared absorbing dye [A-162]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-162].

Near infrared absorbing dye [A-162]

(Manufacturing of near-infrared absorbing dye [A-163])
Near-infrared absorbing dye [A-123], except that 50.6 parts of 2-fluoro-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. ] Was carried out in the same manner as in the production of the near-infrared absorbing dye [A-163] to obtain 85.9 parts (yield: 94%). As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-163].

Near-infrared absorbing dye [A-163]

(Manufacturing of near-infrared absorbing dye [A-164])
Near-infrared absorbing dye [A-123], except that 50.6 parts of 3-fluoro-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. ] Was carried out in the same manner as in the production of the near-infrared absorbing dye [A-164] to obtain 87.7 parts (yield: 96%). As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-164].

Near-infrared absorbing dye [A-164]

(Manufacturing of near-infrared absorbing dye [A-165])
Near-infrared absorbing dye [A], except that 55.2 parts of 2,5-difluoro-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. The same operation as in the production of −123] was carried out to obtain 87.6 parts (yield: 91%) of the near-infrared absorbing dye [A-165]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-165].

Near infrared absorbing dye [A-165]

(Manufacturing of near-infrared absorbing dye [A-166])
Near-infrared absorbing dye [A], except that 63.6 parts of 2,7-dichloro-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. The same operation as in the production of −123] was carried out to obtain 95.1 parts (yield: 91%) of the near-infrared absorbing dye [A-166]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-166].

Near-infrared absorbing dye [A-166]

(Manufacturing of near-infrared absorbing dye [A-167])
Near-infrared absorbing dye [A], except that 63.6 parts of 2,4-dichloro-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. The same operation as in the production of −123] was carried out to obtain 96.7 parts (yield: 93%) of the near-infrared absorbing dye [A-167]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-167].

Near-infrared absorbing dye [A-167]

(Manufacturing of near-infrared absorbing dye [A-168])
Near-infrared absorbing dye [A-123], except that 66.2 parts of 2-bromo-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. ] Was carried out in the same manner as in the production of the near-infrared absorbing dye [A-168] to obtain 100.8 parts (yield: 95%). As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-168].

Near infrared absorbing dye [A-168]

(Manufacturing of near-infrared absorbing dye [A-169])
Near-infrared absorbing dye [A-123], except that 66.2 parts of 4-bromo-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. ] Was carried out in the same manner as in the production of the near-infrared absorbing dye [A-169] to obtain 98.9 parts (yield: 93%). As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-169].

Near-infrared absorbing dye [A-169]

(Manufacturing of near-infrared absorbing dye [A-170])
Near-infrared absorbing dye [A], except that 2,7-dibromo-9-fluorenone 86.3 parts was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. The same operation as in the production of −123] was carried out to obtain 117.8 parts (yield: 94%) of the near-infrared absorbing dye [A-170]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-170].

Near infrared absorbing dye [A-170]

(Manufacturing of near-infrared absorbing dye [A-171])
Instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123], 2-cyclohexyl-1,2-dihydro-12H-benzo [3,4] fluorenone [1,2-d] ] Except for using 90.8 parts of isoxazole-12-one, the same operation as in the production of the near-infrared absorbing dye [A-123] was carried out, and 124.1 parts of the near-infrared absorbing dye [A-171] (yield). : 96%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-171].

Near-infrared absorbing dye [A-171]

(Manufacturing of near-infrared absorbing dye [A-172])
Near-infrared absorbing dye except that 11H-benzo [b] fluorene-11-one 58.8 parts was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. The same operation as in the production of [A-123] was carried out to obtain 94.6 parts (yield: 95%) of the near-infrared absorbing dye [A-172]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-172].

Near infrared absorbing dye [A-172]

(Manufacturing of near-infrared absorbing dye [A-173])
Near-infrared absorbing dye except that 11H-benzo [a] fluoren-11-one 58.8 parts was used in place of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. The same operation as in the production of [A-123] was carried out to obtain 94.9 parts (yield: 95%) of the near-infrared absorbing dye [A-173]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-173].

Near-infrared absorbing dye [A-173]

(Manufacturing of near-infrared absorbing dye [A-174])
Near-infrared absorbing dye [A-123], except that 46.3 parts of 4-aza-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. ] Was carried out in the same manner as in the production of the near-infrared absorbing dye [A-174] to obtain 82.1 parts (yield: 94%). As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-174].

Near-infrared absorbing dye [A-174]

(Manufacturing of near-infrared absorbing dye [A-175])
Near-infrared absorbing dye except that 4,5-diazafluoren-9-one 46.5 parts was used instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123]. The same operation as in the production of [A-123] was carried out to obtain 80.2 parts (yield: 91%) of the near-infrared absorbing dye [A-175]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-175].

Near-infrared absorbing dye [A-175]

(Manufacturing of near-infrared absorbing dye [A-176])
Instead of 46.0 parts of 9-fluorenone used in the production of the near-infrared absorbing dye [A-123], 13H-benzo [g] indeno [2,1-b] quinoxaline-13-on 72.1 parts was used. The same operation as in the production of the near-infrared absorbing dye [A-123] was carried out except that 107.1 parts (yield: 96%) of the near-infrared absorbing dye [A-176] was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-176].

Near-infrared absorbing dye [A-176]

(Manufacturing of near-infrared absorbing dye [A-177])
Near-infrared absorbing dye [A-123], except that 40.0 parts of 4,5-diaminonaphthalene-1-sulfonic acid was used instead of 40.0 parts of 1,8-diaminonaphthalene used in the production. The same operation as in the production of the infrared absorbing dye [A-123] was carried out to obtain 99.8 parts (yield: 94%) of the near infrared absorbing dye [A-177]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-177].

Near infrared absorbing dye [A-177]

(Manufacturing of near-infrared absorbing dye [A-178])
Except for using 80.5 parts of 4,5-diaminonaphthalene-1,8-disulfonic acid instead of 40.0 parts of 1,8-diaminonaphthalene used in the production of the near-infrared absorbing dye [A-123]. , The same operation as in the production of the near-infrared absorbing dye [A-123] was carried out to obtain 116.4 parts (yield: 92%) of the near-infrared absorbing dye [A-178]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-178].

Near-infrared absorbing dye [A-178]

(Manufacturing of near-infrared absorbing dye [A-179])
Except for the use of 49.1 parts of 1,8-diamino-2,4-difluoronaphthalene instead of 40.0 parts of 1,8-diaminonaphthalene used in the production of the near-infrared absorbing dye [A-123]. The same operation as in the production of the near-infrared absorbing dye [A-123] was carried out to obtain 89.4 parts (yield: 93%) of the near-infrared absorbing dye [A-179]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-179].

Near infrared absorbing dye [A-179]

(Manufacturing of near-infrared absorbing dye [A-180])
Except for using 57.4 parts of 1,8-diamino-3,6-dichloronaphthalene instead of 40.0 parts of 1,8-diaminonaphthalene used in the production of the near-infrared absorbing dye [A-123]. The same operation as in the production of the near-infrared absorbing dye [A-123] was carried out to obtain 97.4 parts (yield: 94%) of the near-infrared absorbing dye [A-180]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-180].

Near infrared absorbing dye [A-180]

(Manufacturing of near-infrared absorbing dye [A-181])
Near-infrared rays, except that 59.9 parts of 1,8-diamino-4-bromonaphthalene was used instead of 40.0 parts of 1,8-diaminonaphthalene used in the production of the near-infrared absorbing dye [A-123]. The same operation as in the production of the absorbing dye [A-123] was carried out to obtain 101.7 parts (yield: 96%) of the near infrared absorbing dye [A-181]. As a result of mass spectrometry by TOF-MS, it was identified as a near-infrared absorbing dye [A-181].

Near-infrared absorbing dye [A-181]

(Manufacturing of near-infrared absorbing dye [A-182])
20.0 parts of the near-infrared absorbing dye [A-177] was added to 300 parts of water, stirred and redispersed, and then the pH was adjusted to 7.0 with 26% aqueous ammonia and dissolved. 192.6 parts of an 8% tetrabutylammonium bromide aqueous solution was gradually added to this solution. Precipitates appeared one after another from the dropped portion, and the pH gradually decreased with the addition. No bleeding was observed after the addition was completed. The precipitate was separated from the slurry by filtration, washed with water, and dried at 80 ° C. to obtain 30.7 parts (yield: 99%) of the near-infrared absorbing dye [A-182].

(Manufacturing of near-infrared absorbing dye [A-183])
Instead of 192.6 parts of the 8% tetrabutylammonium bromide aqueous solution used in the production of the near-infrared absorbing dye [A-182], 159.0 parts of the 8% 1,2-dimethyl-3-propylimidazolium iodide aqueous solution was used. Except for the use, the same operation as in the production of the near-infrared absorbing dye [A-182] was carried out to obtain 25.8 parts (yield: 98%) of the near-infrared absorbing dye [A-183].

(Manufacturing of near-infrared absorbing dye [A-184])
Near-infrared absorption except that 102.5 parts of 8% 1-butylpyridinium chloride aqueous solution was used instead of 192.6 parts of the 8% tetrabutylammonium bromide aqueous solution used in the production of the near-infrared absorbing dye [A-182]. The same operation as in the production of the dye [A-182] was carried out to obtain 25.9 parts (yield: 99%) of the near-infrared absorbing dye [A-184].

(Manufacturing of near-infrared absorbing dye [A-185])
Near-infrared absorption except that 221.8 parts of an 8% ethyltriphenylphosphonium bromide aqueous solution was used instead of 192.6 parts of the 8% tetrabutylammonium bromide aqueous solution used in the production of the near-infrared absorbing dye [A-182]. The same operation as in the production of the dye [A-182] was carried out to obtain 32.9 parts (yield: 99%) of the near-infrared absorbing dye [A-185].

(Manufacturing of near-infrared absorbing dye [A-186])
Near-infrared absorbing dye [A-182] except that 93.8 parts of 8% trimethylsulfonium bromide aqueous solution was used instead of 192.6 parts of the 8% tetrabutylammonium bromide aqueous solution used in the production of the near-infrared absorbing dye [A-182]. The same operation as in the production of A-182] was carried out to obtain 23.0 parts (yield: 98%) of the near-infrared absorbing dye [A-186].

(Manufacturing of near-infrared absorbing dye [A-187])
Near-infrared absorbing dye [A-182] except that 62.8 parts of 8% aluminum sulfate aqueous solution was used instead of 192.6 parts of the 8% tetrabutylammonium bromide aqueous solution used in the production of the near-infrared absorbing dye [A-182]. The same operation as in the production of -182] was carried out to obtain 20.2 parts (yield: 99%) of the near-infrared absorbing dye [A-187].

(Manufacturing of near-infrared absorbing dye [A-188])
67.3 parts of methyl ethyl ketone was placed in a four-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, and the temperature was raised to 75 ° C. under a nitrogen stream. Separately, 33.2 parts of methyl methacrylate, 27.3 parts of n-butyl methacrylate, 27.3 parts of 2-ethylhexyl methacrylate, 12.2 parts of dimethylaminoethylmethyl chloride salt methacrylate, 2,2'-azobis (2,4). -Dimethylvaleronitrile) was made uniform in 6.5 parts and 25.1 parts of methyl ethyl ketone, charged in a dropping funnel, attached to a four-neck separable flask, and added dropwise over 2 hours. Two hours after the completion of the dropping, it was confirmed from the solid content that the polymerization yield was 98% or more and the weight average molecular weight (Mw) was 7500, and the mixture was cooled to 50 ° C. Then, 72 parts of isopropyl alcohol was added to obtain a resin having a quaternary ammonium base in the side chain having a resin component of 40% by weight. The ammonium salt value of the obtained resin was 33 mgKOH / g.

To 2000 parts of water, 51 parts of a resin having a quaternary ammonium base is added to the side chain, and the mixture is sufficiently stirred and mixed, and then heated to 60 ° C. On the other hand, an aqueous solution prepared by dissolving 4.17 parts of the near-infrared absorbing dye [A-177] and 0.85 parts of sodium hydroxide in 90 parts of water is gradually added dropwise to the resin solution. .. After the dropping, the mixture is stirred at 60 ° C. for 120 minutes to sufficiently react. To confirm the end point of the reaction, it was judged that the salt-forming compound was obtained by dropping the reaction solution onto the filter paper and using the point where the bleeding disappeared as the end point. After allowing to cool to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing water with a dryer, and 22 parts of the near-infrared absorbing dye [A-188]. ] Was obtained.

<Manufacturing method of other pigments>
(Manufacturing of near-infrared absorbing dye [F-1])
The following near-infrared absorbing dye [F-1] was synthesized in accordance with JP-A-2005-119262.

Near infrared absorbing dye [F-1]

(Manufacturing of near-infrared absorbing dye [F-2])
The following near-infrared absorbing dye [F-2] was synthesized in accordance with JP-A-11-254830.

Near infrared absorbing dye [F-2]

(Manufacturing of near-infrared absorbing dye [F-3])
The following squarylium [F-3] was synthesized in accordance with JP-A-7-25153.

Near-infrared absorbing dye [F-3]

<Manufacturing method of laser marking composition>
[Example 1] (Laser marking composition LM-1)
(Preparation of 10% polyvinyl alcohol aqueous solution)
A 10% polyvinyl alcohol aqueous solution, which is a resin (D), is prepared by adding 50 parts of polyvinyl alcohol and 450 parts of water manufactured by Wako Pure Chemical Industries, Ltd. to a 1 L beaker and heating and stirring at 50 ° C. for 30 minutes. did.

(Preparation of near-infrared absorbing dye [A] dispersion)
The mixture having the following composition is uniformly stirred and mixed, dispersed with an Eiger mill for 3 hours using zirconia beads having a diameter of 0.5 mm, and then filtered through a filter of 0.5 μm to obtain a near-infrared absorbing dye [A] dispersion. Was produced.
Near-infrared absorbing dye [A-1] 4 parts (D) 10% polyvinyl alcohol solution 122 parts Water 74 parts

(Preparation of color former [B] dispersion)
The mixture having the following composition is uniformly stirred and mixed, dispersed with an Eiger mill for 3 hours using zirconia beads having a diameter of 0.5 mm, and then filtered through a filter of 0.5 μm to prepare a color former [B] dispersion. did.
(B) 3,3'-Bis (4-dimethylaminophenyl) -6-dimethylaminophthalide
60 parts (D) 10% polyvinyl alcohol solution 100 parts Water 40 parts

(Adjustment of color developer [C] dispersion)
The mixture having the following composition is uniformly stirred and mixed, dispersed with an Eiger mill for 3 hours using zirconia beads having a diameter of 0.5 mm, and then filtered through a filter of 0.5 μm to obtain a developer [C] dispersion. Made.
(C) 4-Hydroxy-4'-isopropoxydiphenyl sulfone
40 parts (D) 10% polyvinyl alcohol solution 100 parts Water 60 parts

(Preparation of composition LM-1 for laser marking)
The dispersion produced by the above method was mixed at the following ratio to obtain a laser marking composition (LM-1).
Near-infrared absorbing dye [A] dispersion 10 parts Color former [B] dispersion 40 parts Color developer [C] dispersion 10 parts

[Examples 2-228, Comparative Examples 1-3]
(Composition for laser marking LM-2 to 231)
Same as LM-1 except that the types and amounts of the near-infrared absorbing dye [A], the coloring agent [B], and the coloring agent [C] were changed to the compounds and parts by mass shown in Tables 1 to 5. The laser marking compositions LM-2 to 231 were obtained.

<Evaluation of composition for laser marking>
The following evaluations were carried out on the obtained laser marking compositions LM-1 to 231. The results are shown in Tables 6-9.

(Viscosity evaluation)
The obtained composition for laser marking was measured for viscosity at 25 ° C. and a rotation speed of 50 rpm using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.). Evaluation was made based on the following criteria.
⊚: Less than 5 mPa · s ○: 5 mPa · s or more and less than 10 mPa · s Δ: 10 mPa · s or more, less than 30 mPa · s ×: 30 mPa · s or more

(Storage stability)
The obtained laser marking composition was stored in a thermostat at 60 ° C. for 1 week, accelerated over time, and then the viscosity was measured in the same manner as the viscosity evaluation to determine the rate of change in ink viscosity before and after time. Evaluation was made based on the following criteria.
⊚: Change rate is less than ± 3% ○: Change rate is ± 3% or more and less than ± 5% △: Change rate is ± 5% or more and less than ± 15% ×: Change rate is ± 15% or more

(Near infrared absorption capacity)
The obtained composition for laser marking was diluted 1000 times with water, and then the absorption spectrum in the wavelength range of 300 to 1000 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation). At that time, a 10 mm square quartz cell was used as the UV cell. The maximum absorption of the near-infrared absorbing dye [A] of the present invention is in the region of 750 to 950 nm, and the near-infrared absorbing ability was evaluated based on the absorbance at the maximum absorption wavelength according to the following criteria. At the same concentration, the higher the absorbance at the maximum absorption wavelength, the better the near-infrared absorption capacity. The higher the near-infrared absorbing capacity, the more efficiently the laser light can be converted into heat, so that the color development property in laser marking is improved. In other words, it also leads to a reduction in the amount of the near-infrared absorbing dye added.
⊚: Absorbance at maximum absorption wavelength is 1.0 or more ○: Absorbance at maximum absorption wavelength is 0.6 or more and less than 1.0 Δ: Absorbance at maximum absorption wavelength is 0.3 or more and less than 0.6 ×: Maximum absorption Absorbance at wavelength is less than 0.3

(Invisibility)
Using the absorption spectrum in the wavelength range of 300 to 1000 nm obtained by the above method, the invisibility is determined by the following criteria based on the "average absorbance at 400 to 700 nm" when the absorbance at the maximum absorption wavelength is standardized to 1. Evaluated in.
⊚: 0.05 or less ○: 0.05 or more and less than 0.075 Δ: 0.075 or more and less than 0.1 ×: 0.1 or more

The composition for laser marking containing the near-infrared absorbing dye [A] of the present invention showed excellent viscosity, storage stability, near-infrared absorbing ability, and invisibility. Among the near-infrared absorbing dyes [A] represented by the general formula (1), R is higher than the near-infrared absorbing dyes [A-1] to [A-31] in which _{R 1 to} R _{5 are all hydrogen atoms. 1} to R ₅ are found the following at least one ring-substituted by which the near infrared absorbing dye [a-32] ~ [a -74], showed particularly good results in terms of invisibility. Among them, in the general formula (1), _{X 3} and _{X 7} is a methyl _group, one of R 1 to R ₅ is a sulfo group or a _SO ³ - is substituted with _M ^{a +,} and _{M a} is ammonium The salts or metal salts [A-42], [A-68], [A-69] and [A-74] showed extremely good results. Further, in the near-infrared absorbing dye [A] represented by the general formula (2), the heterocyclic ring Y is an unsubstituted tetrahydropyran ring or an unsubstituted tetrahydropyran ring [A-75], [A]. -79] showed extremely good results. Further, one of R _{16 to} R ₂₀ is substituted with a sulfo group or SO ₃ ^- M _b ⁺ _{, and M b} is an ammonium salt or a metal salt [A-93], [A-97], [A-117] and [A-122] also showed good results. Further, in the near-infrared absorbing dye [A] represented by the general formula (3), Q ₁ , Q ₄ , Q ₅ , and Q ₈ are carbon atoms, and X _{11 to} X ₁₈ and R ₂₆ to R 26. [A-123], in which R ₃₀ is a hydrogen atom, showed extremely good results. In addition, one of R _{26 to} R ₃₀ is a resin in which a sulfo group or SO ₃ ^- M _c ⁺ is substituted, and M _c has an ammonium salt, a metal salt, or a quaternary ammonium base [A-]. 177], [A-182], [A-187], and [A-188] also showed good results.

The composition for laser marking of the present invention has very good viscosity and storage stability, which is derived from the fact that the near-infrared absorbing dye [A] of the present invention is easily dispersed and easily dissolved. The main reason for this is that the near-infrared absorbing dye [A] of the present invention imparts appropriate (not too strong) crystallinity by selecting an appropriate skeleton / substituent. .. Therefore, it is considered that π-π stacking, that is, strong cohesiveness, which is seen in general π-conjugated dyes such as cyanine and squarylium, is relaxed, and easy dispersibility and easy solubility are exhibited. Due to these factors, the composition for laser marking using the near-infrared absorbing dye [A] of the present invention is excellent in stability as an ink regardless of the composition and process, and in particular, the storage stability is remarkably good. Therefore, the ink can be stored for a long period of time. Furthermore, it was found that the near-infrared absorbing dye [A] of the present invention has high invisibility and near-infrared absorbing ability, and the performance is further improved by selecting the optimum skeleton and substituent. Since the near-infrared absorbing dye [A] of the present invention has a high near-infrared absorbing ability, efficient heat conversion is possible, which leads to a reduction in the amount of the near-infrared absorbing dye added to the laser marking composition. In addition, since the invisibility is high, it is difficult to visually confirm the coated portion, and the color difference before and after laser irradiation becomes large. In other words, it is conceivable that the color development property will be improved.

<Manufacturing method of laser marking coating>
[Examples 229 to 456, Comparative Examples 4 to 6]
(Manufacturing of laser marking coated products P-1 to 231)
The obtained laser marking composition LM-1 to 221 was ^{solidly coated on plain paper with a bar coater so as to have a dry coating amount of 5.0 g / m 2,} and dried in an oven at 60 ° C. for 1 minute. Coated products P-1 to 231 were obtained.

<Evaluation of laser marking coating>
The following evaluations were carried out on the obtained laser marking coated products P-1 to 231. The results are shown in Tables 10 to 13.

(Color development)
The obtained laser marking coating was irradiated with laser light under the conditions of a laser wavelength of 808 nm, a laser scanning speed of 10 mm / sec, and a laser output of 50 mW to draw clear lines derived from a color former. The color development of the obtained lines was visually compared and evaluated according to the following criteria. 〇 and above are sufficient levels for practical use, and ◎ is able to draw extremely high-concentration lines, and it is possible to reduce near-infrared absorbing dyes.
⊚: The density is very high, and extremely clear lines can be drawn.
◯: The density is high and clear lines can be drawn.
Δ: The line can be visually confirmed.
X: The concentration is low and it is difficult to identify.

The composition for laser marking containing the near-infrared absorbing dye [A] of the present invention showed excellent color development. In particular, the coated product using the laser marking composition containing the near-infrared absorbing dyes [A-32] to [A-188] gave extremely good results, and very high-concentration lines were drawn. It is considered that the amount of the near-infrared absorbing dye added to the laser marking composition can be easily reduced. On the other hand, in the case of the near-infrared absorbing dye which is not the present invention, the color-developing property at a practical level has not been obtained except for Comparative Example 5 in which the near-infrared absorbing dye [F-2] is used. Further, as described above, the near-infrared absorbing dye [F-2] has not reached the practical level because of problems in viscosity and storage stability as ink. The composition for laser marking of the present invention has both "stability as an ink" and "optical characteristics", and is also extremely excellent in color development when laser marking is performed. In particular, it has excellent invisibility, so it can be applied to security applications.

Claims (12)

A composition for laser marking containing a near-infrared absorbing dye [A], a coloring agent [B], a developing agent [C], and a resin [D].
The near-infrared absorbing dye [A] is a compound represented by the following general formula (1) (however, _{excluding X 5} and X ₆ to t-C ₄ H ₉ groups in the formula) represented by the following general formula (2). A composition for laser marking containing at least one compound selected from the group consisting of the above-mentioned compounds and the compounds represented by the following general formula (3).
General formula (1)

[In general formula (1),
R _{1 to} R ₅ independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. an aryloxy group which may have a sulfo ^{_{group, SO 3 - M a +,}} -SO 2 NR 6 R 7, -COOR 8, -CONR 9 R 10, a nitro group, a cyano group or a halogen atom.
X _{1 to} X ₁₀ independently have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, and a substituent. Aralkyl group which may have, alkoxy group which may have substituent, aryloxy group which may have substituent, amino group, substituted amino group, sulfo group, -SO ₂ NR ₁₁ R ₁₂ ,- Represents COOR ₁₃ , -CONR ₁₄ R ₁₅ , nitro group, cyano group or halogen atom. In X _{1 to} X ₁₀ , the substituents may be bonded to each other to form a ring.
M _a ⁺ denotes an inorganic or organic cation, R ₆ to R ₁₅ each independently represent an alkyl group which may have a hydrogen atom or a substituent. ]

General formula (2)

[In general formula (2),
Y represents a heterocycle which may have a substituent.
R _{16 to} R ₂₀ independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. an aryloxy group which may have a sulfo ^{_{group, SO 3 - M b +,}} -SO 2 NR 21 R 22, -COOR 23, -CONR 24 R 25, a nitro group, a cyano group or a halogen atom.
M _b ⁺ represents an inorganic or organic cation, and R _{21 to} R ₂₅ each independently represent an alkyl group which may have a hydrogen atom or a substituent. ]

General formula (3)

[In general formula (3),
Q ₁ , Q ₄ , Q ₅ and Q ₈ each independently represent a carbon atom or a nitrogen atom. If Q ₁ , Q ₄ , Q ₅ or Q ₈ are nitrogen atoms, it is assumed that there are no _{X 11} , X ₁₄ , X ₁₅ or X _{18 bonded to each.}
R _{26 to} R ₃₀ independently represent a hydrogen atom, a sulfo group, -SO ₃ ^- M _c ⁺ or a halogen atom. _Mc ⁺ represents an inorganic or organic cation.
X _{11 to} X ₁₈ independently have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, and a substituent. Aralkyl group which may have, alkoxy group which may have substituent, aryloxy group which may have substituent, hydroxyl group, amino group, -NR ₃₁ R ₃₂ , sulfo group, -SO ₂ NR _{Represents 33} R ₃₄ , -COOR ₃₅ , -CONR ₃₆ R ₃₇ , nitro group, cyano group or halogen atom. In X _{11 to} X ₁₈ , substituents may be bonded to each other to form a ring.
R _{31 to} R ₃₇ each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, and an acyl group or a substituent which may have a substituent. Represents a pyridinyl group that may have. In R ₃₁ and R ₃₂ , R ₃₃ and R _{34, and} R ₃₆ and R ₃₇ , the substituents may be bonded to each other to form a ring. ] The composition for laser marking according to claim 1, wherein the near-infrared absorbing dye [A] contains a compound represented by the general formula (1). _{At least one or more of R 1 to} R ₅ in the general formula (1) are an alkyl group which may have a substituent, an aryl group which may have a substituent, and an alkoxy group which may have a substituent. , an optionally substituted aryloxy group, a sulfo ^{_{group, SO 3 - M a +,}} -SO 2 NR 6 R 7, -COOR 8, -CONR 9 R 10, a nitro group, a cyano group or a halogen atom The composition for laser marking according to claim 1 or 2. The laser marking composition according to any one of claims 1 to ₃ , wherein at least one or more _{of R 1 to} R ₅ in the general formula (1) ^{is a sulfo group or SO 3-} M _a ^+. The composition for laser marking according to claim 1, wherein the near-infrared absorbing dye [A] contains a compound represented by the general formula (2). The laser marking composition according to claim 1 or 5, wherein Y in the general formula (2) is a saturated or unsaturated heterocycle having a 4-membered ring to a 7-membered ring which may have a substituent. The composition for laser marking according to claim 1, wherein the near-infrared absorbing dye [A] contains a compound represented by the general formula (3). The laser marking composition according to claim 1 or 7, wherein _{Q 1} , Q ₄ , Q ₅ and Q ₈ in the general formula (3) are carbon atoms. The composition for laser marking according to any one of claims 1 to 8, wherein the content of the near-infrared absorbing dye [A] in the total solid content of the composition for laser marking is 0.05 to 5% by mass. A coated product obtained by coating the composition for laser marking according to any one of claims 1 to 9. A recording material obtained by irradiating the coated object according to claim 10 with a laser beam and recording the material. A recording method for recording by irradiating a coated object according to claim 10 with a laser beam.