WO2018043150A1

WO2018043150A1 - Colorant composition, planographic printing master plate, method of manufacturing planographic printing plate, and compound

Info

Publication number: WO2018043150A1
Application number: PCT/JP2017/029546
Authority: WO
Inventors: 健太牛島; 洋平石地; 和朗榎本
Original assignee: 富士フイルム株式会社
Priority date: 2016-08-29
Filing date: 2017-08-17
Publication date: 2018-03-08
Also published as: JP2019194274A

Abstract

A colorant composition contains the compound represented by formula 1. A planographic printing master plate comprises at least a layer containing the colorant composition. A method of manufacturing a planographic printing plate uses the planographic printing master plate. Also provided is the compound represented by formula 1, which can be suitably used as a colorant.

Description

Coloring composition, lithographic printing plate precursor, lithographic printing plate preparation method, and compound

The present disclosure relates to a coloring composition, a lithographic printing plate precursor, a method for preparing a lithographic printing plate, and a compound.

In general, a lithographic printing plate is composed of an oleophilic image area that receives ink and a hydrophilic non-image area that receives dampening water in the printing process.
Lithographic printing utilizes the property that water and oil-based ink repel each other, so that the oleophilic image area of the lithographic printing plate is dampened with the ink receiving area and the hydrophilic non-image area is dampened with the water receiving area (ink non-receiving area). ), A difference in ink adhesion is caused on the surface of the lithographic printing plate, the ink is applied only to the image area, and then the ink is transferred to a printing medium such as paper for printing.

At present, in a plate making process for producing a lithographic printing plate from a lithographic printing plate precursor, image exposure is performed by CTP (computer to plate) technology. That is, the image exposure is performed by scanning exposure or the like directly on the lithographic printing plate precursor using a laser or a laser diode without using a lith film.

In addition, due to the growing interest in the global environment, environmental issues related to waste liquids associated with wet processing such as development processing have been highlighted in relation to plate making of lithographic printing plate precursors, and as a result, development processing has been simplified or eliminated. It is oriented. As one simple development process, a method called “on-press development” has been proposed. On-press development is a method in which, after image exposure of a lithographic printing plate precursor, conventional development processing is not carried out, but it is directly attached to a printing press and the non-image area of the image recording layer is removed at the initial stage of the normal printing process .

Generally, as a pre-process for attaching a lithographic printing plate to a printing press, an operation (inspection) is performed to inspect and identify an image on the lithographic printing plate to check whether the image is recorded as intended. In particular, in multi-color printing, it is important in printing work whether a register mark (register mark) that serves as a registration mark can be determined.

A lithographic printing plate precursor with a normal development processing step generally gives a colored image by coloring the image recording layer and developing it, so that the image can be easily confirmed before attaching the printing plate to the printing press. it can.
On the other hand, in an on-press development type or non-processing (no development) type lithographic printing plate precursor that does not involve a normal development processing step, an image on the lithographic printing plate precursor is confirmed at the stage of attaching the lithographic printing plate precursor to the printing press. It is difficult to perform plate inspection sufficiently. Therefore, on-machine development type or non-processed (no development) type lithographic printing plate precursor is formed with a means for confirming an image at the stage of exposure, that is, a so-called printout image in which the exposed area is colored or erased is formed. Is required. Furthermore, from the viewpoint of improving workability, it is also important to maintain the color developed or erased exposure area after the passage of time.

As conventional techniques, those described in Patent Document 1 or 2 are known.

EP 1736312 International Publication No. 2016/027866

The problem to be solved by one embodiment of the present invention is to provide a coloring composition having excellent coloring properties.
The problem to be solved by another embodiment of the present invention is to provide a lithographic printing plate precursor excellent in plate inspection by color development and a method for preparing a lithographic printing plate using the lithographic printing plate precursor.
Another problem to be solved by another embodiment of the present invention is to provide a novel compound that can be suitably used as a color former.

Means for solving the above problems include the following aspects.
<1> A coloring composition comprising a compound represented by the following formula 1.

In Formula 1, A represents a ring structure containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, A ⁺ represents a ring structure containing N ⁺ , O ⁺ or S ⁺ , Each X independently represents a carbon atom or a nitrogen atom, and at least one of X is a nitrogen atom, and when X is a nitrogen atom, R ¹ , R ² or R ³ bonded to the nitrogen atom is present R ¹ , R ² and R ³ are each independently a hydrogen atom, halogen atom, hydrocarbon group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, hydroxy group, alkoxycarbonyl group, acyloxy group, an amino group, a urethane group, a urea group, an amide group, a nitrile group or an imino group, the 2 or more of R ^{1 ~} R ³ may form a ring structure, one or more of R ¹ R ³ and A or A ⁺ and may form a ring structure, n is an integer of 1 ~ 6, Z represents a counter ion for neutralizing a charge.

<2> The coloring composition according to <1>, wherein the compound represented by Formula 1 is a compound represented by Formula 2 below.

In Formula 2, A represents a ring structure containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, Ar represents a ring structure containing N ⁺ , O ⁺ or S ⁺ , and L Represents —CH ₂ —, —CHR ^a —, —C (R ^a ) ₂ —, —NR ^a —, —O— or —S—, each R ^a independently represents a hydrocarbon group, R ¹ , R ² and R ³ are each independently a hydrogen atom, halogen atom, hydrocarbon group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, hydroxy group, alkoxycarbonyl group, acyloxy group, amino group, urethane Represents a group, a urea group, an amide group, a nitrile group or an imino group, and two or more R ¹ to R ³ may combine to form a ring structure and one or more R ¹ to R ³ and A, L or Combines with Ar to form a ring structure N represents an integer of 1 to 6, and Z represents a counter ion for neutralizing the electric charge.

<3> The coloring composition according to <1> or <2>, wherein the compound represented by the formula 1 is a compound represented by the following formula 3.

In Formula 3, A represents a ring structure containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, one of the two A ¹ represents N ⁺ , and the other represents a carbon atom. L represents —CH ₂ —, —CHR ^a —, —C (R ^a ) ₂ —, —NR ^a —, —O— or —S—, and each R ^a independently represents a hydrocarbon group. , R ¹ , R ² and R ³ are each independently a hydrogen atom, halogen atom, hydrocarbon group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, hydroxy group, alkoxycarbonyl group, acyloxy group, amino group Represents a group, a urethane group, a urea group, an amide group, a nitrile group or an imino group, and two or more R ¹ to R ³ may combine to form a ring structure, and one or more of R ¹ to R ³ and A , L or one or more R ⁴ to R ⁷ may combine with each other to form a ring structure, and R ⁴ to R ⁷ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, Represents a hydroxy group, an alkoxycarbonyl group, an acyloxy group, an amino group, a urethane group, a urea group, an amide group, a nitrile group, an imino group, a carboxylic acid group, a sulfonic acid group or a phosphoric acid group, and two or more R ⁴ to R ⁷ May combine to form a ring structure, n represents an integer of 1 to 6, and Z represents a counter ion for neutralizing the charge.

<4> The coloring composition according to any one of <1> to <3>, wherein the compound represented by the formula 1 is a compound represented by the following formula 4.

In Formula 4, A represents a ring structure containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, one of the two A ¹ represents N ⁺ , and the other represents a carbon atom. L represents —CH ₂ —, —CHR ^a —, —C (R ^a ) ₂ —, —NR ^a —, —O— or —S—, and each R ^a independently represents a hydrocarbon group. R ⁴ to R ¹⁴ are each independently a hydrogen atom, halogen atom, hydrocarbon group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, hydroxy group, alkoxycarbonyl group, acyloxy group, amino group, urethane Group, urea group, amide group, nitrile group, imino group, carboxylic acid group, sulfonic acid group or phosphoric acid group, and two or more R ⁴ to R ¹⁴ may be bonded to form a ring structure. or more of ^R 4 ~ ¹⁴ and the A or L may form a ring structure, Z is a counter ion for neutralizing a charge.

<5> The coloring composition according to <4>, wherein R ¹⁰ and R ¹² are bonded to form a ring structure.
<6> The color forming composition according to any one of <1> to <3>, wherein at least one of R ¹ to R ³ is a group represented by the following formula 5.

In Formula 5, R ¹⁵ represents a hydrocarbon group, and R ¹⁶ each independently represents a group represented by the following Formula 6, a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group Represents an acyl group, a hydroxy group, an alkoxycarbonyl group, an acyloxy group, an amino group, a urethane group, a urea group, an amide group, a nitrile group, or an imino group, and at least one of R ¹⁶ is represented by the following formula 6. Group.

In Formula 6, * represents a connecting position with the pyridinium ring in Formula 5, ** represents a connecting position with the polymethine chain in Formula 1 to Formula 4, and L ¹ is a single bond or a carbon number of 1 to 10 Represents a divalent hydrocarbon group, the methylene group in the divalent hydrocarbon group is partly an ether bond, thioether bond, carbonyl bond, ester bond, amino bond, urethane bond, urea bond, amide bond, and imino It may be replaced with at least one structure selected from the group consisting of bonds.

<7> The coloring composition according to <4>, wherein R ¹¹ is a group represented by the following formula 5.

<8> The color forming composition according to any one of <1> to <7>, further including a polymer.
<9> The color forming composition according to any one of <1> to <8>, further including a polymerization initiator and a polymerizable compound.
<10> The coloring composition according to <8> or <9>, which is a curable composition that is cured by infrared irradiation.
<11> A lithographic printing plate precursor having at least one layer containing the color forming composition according to any one of the above <1> to <10> on a support.
<12> Step of irradiating the lithographic printing plate precursor as described in <11> with infrared rays, at least one selected from the group consisting of printing ink and fountain solution on the lithographic printing plate irradiated with infrared rays on a printing press A method for producing a lithographic printing plate, comprising a step of supplying the toner and developing on-press.
<13> A compound represented by the following formula 1.

According to one embodiment of the present invention, it is possible to provide a color forming composition having excellent color developability.
In addition, according to another embodiment of the present invention, it is possible to provide a lithographic printing plate precursor having excellent plate inspection property by color development and a method for preparing a lithographic printing plate using the lithographic printing plate precursor.
Furthermore, according to another embodiment of the present invention, a novel compound that can be suitably used as a color former can be provided.

Hereinafter, the present disclosure will be described in detail.
In the present specification, the description “xx to yy” represents a numerical range including xx and yy.
In the present specification, “(meth) acryl” represents both and / or acryl and methacryl, and “(meth) acrylate” represents both and / or acrylate and methacrylate. In the present specification, “mass%” and “wt%” are synonymous, and “part by mass” and “part by weight” are synonymous. Moreover, in this specification, the combination of two or more preferable aspects is a more preferable aspect. In the present specification, regarding the notation of the group in the compound represented by the formula, when there is no substitution or no substitution, the above group can further have a substituent unless otherwise specified. In addition to an unsubstituted group, a group having a substituent is also included. For example, in the formula, if there is a description that “R represents an alkyl group, an aryl group or a heterocyclic group”, “R is an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted aryl group, a substituted aryl group, an unsubstituted group” Represents a heterocyclic group or a substituted heterocyclic group. In this specification, the term “process” is not only an independent process, but is included in this term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes.

[Coloring composition]
The color forming composition according to the present disclosure includes a compound represented by Formula 1.
Moreover, the coloring composition according to the present disclosure can be suitably used as a heat-sensitive, infrared-sensitive, or heat-sensitive and infrared-sensitive coloring composition.
Furthermore, the color forming composition according to the present disclosure can be suitably used for producing an image recording layer, a protective layer, or both an image recording layer and a protective layer of a lithographic printing plate precursor.

<Compound represented by Formula 1>
The compound represented by Formula 1 is a compound that is denatured or decomposed by exposure to heat or infrared rays to generate a color-forming compound.
In the present disclosure, color development means that there is almost no absorption in the visible light region (400 or more and less than 750 nm) before heating or infrared exposure, and there is a strong coloring after heating or infrared exposure, or the absorption becomes shorter in wavelength and visible light. Indicates that the region has absorption.
Note that the infrared ray in the present disclosure has a wavelength of 750 nm to 1 mm, and preferably a wavelength of 750 nm to 1,400 nm.
Although the details of the color development mechanism of the compound represented by Formula 1 are unknown, it has N ⁺ , O ⁺ or S ⁺ cation structure in the conjugated chain, so that N ⁺ in A ⁺ of Formula 1 is exposed by thermal or infrared exposure. , O ⁺ or S ^{+ in} the vicinity of the chemical structure is denatured or decomposed, and the length of the conjugated chain between A ⁺ to A in Formula 1 and the electronic state change, whereby the absorption wavelength changes and the color develops. The inventors have estimated.

Moreover, it is preferable that the compound represented by Formula 1 has a decomposable group which couple | bonds with a conjugated chain through the hetero atom mentioned later in R < ¹ >, R < ² > and R < ³ >.
By having the decomposable group, not only the coloring mechanism in the vicinity of the N ⁺ , O ⁺ or S ⁺ , but also the structure of the heteroatom by the decomposition of the decomposable group by heat or infrared exposure. The present inventors presume that the electronic state changes, structurally and electronically affects the conjugated chain, the absorption wavelength changes, and the color development improves.
Hereinafter, details of Formula 1 will be described.

A ⁺ in Formula 1 is preferably a ring structure having 3 to 20 carbon atoms including N ⁺ , O ^+, or S ⁺ . A ⁺ preferably contains an aromatic ring structure. Furthermore, A ⁺ preferably contains N ⁺ from the viewpoint of color developability, more preferably has at least one 5-membered or 6-membered ring structure containing N ^+, and a pyridinium ring structure It is particularly preferred that Further, the group on the nitrogen atom in the pyridinium ring structure preferably has a hydrocarbon group having 1 to 20 carbon atoms, more preferably has a hydrocarbon group having 1 to 15 carbon atoms, and has 1 to 10 carbon atoms. It is particularly preferable to have the following hydrocarbon group.
A in Formula 1 is preferably a ring structure having 3 to 20 carbon atoms including N, O, or S. Further, A preferably contains N from the viewpoint of color developability, more preferably has at least one 5-membered ring or 6-membered ring structure containing N, and a 6-membered ring containing N A structure is particularly preferred.
At least one of X in Formula 1 is a nitrogen atom. Since at least one is a nitrogen atom, the color developability is excellent. Further, from the viewpoint of color developability, X that is directly bonded to A ⁺ is preferably a nitrogen atom.
Further, from the viewpoint of color developability, at least two of X are preferably nitrogen atoms.
In Expression 1, since the bonds of the nitrogen atom is a 3, X may be nitrogen atom, R ^1, R ² or R ³ which binds to the nitrogen atom and are not present.

R ¹ , R ² and R ³ in formula 1 are each independently a hydrogen atom, halogen atom, hydrocarbon group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, alkoxycarbonyl group, acyloxy group, amino group , Urethane group, urea group, amide group, nitrile group or imino group, and at least one of R ¹ , R ² and R ³ is a hydrogen atom, hydrocarbon group, alkoxy group, aryloxy group, alkylthio A group, an arylthio group, an amino group, or an anilino group is more preferable. ^Further, at least one of R 1, ^{R 2} and ^{R 3} is preferably form a ring ^structure, at least two of R 1, ^{R 2} and ^{R 3} can form a ring structure More preferred.
Further, R ¹ , R ² and R ³ are each independently preferably a group having 0 to 60 carbon atoms, more preferably a group having 0 to 40 carbon atoms, and a group having 0 to 20 carbon atoms. It is particularly preferred.
Further, the alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, alkoxycarbonyl group, acyloxy group, amino group, urethane group, urea group, amide group and imino group in R ¹ , R ² and R ³ are 1 You may have the above substituent. Substituents include halogen atoms, hydrocarbon groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, acyl groups, alkoxycarbonyl groups, acyloxy groups, amino groups, urethane groups, urea groups, amide groups, nitrile groups, imino groups. Group and pyridinium group.
Further, the urethane group is preferably —NR ^N —CO—OR ^X or —O—CO—NR ^N R ^X , and the urea group is —NR ^N —CO—NR ^N R ^X The imino group is preferably —N═C (R ^X ) ₂ . Note that each R ^N independently represents a hydrogen atom or an alkyl group, R ^X independently represents a hydrocarbon group.

N in Formula 1 is preferably an integer of 2 to 6, more preferably an integer of 3 to 6, and particularly preferably 4 or 5.
Z in Formula 1 represents a counter ion for neutralizing the charge, but the compound represented by Formula 1 has a corresponding ionic substituent in its structure, and charge neutralization is not necessary Does not have to exist. When Z is an anion, halide ion, sulfonate ion, carboxylate ion, tetrafluoroborate ion, hexafluorophosphate ion, p-toluenesulfonate ion, p-chlorobenzenesulfonate ion, or perchlorate ion is preferable, and halide Ions, tetrafluoroborate ions, hexafluorophosphate ions, or p-toluenesulfonate ions are more preferable, and hexafluorophosphate ions are still more preferable. When Z is a cation, an alkali metal ion, an alkaline earth metal ion, an ammonium ion, a pyridinium ion, or a sulfonium ion is preferable, a sodium ion, a potassium ion, an ammonium ion, a pyridinium ion, or a sulfonium ion is more preferable, and sodium Ions, potassium ions, or ammonium ions are more preferable.

In addition, the compound represented by Formula 1 preferably has a decomposable group that is bonded to a conjugated chain via a heteroatom from the viewpoints of color developability and color retention after time, and R ¹ , R ² And R ³ more preferably has a decomposable group bonded to the conjugated chain via a hetero atom.
As the hetero atom in the decomposable group bonded to the conjugated chain via the hetero atom, an oxygen atom, a nitrogen atom, or a sulfur atom is preferably mentioned from the viewpoint of color developability and decomposability, and the oxygen atom is particularly preferable. Preferably mentioned.
The decomposable group bonded to the conjugated chain through the heteroatom is preferably a group having a pyridinium structure, more preferably a group represented by the following formula 5, and represented by the following formula D. Particularly preferred is a group.

R ¹⁵ in Formula 5 is preferably an alkyl group having 1 to 12 carbon atoms, more preferably a linear alkyl group having 1 to 12 carbon atoms, and a linear alkyl group having 1 to 8 carbon atoms. More preferred is a methyl group.
In Formula 5, it is preferable that one of R ¹⁶ is a group represented by Formula 6 above.
In addition, R ¹⁶ in Formula 5 is preferably independently a group represented by Formula 6 above, a hydrogen atom, or a hydrocarbon group, and is a group represented by Formula 6 above or a hydrogen atom. It is more preferable.
In Formula 6, it is preferable to bond to the polymethine chain in Formulas 1 to 4 through a hetero atom from the viewpoint of color development. As said hetero atom, an oxygen atom, a nitrogen atom, or a sulfur atom is mentioned preferably from a coloring property and a decomposable viewpoint, An oxygen atom is especially preferable.

In Formula D, R ^D1 represents an alkyl group, R ^D2 represents a hydrogen atom or an alkyl group, and Z ^D represents a counter ion that neutralizes charge.

The bonding position between the pyridinium ring in Formula D and the hydrocarbon group containing R ^D2 is preferably the 3rd or 4th position of the pyridinium ring, and more preferably the 4th position of the pyridinium ring.
The alkyl groups in R ^D1 and R ^D2 in Formula D may be linear, branched, or have a ring structure.
The alkyl group may have a substituent, and preferred examples of the substituent include an alkoxy group and a terminal alkoxy polyalkyleneoxy group.
R ^D1 in Formula D is preferably an alkyl group having 1 to 12 carbon atoms, more preferably a linear alkyl group having 1 to 12 carbon atoms, and a linear alkyl group having 1 to 8 carbon atoms. More preferred is a methyl group.
R ^D2 in Formula D is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and a branched alkyl group having 3 to 8 carbon atoms. It is more preferable that it is an isopropyl group or a t-butyl group.
Z ^D in formula D may be any counterion for neutralizing the electric charge, also the Z and the above Z ^D are the same, i.e., the Z ^D in Formula 1 may exist as the Z . Z ^D is preferably a sulfonate ion, a carboxylate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, a p-toluenesulfonate ion, or a perchlorate ion, and a p-toluenesulfonate ion, or More preferably, it is a hexafluorophosphate ion.

The compound represented by Formula 1 contained in the coloring composition according to the present disclosure is preferably a compound represented by Formula 2 from the viewpoint of color developability.

A, n, and Z in Formula 2 are the same as A, n, and Z in Formula 1, respectively, and the preferred embodiments are also the same.
Further, each of ^R 1, ^{R 2} and ^{R 3} in Formula 2, except that which may form one or more ^R 1 ~ ^{R 3} and L or Ar and is bonded to a ring structure, ^{R 1} in Formula 1 , R ² and R ³ , and preferred embodiments are also the same.
Ar in Formula 2 is preferably a ring structure having 3 to 20 carbon atoms including any of N ⁺ , O ⁺ , and S ⁺ . Ar preferably includes an aromatic ring structure. Furthermore, Ar preferably contains N ⁺ from the viewpoint of color developability, more preferably contains at least one 6-membered ring structure containing N ^+, and particularly preferably a pyridinium ring structure.
L in Formula 2 is preferably —CH ₂ —, —CHR ^a —, —C (R ^a ) ₂ —, —O—, or —S—, and —C (R ^a ) ₂ —, —O -Or -S- is more preferable, and -C (R ^a ) _2- or -O- is particularly preferable.
R ^a in Formula 2 is preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrocarbon group having 1 to 15 carbon atoms, and a hydrocarbon group having 1 to 10 carbon atoms. Is particularly preferred.

The compound represented by Formula 1 contained in the coloring composition according to the present disclosure is more preferably a compound represented by Formula 3 from the viewpoint of color developability.

A, n, and Z in Formula 3 are the same as A, n, and Z in Formula 1, respectively, and the preferred embodiments are also the same.
Further, ^R 1, ^{R 2} and ^{R 3,} except that which may form one or more ^R 1 ~ ^{R 3} and L or one or more ^R 4 ~ ^{R 7} are bonded to the ring structure in Formula 3 Is synonymous with R ¹ , R ² and R ³ in Formula 1, and the preferred embodiments are also the same.
One of the two ^{A 1} in Formula 3 represents ^{N +,} the other represents a carbon atom, it is preferable ^{A 1} ^{where R 4} is bound is ^{N +.}
R ⁴ to R ⁷ in Formula 3 are each independently a hydrogen atom, halogen atom, hydrocarbon group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, hydroxy group, alkoxycarbonyl group, acyloxy group, amino group , Anilino group, urethane group, urea group, amide group, nitrile group or imino group, preferably a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, an amino group, an anilino group. A group, a urethane group, a urea group, or an amide group is more preferable. Further, two or more R ⁴ to R ⁷ are preferably bonded to form a ring structure.

The compound represented by Formula 1 contained in the coloring composition according to the present disclosure is more preferably a compound represented by Formula 4 from the viewpoint of color developability.

A and Z in Formula 4 have the same meanings as A and Z in Formula 1, respectively, and preferred embodiments are also the same.
Further, each of ^A 1, L and ^{R a} in Formula 4, has the same meaning as ^A 1, L and ^{R a} in Formula 3, preferred embodiment is also the same.
R ⁸ to R ¹⁴ in Formula 4 are each independently a hydrogen atom, halogen atom, hydrocarbon group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, alkoxycarbonyl group, acyloxy group, amino group, urethane group , Urea group, amide group, nitrile group, or imino group, hydrogen atom, halogen atom, hydrocarbon group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, alkoxycarbonyl group, acyloxy It is more preferably a group or an amino group, and particularly preferably a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, or an amino group. From the viewpoint of color development, two or more R ⁴ to R ¹⁴ are preferably bonded to form a ring structure, and R ¹⁰ and R ¹² are bonded to form a ring structure. More preferred.
The ring structure formed by combining R ¹⁰ and R ¹² is preferably a ring structure having at least one 5- or 6-membered ring structure from the viewpoint of color development, and preferably has at least one 5-membered ring structure. It is more preferable that the ring structure has one or more.
R ¹¹ in Formula 4 is preferably a group represented by Formula 5 from the viewpoint of color developability.

Preferred examples of the compound represented by Formula 1 are listed below, but the present disclosure is not limited thereto. TsO ⁻ represents a tosylate anion.

The compound represented by Formula 1 may be used individually by 1 type, or may use 2 or more types together.
In the color forming composition according to the present disclosure, the content of the compound represented by Formula 1 is preferably 0.1 to 95% by mass, more preferably 1 to 50% by mass, based on the total solid content of the color forming composition. More preferable is 40 mass%. The total solid content in the present disclosure is the total amount of components excluding volatile components such as a solvent in the composition.

The compound represented by Formula 1 can be synthesized by applying a known method. For example, after synthesizing 2,3,3-trimethyl-3H-pyrrolo [2,3-b] pyridine by the method described in JP-A-2006-299230, the method described in International Publication No. 2016/027886 is used. It can be synthesized by dyeing and substitution reaction at the meso position.

[polymer]
The coloring composition according to the present disclosure preferably contains a polymer from the viewpoints of coatability and film formability. The type of polymer is not particularly limited as long as it is a known polymer, but a film-forming polymer, a microgel described later, or a polymer particle described later is preferably exemplified. Examples of the film-forming polymer include (meth) acrylic resin, polyurethane, polyester, polyamide, polyether, polycarbonate, polyurea, polyolefin, vinyl resin, polyamine and the like. The polymer used in the coloring composition may be added after being dissolved in the composition, or may be added as a polymer dispersion such as a microgel described later or polymer particles described later. The polymer added by dissolving in the composition is preferably a (meth) acrylic resin, polyurethane, polyester, or vinyl resin, and the microgel or polymer particle dispersion is a (meth) acrylic resin, polyurethane, polyamide, polyurea, polyolefin, Vinyl resin is preferred.

In the case where it is added after being dissolved in the composition, the polymer suitable for the on-press development type lithographic printing plate precursor is preferably a (meth) acrylic resin, polyurethane, polyester or vinyl resin, more preferably a (meth) acrylic resin or polyurethane. preferable.
As the polymer, a polymer having an alkylene oxide chain is particularly preferable. The polymer having an alkylene oxide chain may have a poly (alkylene oxide) moiety in the main chain or a side chain. Further, it may be a graft polymer having poly (alkylene oxide) in the side chain, or a block copolymer of a block composed of poly (alkylene oxide) -containing repeating units and a block composed of (alkylene oxide) -free repeating units.
Polyurethane is preferred when it has a poly (alkylene oxide) moiety in the main chain. The main chain polymer with a poly (alkylene oxide) moiety in the side chain is (meth) acrylic resin, polyvinyl acetal, polyurethane, polyurea, polyimide, polyamide, epoxy resin, polystyrene, novolac phenolic resin, polyester, synthesis Examples thereof include rubber and natural rubber, and (meth) acrylic resin is particularly preferable.

As the alkylene oxide, an alkylene oxide having 2 to 6 carbon atoms is preferable, and ethylene oxide or propylene oxide is particularly preferable.
The repeating number of alkylene oxide at the poly (alkylene oxide) site is preferably 2 to 120, more preferably 2 to 70, and still more preferably 2 to 50.
If the repeating number of alkylene oxide is 120 or less, a decrease in film strength is suppressed.

The poly (alkylene oxide) moiety is preferably contained as a side chain of the polymer in a structure represented by the following formula (AO), and is represented by the following formula (AO) as a side chain of the (meth) acrylic resin. More preferably, it is contained in a structure.

In the formula (AO), y represents 2 to 120, R ₁ represents a hydrogen atom or an alkyl group, and R ₂ represents a hydrogen atom or a monovalent organic group.
As the monovalent organic group, an alkyl group having 1 to 6 carbon atoms is preferable. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n- Examples include a hexyl group, an isohexyl group, a 1,1-dimethylbutyl group, a 2,2-dimethylbutyl group, a cyclopentyl group, and a cyclohexyl group.
In the formula (AO), y is preferably 2 to 70, more preferably 2 to 50. R ₁ is preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom. R ₂ is particularly preferably a hydrogen atom or a methyl group.

The polymer preferably has crosslinkability in order to improve the film strength of the layer. In order to impart crosslinkability to the polymer, a crosslinkable group such as an ethylenically unsaturated bond may be introduced to impart photocrosslinkability, or thermoplasticity may be imparted to impart thermal crosslinkability. The crosslinkable group can be introduced into either the main chain or the side chain of the polymer, and examples thereof include a method of introducing by copolymerization and a method of introducing by polymerization after polymerization. In order to impart thermoplasticity, the glass transition temperature of the polymer may be adjusted.
Examples of the polymer having an ethylenically unsaturated bond in the main chain include polybutadiene and polyisoprene.
Examples of the polymer having an ethylenically unsaturated bond in the side chain include a polymer having a (meth) acrylate group, a (meth) acrylamide group, a vinyl group, or an allyl group in the side chain.
As a method for adjusting the glass transition temperature, the composition of the monomer to be copolymerized and the molecular weight of the polymer can be changed and adjusted.

The content of the crosslinkable group in the polymer (content of unsaturated double bond capable of radical polymerization by iodine titration) is preferably 0.1 to 10.0 mmol per 1 g of the binder polymer from the viewpoint of film strength. 0.0 to 7.0 mmol is more preferable, and 2.0 to 5.5 mmol is particularly preferable.

Specific examples 1 to 11 of the polymer are shown below, but the present disclosure is not limited thereto. In the following exemplary compounds, a numerical value written together with each repeating unit (a numerical value written together with the main chain repeating unit) represents a mole percentage of the repeating unit. The numerical value written together with the repeating unit of the side chain indicates the number of repeating parts. Me represents a methyl group, Et represents an ethyl group, and Ph represents a phenyl group.

As for the molecular weight of the polymer used in the present disclosure, the weight average molecular weight (Mw) is preferably 2,000 or more, preferably 5,000 or more, as a polystyrene conversion value by gel permeation chromatography (GPC). More preferably, it is 10,000 to 300,000.
In the present disclosure, the oligomer is Mw 800 or more and less than 2,000, and the polymer is Mw 2,000 or more.

If necessary, hydrophilic polymers such as polyacrylic acid and polyvinyl alcohol described in JP-A-2008-195018 can be used in combination. Further, a lipophilic polymer and a hydrophilic polymer can be used in combination.

In the coloring composition according to the present disclosure, the polymers may be used alone or in combination of two or more.
The polymer can be contained in the coloring composition in any amount.
The content of the polymer can be appropriately selected depending on the use of the color forming composition, but is preferably 1 to 90% by mass, and more preferably 5 to 80% by mass with respect to the total solid content of the color forming composition.

[Polymerization initiator]
The coloring composition according to the present disclosure may contain a polymerization initiator. The polymerization initiator used in the coloring composition is a compound that generates polymerization initiation species such as radicals and cations by energy of light, heat, or both, and has a known thermal polymerization initiator and a bond with small bond dissociation energy. It can be appropriately selected from compounds, photopolymerization initiators, and the like.
As a polymerization initiator, an infrared photosensitive polymerization initiator is preferable. Moreover, as a polymerization initiator, a radical polymerization initiator is preferable.
Examples of the radical polymerization initiator include (a) an organic halide, (b) a carbonyl compound, (c) an azo compound, (d) an organic peroxide, (e) a metallocene compound, (f) an azide compound, (g ) Hexaarylbiimidazole compounds, (h) disulfone compounds, (i) oxime ester compounds, and (j) onium salt compounds.

As the (a) organic halide, for example, compounds described in paragraphs 0022 to 0023 of JP-A-2008-195018 are preferable.
As the (b) carbonyl compound, for example, compounds described in paragraph 0024 of JP-A-2008-195018 are preferable.
Examples of (c) azo compounds include the azo compounds described in JP-A-8-108621.
As the (d) organic peroxide, for example, compounds described in paragraph 0025 of JP-A-2008-195018 are preferable.
As the (e) metallocene compound, for example, compounds described in paragraph 0026 of JP-A-2008-195018 are preferred.
Examples of (f) an azide compound include compounds such as 2,6-bis (4-azidobenzylidene) -4-methylcyclohexanone.
(G) As the hexaarylbiimidazole compound, for example, a compound described in paragraph 0027 of JP-A-2008-195018 is preferable.
Examples of (h) disulfone compounds include compounds described in JP-A Nos. 61-166544 and 2002-328465.
(I) As the oxime ester compound, for example, compounds described in paragraphs 0028 to 0030 of JP-A-2008-195018 are preferable.

Among the polymerization initiators, from the viewpoint of curability, oxime ester compounds and onium salts are more preferable, and onium salts such as iodonium salts, sulfonium salts, and azinium salts are more preferable. When used for a lithographic printing plate precursor, iodonium salts and sulfonium salts are particularly preferred. Specific examples of the iodonium salt and the sulfonium salt are shown below, but the present disclosure is not limited thereto.

As an example of the iodonium salt, a diphenyl iodonium salt is preferable, and a diphenyl iodonium salt having an electron donating group as a substituent, for example, substituted with an alkyl group or an alkoxyl group is preferable, and an asymmetric diphenyl iodonium salt is also preferable. preferable. Specific examples include diphenyliodonium = hexafluorophosphate, 4-methoxyphenyl-4- (2-methylpropyl) phenyliodonium = hexafluorophosphate, 4- (2-methylpropyl) phenyl-p-tolyliodonium = hexa Fluorophosphate, 4-hexyloxyphenyl-2,4,6-trimethoxyphenyliodonium = hexafluorophosphate, 4-hexyloxyphenyl-2,4-diethoxyphenyliodonium = tetrafluoroborate, 4-octyloxy Phenyl-2,4,6-trimethoxyphenyliodonium = 1-perfluorobutanesulfonate, 4-octyloxyphenyl-2,4,6-trimethoxyphenyliodonium = hexafluorophosphate, and Scan (4-t- butylphenyl) iodonium hexafluorophosphate and the like.

As an example of the sulfonium salt, a triarylsulfonium salt is preferable, and in particular, a triarylsulfonium salt having an electron withdrawing group as a substituent, for example, at least a part of the group on the aromatic ring is substituted with a halogen atom is preferable. A triarylsulfonium salt in which the total number of halogen atoms on the aromatic ring is 4 or more is more preferable. Specific examples include triphenylsulfonium = hexafluorophosphate, triphenylsulfonium = benzoylformate, bis (4-chlorophenyl) phenylsulfonium = benzoylformate, bis (4-chlorophenyl) -4-methylphenylsulfonium = tetrafluoro. Borate, tris (4-chlorophenyl) sulfonium = 3,5-bis (methoxycarbonyl) benzenesulfonate, tris (4-chlorophenyl) sulfonium = hexafluorophosphate, and tris (2,4-dichlorophenyl) sulfonium = hexa Fluorophosphate is mentioned.

A polymerization initiator may be used individually by 1 type, and may use 2 or more types together.
The content of the polymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and particularly preferably 0.8 to 20% by mass with respect to the total solid content of the color forming composition. .

[Polymerizable compound]
The coloring composition according to the present disclosure may contain a polymerizable compound. The color forming composition according to the present disclosure containing a polymerizable compound is preferably a curable color forming composition having a polymerization curing function in addition to the color formation by application of heat and infrared exposure.
Further, the coloring composition according to the present disclosure can be suitably used as a curable composition containing a polymerization initiator and a polymerizable compound from the viewpoint of curability, and as an infrared curable and infrared photosensitive coloring composition. It can be used more suitably.
The polymerizable compound used in the coloring composition may be, for example, a radical polymerizable compound or a cationic polymerizable compound, but an addition polymerizable compound having at least one ethylenically unsaturated bond (ethylene A unsaturated unsaturated compound). As the ethylenically unsaturated compound, a compound having at least one terminal ethylenically unsaturated bond is preferable, and a compound having two or more terminal ethylenically unsaturated bonds is more preferable. The polymerizable compound can have a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer or an oligomer, or a mixture thereof.

Examples of monomers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid), esters thereof, and amides. Preferably, esters of unsaturated carboxylic acid and polyhydric alcohol compound, and amides of unsaturated carboxylic acid and polyvalent amine compound are used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or A dehydration condensation reaction product with a polyfunctional carboxylic acid is also preferably used. In addition, an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group and an addition reaction product of a monofunctional or polyfunctional alcohol, amine or thiol, further a halogen atom, A substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, a compound group in which the unsaturated carboxylic acid is replaced with unsaturated phosphonic acid, styrene, vinyl ether, or the like can be used. These compounds are disclosed in JP-T-2006-508380, JP-A-2002-287344, JP-A-2008-256850, JP-A-2001-342222, JP-A-9-179296, JP-A-9-179297. JP, 9-179298, JP 2004-294935, JP 2006-243493, JP 2002-275129, JP 2003-64130, JP 2003-280187, It is described in JP-A-10-333321.

Specific examples of monomers of esters of polyhydric alcohol compounds and unsaturated carboxylic acids include acrylic acid esters such as ethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, Examples include trimethylolpropane triacrylate, hexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, isocyanuric acid ethylene oxide (EO) -modified triacrylate, and polyester acrylate oligomer. Methacrylic acid esters include tetramethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, pentaerythritol trimethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl] Examples thereof include dimethylmethane and bis [p- (methacryloxyethoxy) phenyl] dimethylmethane. Specific examples of amide monomers of polyamine compounds and unsaturated carboxylic acids include methylene bisacrylamide, methylene bismethacrylamide, 1,6-hexamethylene bisacrylamide, 1,6-hexamethylene bismethacrylamide, Examples include diethylenetriamine trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide.

Also suitable are urethane-based addition-polymerizable compounds produced by the addition reaction of isocyanate and hydroxy groups. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. Vinyl containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxy group represented by the following formula (M) to a polyisocyanate compound having two or more isocyanate groups A urethane compound etc. are mentioned.
CH ₂ ═C (R ^M4 ) COOCH ₂ CH (R ^M5 ) OH (M)
In formula (M), R ^M4 and R ^M5 each independently represent a hydrogen atom or a methyl group.

Further, urethane acrylates described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-A-2003-344997, JP-A-2006-65210, Ethylene described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, JP-B-62-39418, JP-A-2000-250211, and JP-A-2007-94138 Urethane compounds having an oxide skeleton, urethane compounds having a hydrophilic group described in US Pat. No. 7,153,632, JP-A-8-505958, JP-A-2007-293221, and JP-A-2007-293223 Are also suitable.

Details of the method of use such as the structure of the polymerizable compound, whether it is used alone or in combination, and the amount added can be arbitrarily set in consideration of the intended use of the final color forming composition.
The content of the polymerizable compound is preferably 5 to 75% by mass, more preferably 10 to 70% by mass, and particularly preferably 15 to 60% by mass with respect to the total solid content of the color forming composition.

[Radical generation aid]
The coloring composition according to the present disclosure may contain a radical generation aid. The radical generation aid contributes to the improvement of the printing durability in the lithographic printing plate when the color forming composition is used in the image recording layer of the lithographic printing plate precursor. Examples of radical generation aids include the following five types.
(I) Alkyl or aryl ate complex: It is considered that a carbon-hetero bond is oxidatively cleaved to generate an active radical. Specific examples include borate compounds.
(Ii) Aminoacetic acid compound: It is considered that a C—X bond on carbon adjacent to nitrogen is cleaved by oxidation to generate an active radical. X is preferably a hydrogen atom, a carboxy group, a trimethylsilyl group or a benzyl group. Specific examples include N-phenylglycines (which may have a substituent on the phenyl group), N-phenyliminodiacetic acid (which may have a substituent on the phenyl group), and the like. It is done.
(Iii) Sulfur-containing compound: A compound in which the nitrogen atom of the aminoacetic acid compound described above is replaced with a sulfur atom can generate an active radical by the same action. Specific examples include phenylthioacetic acid (which may have a substituent on the phenyl group).
(Iv) Tin-containing compound: A compound in which the nitrogen atom of the above-mentioned aminoacetic acid compound is replaced with a tin atom can generate an active radical by the same action.
(V) Sulfinic acid salts: Active radicals can be generated by oxidation. Specific examples include sodium arylsulfinate.

Among these radical generation aids, the color forming composition preferably contains a borate compound. As the borate compound, a tetraarylborate compound or a monoalkyltriarylborate compound is preferable. From the viewpoint of stability of the compound and a potential difference described later, a tetraarylborate compound is more preferable, and from the viewpoint of a potential difference described later, an electron withdrawing property. A tetraaryl borate compound having one or more aryl groups having a group is particularly preferable.
The electron withdrawing group is preferably a group having a positive Hammett's σ value, and more preferably a group having a Hammett's σ value of 0 to 1.2. For Hammett σ values (σ _p value and σ _m value), Hansch, C .; Leo, A .; Taft, R .; W. , Chem. Rev. 1991, 91, 165-195.
As the electron withdrawing group, a halogen atom, a trifluoromethyl group or a cyano group is preferable, and a fluorine atom, a chlorine atom, a trifluoromethyl group or a cyano group is more preferable.
The counter cation possessed by the borate compound is preferably an alkali metal ion or a tetraalkylammonium ion, more preferably a sodium ion, a potassium ion or a tetrabutylammonium ion.

When the coloring composition contains a borate compound, the potential difference ΔG2 between the highest occupied orbit (HOMO) of the compound represented by the formula 1 and the highest occupied orbit of the borate compound (ΔG2 = expressed by the above formula (1)). HOMO-borate compound HOMO) is preferably 0.500 eV or more, more preferably 0.585 eV or more, particularly preferably 0.608 eV or more and 1.000 eV or less.
When the potential difference between the HOMO of the compound represented by the formula 1 and the HOMO of the borate compound is in the above range and the compound represented by the formula 1 has a pyridinium ring structure, the borate other than at the time of heat or infrared exposure In addition to excellent stability of the compound, electron transfer occurs from the HOMO of the borate compound to the HOMO of the compound represented by the above formula 1 at the time of heat or infrared exposure, so that the lowest empty orbit of the compound represented by the above formula 1 It is considered that the excitation to (LUMO) is promoted and the decomposition of the compound represented by Formula 1 is promoted. In addition, the electron transfer from the compound represented by the above formula 1 to the polymerization initiator is promoted, and when the color forming composition is used for the image recording layer of the lithographic printing plate precursor, it contributes to the improvement of printing durability in the lithographic printing plate. I think that.

Calculation of HOMO and LUMO of the compound represented by Formula 1 is performed by the following method.
First, the counter anion in the compound to be calculated is ignored.
The structure optimization is performed by DFT (B3LYP / 6-31G (d)) using quantum chemistry calculation software Gaussian09.
The MO (molecular orbital) energy calculation is performed by DFT (B3LYP / 6-31 + G (d, p) / CPCM (solvent = methanol)) with the structure obtained by the above structure optimization.
The MO energy Epre (unit: hartree) obtained by the MO energy calculation is converted into Eaft (unit: eV) used as values of HOMO and LUMO in the present disclosure by the following formula.
Eaft = 0.823168 × 27.2114 × Epre−1.07634
Note that 27.2114 is a coefficient for simply converting hartree to eV, 0.823168 and -1.07634 are adjustment coefficients, and HOMO and LUMO of the compound to be calculated are calculated values. It was decided to suit.
ΔG2 is determined from the difference between the HOMO of the compound represented by Formula 1 and the HOMO of the borate compound (ΔG2 = HOMO of the compound represented by Formula 1—HOMO of the borate compound).

Specific examples of the borate compound include the following compounds. Here, X _c ⁺ represents a monovalent cation, preferably an alkali metal ion or a tetraalkylammonium ion, and more preferably an alkali metal ion or a tetrabutylammonium ion. Bu represents an n-butyl group.

Only one type of radical generation aid may be added, or two or more types may be used in combination.
The content of the radical generation aid is preferably 0.01 to 30% by mass, more preferably 0.05 to 25% by mass, and still more preferably 0.1 to 20% by mass with respect to the total solid content of the color forming composition. .

[Chain transfer agent]
The coloring composition according to the present disclosure may contain a chain transfer agent. The chain transfer agent contributes to the improvement of the printing durability in the lithographic printing plate when the color forming composition is used for the image recording layer of the lithographic printing plate precursor.
As the chain transfer agent, a thiol compound is preferable, a thiol compound having 7 or more carbon atoms is more preferable from the viewpoint of boiling point (difficult to volatilize), and a compound having a mercapto group on an aromatic ring (aromatic thiol compound) is more preferable. . The thiol compound is preferably a monofunctional thiol compound.

Specific examples of the chain transfer agent include the following compounds.

A chain transfer agent may add only 1 type or may use 2 or more types together.
The content of the chain transfer agent is preferably 0.01 to 50% by mass, more preferably 0.05 to 40% by mass, and still more preferably 0.1 to 30% by mass with respect to the total solid content of the color forming composition.

[Infrared absorber]
The color forming composition according to the present disclosure may contain an infrared absorber. By containing an infrared absorber, the coloring composition according to the present disclosure can be more suitably used as an infrared photosensitive coloring composition.
Moreover, even if it is a case where the coloring composition which concerns on this indication is used as a heat-sensitive coloring composition, it may contain the infrared absorber.
An infrared absorber is a compound having a function of converting absorbed infrared rays into heat. Further, the infrared absorber may have a function of transferring electrons or transferring energy to a polymerization initiator or the like to be described later when excited by infrared rays.
The infrared absorber preferably has a maximum absorption in a wavelength region of 750 to 1,400 nm. As the infrared absorber, a dye or a pigment is preferably used.

As the dye, commercially available dyes and known dyes described in documents such as “Dye Handbook” (edited by the Society for Synthetic Organic Chemistry, published in 1970) can be used. Specifically, dyes such as azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes Is mentioned.
Among these dyes, cyanine dyes, squarylium dyes, and pyrylium salts are preferable. Among these, cyanine dyes are preferable, and indolenine cyanine dyes are particularly preferable.

Specific examples of cyanine dyes include compounds described in paragraphs 0017 to 0019 of JP-A-2001-133969, paragraphs 0016 to 0021 of JP-A-2002-023360, paragraphs 0012 to 0037 of JP-A-2002-040638. Compounds described in JP-A-2002-278057, preferably paragraphs 0034 to 0041 of JP-A-2002-278057, JP-A-2008-195018, paragraphs 0080 to 0086, particularly preferably JP-A-2007-90850, paragraph 0035 To 0043 are mentioned.
Further, compounds described in paragraphs 0008 to 0009 of JP-A-5-5005 and paragraphs 0022 to 0025 of JP-A-2001-222101 can also be preferably used.
As the pigment, compounds described in paragraphs 0072 to 0076 of JP-A-2008-195018 are preferable.

Only 1 type may be used for an infrared absorber and it may use 2 or more types together. Moreover, you may use together a pigment and dye as an infrared absorber.
The infrared absorber can be contained in an arbitrary amount in the coloring composition. The content of the infrared absorber is preferably 0.05 to 30% by mass, more preferably 0.1 to 20% by mass, based on 100 parts by mass of the total solid content of the color forming composition. More preferably, it is 2 to 10% by mass.

The coloring composition according to the present disclosure may contain additives other than those described above (for example, a surfactant) as necessary.

Each component contained in the coloring composition according to the present disclosure is dissolved or dispersed in an appropriate solvent to prepare a coating solution, and the coating solution is applied to a support and dried to form a coloring composition film. be able to.
A known solvent can be used as the solvent. Specifically, for example, water, acetone, methyl ethyl ketone (2-butanone), cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene Glycol monoethyl ether, acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 1-methoxy-2-propanol, 3-methoxy -1-propanol, methoxymethoxy ester Nord, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone , Methyl lactate, ethyl lactate and the like. A solvent can be used individually by 1 type or in mixture of 2 or more types. The solid concentration in the coating solution is preferably about 1 to 50% by mass. The solid content concentration is the concentration of all components excluding the solvent.

The coloring composition according to the present disclosure can be used for heat-sensitive coloring materials, infrared-sensitive coloring materials, and the like. Thermosensitive coloring materials can be widely used as thermal recording media such as tickets and receipts in facsimile machines, computer terminal printers, automatic ticket vending machines, measurement recorders, supermarkets and convenience store cash registers.

Further, the color forming composition according to the present disclosure is preferably used for an image forming material. Examples of image forming materials include lithographic printing plate precursors, printed wiring boards, color filters, photomasks, and other image forming materials that use color development by image exposure, and image forming materials that use color development and polymerization curing.
The image forming material using the color forming composition according to the present disclosure forms a color image by being exposed to heat or a light source that emits infrared rays. As the heating means, known heating means can be used, and examples thereof include a heater, an oven, a hot plate, an infrared lamp, and an infrared laser. Examples of light sources that emit infrared light include solid-state lasers and semiconductor lasers that emit infrared light.

[Lithographic printing plate precursor]
Next, an example in which the color forming composition according to the present disclosure is applied to a lithographic printing plate precursor will be described.
The lithographic printing plate precursor according to the present disclosure preferably has at least one layer containing the color forming composition according to the present disclosure on a support. The coloring composition according to the present disclosure can be used for any of the undercoat layer, the image recording layer, and the protective layer in the lithographic printing plate precursor, but is particularly preferably used for the image recording layer. The type of the lithographic printing plate precursor according to the present disclosure is not particularly limited, and examples thereof include an alkali developing type and an on-press developing type, and an on-press developing type is particularly preferable.
Hereinafter, an on-press development type lithographic printing plate precursor in which the characteristics of the color forming composition according to the present disclosure are remarkably exhibited will be described as an example.

(Image recording layer)
The image recording layer in the lithographic printing plate precursor is required to have developability and printability. The coloring composition preferably contains the compound represented by Formula 1 and the polymer. In the case of an on-press development type lithographic printing plate precursor, the above-mentioned polymer for film formation is preferably used as the polymer.
The color forming composition used for the image recording layer preferably further contains a polymerizable compound and a polymerization initiator, and further contains a radical generation aid and a chain transfer agent alone or in combination. Is more preferable.
Moreover, it is preferable that the coloring composition used for the image recording layer further contains microgel or polymer particles.
That is, the image recording layer of the lithographic printing plate precursor according to the present disclosure preferably contains each component contained in the color forming composition.
Each of the compounds represented by Formula 1 contained in the image recording layer, such as a polymer (for example, a film-forming polymer, microgel, polymer particles, etc.), a polymerizable compound, a polymerization initiator, a radical generation aid, a chain transfer agent, etc. Regarding the constituent components and the content thereof, the description in the color forming composition according to the present disclosure can also be referred to.

The image recording layer may further contain a low molecular weight hydrophilic compound, a sensitizer, a solvent, and other components in addition to the above-described components.

(Microgel and polymer particles)
In order to improve the on-press developability of the lithographic printing plate precursor, the image recording layer may contain microgel and / or polymer particles. The microgel and polymer particles are preferably crosslinked, melted, or both caused by light or heat generated by infrared irradiation, or changed to hydrophobicity. The microgel and polymer particles are preferably at least one selected from the group consisting of non-crosslinkable microgels, crosslinkable microgels, thermoplastic polymer particles, thermally reactive polymer particles, and polymer particles having a polymerizable group. These may have a core-shell structure and may contain other compounds.

Thermoplastic polymer particles include Research Disclosure No. 1 of January 1992. Preferred examples include polymer particles described in Japanese Patent No. 33303, JP-A-9-123387, JP-A-9-131850, JP-A-9-171249, JP-A-9-171250 and European Patent 931647.
Specific examples of the polymer constituting the thermoplastic polymer particles include ethylene, styrene, vinyl chloride, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinylidene chloride, acrylonitrile, vinyl carbazole, and polyalkylene structures. Mention may be made of homopolymers or copolymers of monomers such as acrylates or methacrylates or mixtures thereof. Preferably, polystyrene, a copolymer containing styrene and acrylonitrile, and polymethyl methacrylate are used.

Examples of the thermally reactive polymer particles include polymer particles having a thermally reactive group. The polymer particles having a thermoreactive group form a hydrophobized region by crosslinking by a thermal reaction and a functional group change at that time.

The thermoreactive group in the polymer particles having a thermoreactive group may be any functional group that performs any reaction as long as a chemical bond is formed, and is preferably a polymerizable group. Examples include ethylenically unsaturated groups that undergo radical polymerization reactions (eg, acryloyl groups, methacryloyl groups, vinyl groups, allyl groups, etc.), cationic polymerizable groups (eg, vinyl groups, vinyloxy groups, epoxy groups, oxetanyl groups). Etc.), isocyanato group that performs an addition reaction or a block thereof, an epoxy group, a vinyloxy group, and a functional group having an active hydrogen atom that is a reaction partner thereof (for example, an amino group, a hydroxy group, a carboxy group, etc.), a condensation reaction Preferred examples include a carboxyl group to be performed and a hydroxy group or amino group which is a reaction partner, an acid anhydride which performs a ring-opening addition reaction, and an amino group or hydroxy group which is a reaction partner.

Examples of the microcapsule include those in which all or part of the constituent components of the image recording layer are encapsulated in the microcapsule as described in JP-A Nos. 2001-277740 and 2001-277742. The constituent components of the image recording layer can also be contained outside the microcapsules. The image recording layer containing microcapsules is preferably a mode in which hydrophobic constituent components are encapsulated in microcapsules and hydrophilic constituent components are contained outside the microcapsules.

The microgel can contain a part of the constituent components of the image recording layer in at least one of the inside and the surface thereof. In particular, an embodiment in which a reactive microgel is formed by having a radical polymerizable group on the surface thereof is preferable from the viewpoint of image forming sensitivity and printing durability.

In order to microencapsulate or microgel the constituent components of the image recording layer, a known method can be used.
When the coloring composition according to the present disclosure contains a polymer in the form of microcapsules, microgels or polymer particles, the average primary particle diameter of the microcapsules, microgels or polymer particles is preferably 10 to 1,000 nm. 20 to 300 nm is more preferable, and 30 to 120 nm is still more preferable.
The average primary particle diameter of each particle in the present disclosure is measured by a light scattering method, or an electron micrograph of the particle is taken, and a total of 5,000 particle diameters are measured on the photograph. The value shall be calculated. For non-spherical particles, the particle size of spherical particles having the same particle area as that on the photograph is used as the particle size.
The content of the microgel or polymer particles is preferably 5 to 90% by mass with respect to the total solid content of the image recording layer.

(Low molecular hydrophilic compound)
The image recording layer may contain a low molecular weight hydrophilic compound in order to improve the on-press developability without reducing the printing durability. The low molecular weight hydrophilic compound is preferably a compound having a molecular weight of less than 1,000, more preferably a compound having a molecular weight of less than 800, and still more preferably a compound having a molecular weight of less than 500.
As the low molecular weight hydrophilic compound, for example, as the water-soluble organic compound, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and the like glycols and ether or ester derivatives thereof, glycerin, Polyols such as pentaerythritol and tris (2-hydroxyethyl) isocyanurate, organic amines such as triethanolamine, diethanolamine and monoethanolamine and salts thereof, organic sulfones such as alkylsulfonic acid, toluenesulfonic acid and benzenesulfonic acid Acids and salts thereof, organic sulfamic acids such as alkylsulfamic acid and salts thereof, organic sulfuric acids such as alkylsulfuric acid and alkylethersulfuric acid and salts thereof, phenylphosphonic acid Organic phosphonic acids and salts thereof, tartaric acid, oxalic acid, citric acid, malic acid, lactic acid, gluconic acid, organic carboxylic acids and salts thereof such as amino acids, betaines, and the like.

As the low molecular weight hydrophilic compound, it is preferable to contain at least one selected from the group consisting of polyols, organic sulfates, organic sulfonates, and betaines.

Specific examples of the organic sulfonates include alkyl sulfonates such as sodium n-butyl sulfonate, sodium n-hexyl sulfonate, sodium 2-ethylhexyl sulfonate, sodium cyclohexyl sulfonate, sodium n-octyl sulfonate; 5 , 8,11-Trioxapentadecane-1-sulfonic acid sodium salt, 5,8,11-trioxaheptadecane-1-sulfonic acid sodium salt, 13-ethyl-5,8,11-trioxaheptadecane-1-sulfone Alkyl sulfonates containing ethylene oxide chains such as sodium acid, sodium 5,8,11,14-tetraoxatetracosane-1-sulfonate; sodium benzenesulfonate, sodium p-toluenesulfonate, p-hydroxybenzenesulfonic acid Na Sodium, sodium p-styrenesulfonate, sodium dimethyl-5-sulfonate isophthalate, sodium 1-naphthylsulfonate, sodium 4-hydroxynaphthylsulfonate, disodium 1,5-naphthalenedisulfonate, 1,3,6- Examples thereof include aryl sulfonates such as trisodium naphthalene trisulfonate, compounds described in paragraphs 0026 to 0031 of JP-A-2007-276454 and paragraphs 0020 to 0047 of JP-A-2009-154525. The salt may be a potassium salt or a lithium salt.

Examples of organic sulfates include polyethylene oxide alkyl, alkenyl, alkynyl, aryl, or heterocyclic monoether sulfates. The number of ethylene oxide units is preferably 1 to 4, and the salt is preferably a sodium salt, potassium salt or lithium salt. Specific examples include the compounds described in paragraphs 0034 to 0038 of JP-A-2007-276454.

The betaines are preferably compounds in which the hydrocarbon substituent on the nitrogen atom has 1 to 5 carbon atoms. Specific examples include trimethylammonium acetate, dimethylpropylammonium acetate, 3-hydroxy-4-trimethylammonium. Obtylate, 4- (1-pyridinio) butyrate, 1-hydroxyethyl-1-imidazolioacetate, trimethylammonium methanesulfonate, dimethylpropylammonium methanesulfonate, 3-trimethylammonio-1-propanesulfonate, 3 -(1-pyridinio) -1-propanesulfonate and the like.

A low molecular weight hydrophilic compound has a small hydrophobic part structure and almost no surface activity, so that dampening water penetrates into the exposed part of the image recording layer (image part) and decreases the hydrophobicity and film strength of the image part. The ink receptivity and printing durability of the image recording layer can be maintained satisfactorily.

The content of the low molecular weight hydrophilic compound is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, and still more preferably 2 to 10% by mass with respect to the total solid content of the image recording layer. Within the above range, good on-press developability and printing durability can be obtained.
A low molecular weight hydrophilic compound may be used individually by 1 type, and 2 or more types may be mixed and used for it.

(Grease sensitizer)
The image recording layer may contain a sensitizing agent such as a phosphonium compound, a nitrogen-containing low molecular weight compound, or an ammonium group-containing polymer in order to improve the inking property. In particular, when an inorganic layered compound is contained in the protective layer, these compounds function as a surface coating agent for the inorganic layered compound, and can suppress a decrease in the inking property during printing by the inorganic layered compound.
As the sensitizer, it is preferable to use a phosphonium compound, a nitrogen-containing low molecular weight compound, and an ammonium group-containing polymer in combination, and use a phosphonium compound, a quaternary ammonium salt, and an ammonium group-containing polymer in combination. Is more preferable.

Examples of the phosphonium compound include phosphonium compounds described in JP-A-2006-297907 and JP-A-2007-50660. Specific examples include tetrabutylphosphonium iodide, butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, 1,4-bis (triphenylphosphonio) butanedi (hexafluorophosphate), 1,7-bis (tri Phenylphosphonio) heptane = sulfate, 1,9-bis (triphenylphosphonio) nonane = naphthalene-2,7-disulfonate, and the like.

Examples of nitrogen-containing low molecular weight compounds include amine salts and quaternary ammonium salts. Also included are imidazolinium salts, benzimidazolinium salts, pyridinium salts, and quinolinium salts. Of these, quaternary ammonium salts and pyridinium salts are preferred. Specific examples include tetramethylammonium = hexafluorophosphate, tetrabutylammonium = hexafluorophosphate, dodecyltrimethylammonium = p-toluenesulfonate, benzyltriethylammonium = hexafluorophosphate, benzyldimethyloctylammonium = hexafluorophosphate. And the compounds described in paragraphs 0021 to 0037 of JP2008-284858A, paragraphs 0030 to 0057 of JP2009-90645A, and the like.

The ammonium group-containing polymer may have an ammonium group in its structure, and a polymer containing 5 to 80 mol% of (meth) acrylate having an ammonium group in the side chain as a copolymerization component is preferable. Specific examples include the polymers described in paragraphs 0089 to 0105 of JP2009-208458A.

The ammonium salt-containing polymer preferably has a reduced specific viscosity (unit: ml / g) determined in accordance with the measurement method described in JP-A-2009-208458, in the range of 5 to 120, and in the range of 10 to 110. Are more preferable, and those in the range of 15 to 100 are particularly preferable. When the reduced specific viscosity is converted into a weight average molecular weight (Mw), it is preferably 10,000 to 150,000, more preferably 17,000 to 140,000, and particularly preferably 20,000 to 130,000.

Specific examples of the ammonium group-containing polymer are shown below.
(1) 2- (Trimethylammonio) ethyl methacrylate = p-toluenesulfonate / 3,6-dioxaheptyl methacrylate copolymer (molar ratio 10/90, Mw 45,000)
(2) 2- (Trimethylammonio) ethyl methacrylate = hexafluorophosphate / 3,6-dioxaheptyl methacrylate copolymer (molar ratio 20/80, Mw 60,000)
(3) 2- (Ethyldimethylammonio) ethyl methacrylate = p-toluenesulfonate / hexyl methacrylate copolymer (molar ratio 30/70, Mw 45,000)
(4) 2- (Trimethylammonio) ethyl methacrylate = hexafluorophosphate / 2-ethylhexyl methacrylate copolymer (molar ratio 20/80, Mw 60,000)
(5) 2- (Trimethylammonio) ethyl methacrylate = methyl sulfate / hexyl methacrylate copolymer (molar ratio 40/60, Mw 7 million)
(6) 2- (butyldimethylammonio) ethyl methacrylate = hexafluorophosphate / 3,6-dioxaheptyl methacrylate copolymer (molar ratio 25/75, Mw 650,000)
(7) 2- (Butyldimethylammonio) ethyl acrylate = hexafluorophosphate / 3,6-dioxaheptyl methacrylate copolymer (molar ratio 20/80, Mw 650,000)
(8) 2- (Butyldimethylammonio) ethyl methacrylate = 13-ethyl-5,8,11-trioxa-1-heptadecanesulfonate / 3,6-dioxaheptyl methacrylate copolymer (molar ratio 20/80 , Mw75,000)
(9) 2- (butyldimethylammonio) ethyl methacrylate = hexafluorophosphate / 3,6-dioxaheptyl methacrylate / 2-hydroxy-3-methacryloyloxypropyl methacrylate copolymer (molar ratio 15/80/5, (Mw 650,000)

The content of the sensitizer is preferably 0.01 to 30.0% by mass, more preferably 0.1 to 15.0% by mass, and more preferably 1 to 10% by mass, based on the total solid content of the image recording layer. Is more preferable.

(Other ingredients)
The image recording layer can contain, as other components, a surfactant, a polymerization inhibitor, a higher fatty acid derivative, a plasticizer, inorganic particles, an inorganic layered compound, and the like. Specifically, reference can be made to the descriptions in paragraphs 0114 to 0159 of JP-A-2008-284817.

[Formation of image recording layer]
The image recording layer in the lithographic printing plate precursor according to the present disclosure is coated by dispersing or dissolving the necessary components in a known solvent as described in paragraphs 0142 to 0143 of JP-A-2008-195018, for example. It can be formed by preparing a liquid, coating the coating liquid on a support by a known method such as bar coater coating, and drying. The coating amount (solid content) of the image recording layer after coating and drying varies depending on the application, but is preferably 0.3 to 3.0 g / m ² . Within the above range, good sensitivity and good film properties of the image recording layer can be obtained.

(Undercoat layer)
The lithographic printing plate precursor according to the present disclosure preferably has an undercoat layer (sometimes referred to as an intermediate layer) between the image recording layer and the support. The undercoat layer enhances the adhesion between the support and the image recording layer in the exposed area and easily peels off the image recording layer from the support in the unexposed area. It contributes to improving. In addition, in the case of infrared laser exposure, the undercoat layer functions as a heat insulating layer, and thus has an effect of preventing the heat generated by the exposure from diffusing to the support and lowering the sensitivity.

Examples of the compound used for the undercoat layer include polymers having an adsorptive group and a hydrophilic group that can be adsorbed on the surface of the support. In order to improve the adhesion to the image recording layer, a polymer having an adsorptive group and a hydrophilic group and further having a crosslinkable group is preferable. The compound used for the undercoat layer may be a low molecular compound or a polymer. The compounds used for the undercoat layer may be used as a mixture of two or more if necessary.

When the compound used for the undercoat layer is a polymer, a copolymer of a monomer having an adsorptive group, a monomer having a hydrophilic group, and a monomer having a crosslinkable group is preferable.
Examples of the adsorptive group that can be adsorbed on the support surface include a phenolic hydroxy group, a carboxy group, —PO ₃ H ₂ , —OPO ₃ H ₂ , —CONHSO ₂ —, —SO ₂ NHSO ₂ —, —COCH ₂ COCH ₃ Is preferred. As the hydrophilic group, a sulfo group or a salt thereof, or a salt of a carboxy group is preferable. As the crosslinkable group, an acryl group, a methacryl group, an acrylamide group, a methacrylamide group, an allyl group, and the like are preferable.
The polymer may have a crosslinkable group introduced by salt formation between a polar substituent of the polymer, a substituent having a counter charge with the polar substituent, and a compound having an ethylenically unsaturated bond, Other monomers, preferably hydrophilic monomers, may be further copolymerized.

Specifically, a silane coupling agent having an ethylenic double bond reactive group capable of addition polymerization described in JP-A No. 10-282679 and an ethylenic compound described in JP-A No. 2-304441. The phosphorus compound which has a heavy bond reactive group is mentioned suitably. Crosslinkable groups (preferably ethylenically unsaturated bond groups) described in JP-A-2005-238816, JP-A-2005-12549, JP-A-2006-239867, and JP-A-2006-215263, a support A low molecular or high molecular compound having a functional group interacting with the surface and a hydrophilic group is also preferably used.
More preferable are polymer polymers having an adsorbing group, a hydrophilic group, and a crosslinkable group that can be adsorbed on the surface of the support described in JP-A Nos. 2005-125749 and 2006-188038.

The content of the ethylenically unsaturated bond group in the polymer used for the undercoat layer is preferably from 0.1 to 10.0 mmol, more preferably from 0.2 to 5.5 mmol, per 1 g of the polymer.
The weight average molecular weight (Mw) of the polymer used for the undercoat layer is preferably 5,000 or more, and more preferably 10,000 to 300,000.

In addition to the above compound for the undercoat layer, the undercoat layer is a chelating agent, a secondary or tertiary amine, a polymerization inhibitor, an amino group, or a functional group having a polymerization inhibitory ability and a support surface in order to prevent contamination with time. Having a group that interacts with (eg, 1,4-diazabicyclo [2.2.2] octane (DABCO), 2,3,5,6-tetrahydroxy-p-quinone, chloranil, sulfophthalic acid, hydroxy Ethylethylenediaminetriacetic acid, dihydroxyethylethylenediaminediacetic acid, hydroxyethyliminodiacetic acid, and the like).

The undercoat layer is applied by a known method. The coating amount (solid content) of the undercoat layer is preferably 0.1 ~ 100mg / ^{m 2,} and more preferably 1 ~ 30mg / ^{m 2.}

[Protective layer]
The lithographic printing plate precursor according to the present disclosure preferably has a protective layer (sometimes referred to as an overcoat layer) on the image recording layer. The protective layer has a function of preventing the formation of scratches in the image recording layer and ablation during high-illuminance laser exposure, in addition to the function of suppressing the image formation inhibition reaction by blocking oxygen.
In addition, the protective layer in the lithographic printing plate precursor according to the present disclosure may include a coloring composition according to the present disclosure, that is, a compound represented by Formula 1.

The protective layer having such characteristics is described in, for example, US Pat. No. 3,458,311 and Japanese Patent Publication No. 55-49729. As the low oxygen permeability polymer used in the protective layer, either a water-soluble polymer or a water-insoluble polymer can be appropriately selected and used, and two or more types can be mixed and used as necessary. it can. Specific examples include polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble cellulose derivatives, poly (meth) acrylonitrile, and the like.
As the modified polyvinyl alcohol, acid-modified polyvinyl alcohol having a carboxy group or a sulfo group is preferably used. Specific examples include modified polyvinyl alcohols described in JP-A-2005-250216 and JP-A-2006-259137.

The protective layer preferably contains an inorganic layered compound in order to enhance oxygen barrier properties. The inorganic layered compound is a particle having a thin flat plate shape, for example, mica group such as natural mica and synthetic mica, talc, teniolite, montmorillonite, saponite, hector represented by the formula: 3MgO · 4SiO · H ₂ O Light, zirconium phosphate, etc. are mentioned.
The inorganic layered compound preferably used is a mica compound. Examples of the mica compound include, for example, the formula: A (B, C) _2-5 D ₄ O ₁₀ (OH, F, O) ₂ [where A is at least one selected from the group consisting of K, Na, and Ca. B and C are at least one element selected from the group consisting of Fe (II), Fe (III), Mn, Al, Mg and V, and D is Si or Al. is there. ] Mica groups such as natural mica and synthetic mica represented by

In the mica group, natural mica includes muscovite, soda mica, phlogopite, biotite, and sericite. As the synthetic mica, non-swelling mica such as fluor-phlogopite mica KMg ₃ (AlSi ₃ O ₁₀ ) F ₂ , potassium tetrasilicon mica KMg _2.5 Si ₄ O ₁₀ ) F ₂ , and Na tetrasilicic mica NaMg2 _{. 5} (Si ₄ O ₁₀ ) F ₂ , Na or Li Teniolite (Na, Li) Mg ₂ Li (Si ₄ O ₁₀ ) F ₂ , Montmorillonite Na or Li Hectorite (Na, Li) _1/8 Mg _{2 /} Examples include swellable mica such as ₅ Li _1/8 (Si ₄ O ₁₀ ) F ₂ . Synthetic smectite is also useful.

Of the mica compounds, fluorine-based swellable mica is particularly useful. That is, the swellable synthetic mica has a laminated structure composed of unit crystal lattice layers with a thickness of about 10 to 15 Å (angstrom, 1 Å = 0.1 nm), and the metal atom substitution in the lattice is significantly larger than other clay minerals. . As a result, the lattice layer is deficient in positive charge, and in order to compensate for this, cations such as Li ⁺ , Na ⁺ , Ca ²⁺ , and Mg ²⁺ are adsorbed between the layers. The cations present between these layers are called exchangeable cations and can be exchanged with various cations. In particular, when the cation between layers is Li ⁺ or Na ⁺ , the bond between the layered crystal lattices is weak because the ionic radius is small, and the layer swells greatly with water. If shear is applied in this state, it will easily cleave and form a stable sol in water. Swelling synthetic mica has a strong tendency and is particularly preferably used.

As the shape of the mica compound, from the viewpoint of diffusion control, the thinner the better, the better the plane size, as long as the smoothness of the coated surface and the transmittance of actinic rays are not impaired. Accordingly, the aspect ratio is preferably 20 or more, more preferably 100 or more, and particularly preferably 200 or more. The aspect ratio is the ratio of the major axis to the thickness of the particle, and can be measured, for example, from a projection drawing of a particle by a micrograph. The larger the aspect ratio, the greater the effect that can be obtained.

The average major axis of the mica compound is preferably 0.3 to 20 μm, more preferably 0.5 to 10 μm, and particularly preferably 1 to 5 μm. The average thickness of the particles is preferably 0.1 μm or less, more preferably 0.05 μm or less, and particularly preferably 0.01 μm or less. Specifically, for example, in the case of swellable synthetic mica, which is a representative compound, preferred embodiments have a thickness of about 1 to 50 nm and a surface size (major axis) of about 1 to 20 μm.

The content of the inorganic stratiform compound is preferably 0 to 60% by mass and more preferably 3 to 50% by mass with respect to the total solid content of the protective layer. Even when a plurality of types of inorganic layered compounds are used in combination, the total amount of the inorganic layered compounds is preferably the above content. Within the above range, the oxygen barrier property is improved and good sensitivity can be obtained. Further, it is possible to prevent a decrease in inking property.

The protective layer may contain known additives such as a plasticizer for imparting flexibility, a surfactant for improving coating properties, and inorganic fine particles for controlling the slipperiness of the surface. Further, the protective layer may contain the sensitizer described in the image recording layer.

The protective layer is applied by a known method. The coating amount of the protective layer (solid content) is preferably 0.01 ~ 10g / ^{m 2,} more preferably 0.02 ~ 3g / ^{m 2,} particularly preferably 0.02 ~ 1g / ^{m 2.}

<Support>
The support of the lithographic printing plate precursor according to the present disclosure can be appropriately selected from known lithographic printing plate precursor supports. As the support, an aluminum plate which has been roughened and anodized by a known method is preferable.
If necessary, the aluminum plate may further be subjected to micropore enlargement treatment or sealing treatment of an anodized film described in JP-A-2001-253181 and JP-A-2001-322365, US Pat. No. 2,714, Surface hydrophilization treatment with alkali metal silicate as described in US Pat. Nos. 066, 3,181,461, 3,280,734 and 3,902,734, US The surface hydrophilization treatment with polyvinyl phosphonic acid or the like as described in the specifications of Patent Nos. 3,276,868, 4,153,461 and 4,689,272 is appropriately selected. You may go.
The support preferably has a center line average roughness of 0.10 to 1.2 μm.

If necessary, the support may be provided on the surface opposite to the image recording layer, such as an organic polymer compound described in JP-A-5-45885, or an alkoxy compound of silicon described in JP-A-6-35174. You may have the backcoat layer containing.

[Preparation method of planographic printing plate]
The method of preparing a lithographic printing plate according to the present disclosure includes a step of exposing the lithographic printing plate precursor according to the present disclosure (exposure step), and printing the lithographic printing plate precursor after imagewise exposure on a printing machine with printing ink and moisture. It is preferable to include a step (on-press development step) of removing an unexposed portion of the image recording layer by at least one selected from the group consisting of water.

<Exposure process>
Image exposure is preferably performed by a method of scanning exposure of digital data with an infrared laser or the like.
The wavelength of the exposure light source is preferably 750 to 1,400 nm. As the light source of 750 to 1,400 nm, a solid laser or semiconductor laser that emits infrared light is suitable. The exposure mechanism may be any of an internal drum system, an external drum system, a flat bed system, and the like.
The exposure step can be performed by a known method using a plate setter or the like. Alternatively, the exposure may be performed on the printing machine after the planographic printing plate precursor is mounted on the printing machine using a printing machine equipped with an exposure device.

<On-machine development process>
In the on-press development process, at least one selected from the group consisting of printing ink and fountain solution on the printing press without performing any development treatment on the lithographic printing plate precursor after image exposure, preferably printing ink When dampening water is supplied and printing (on-press development) is started, the unexposed portion of the lithographic printing plate precursor is removed at an early stage of printing, and the hydrophilic support surface is exposed accordingly, and a non-image is formed. Part is formed. As the printing ink and fountain solution, known lithographic printing ink and fountain solution are used. The lithographic printing plate precursor may be initially supplied with the printing ink or fountain solution, but the printing ink is first used in order to prevent the fountain solution from being contaminated by the removed image recording layer components. Is preferably supplied.
In this way, the lithographic printing plate precursor is subjected to on-press development on an offset printing machine and used as it is for printing a large number of sheets.

The method for producing a lithographic printing plate according to the present disclosure may include other known steps in addition to the above steps. Examples of other processes include a plate inspection process for confirming the position and orientation of the lithographic printing plate precursor before each process, a confirmation process for confirming a printed image after the on-machine development process, and the like.

The lithographic printing plate precursor according to the present disclosure can be prepared as a lithographic printing plate by a development process using a developer by appropriately selecting a polymer or the like which is a constituent component of the image recording layer. The development process using a developer is at least one selected from the group consisting of an embodiment (also referred to as alkali development) using a developer having a high pH of 14 or less containing an alkali agent, and a surfactant and a water-soluble polymer compound. This includes an embodiment (also referred to as simple development) that uses a developer containing a seed compound and having a pH of about 2 to 11. Alkali development and simple development can be carried out by known methods.

[Compound represented by Formula 1 and Coloring Agent]
The compound represented by the above formula 1 is a novel compound, and can be suitably used as a color former, particularly a heat-sensitive color former, an infrared-sensitive color former, or a heat-sensitive and infrared-sensitive color former.
A preferred embodiment of the compound represented by Formula 1 as the novel compound is the same as the preferred embodiment of the compound represented by Formula 1 in the color forming composition according to the present disclosure described above.

Hereinafter, embodiments of the present invention will be described in detail by way of examples, but the present disclosure is not limited thereto. In the polymer compound, unless otherwise specified, the molecular weight is a weight average molecular weight (Mw) in terms of polystyrene converted by a gel permeation chromatography (GPC) method, and the ratio of repeating units is a mole percentage. Further, “part” means “part by mass” unless otherwise specified.

Synthesis examples of the compound represented by Formula 1 are described below. Other compounds represented by Formula 1 can also be synthesized in the same manner by appropriately changing raw materials and reaction intermediates. In the examples, compounds D-1 to D-25 represent the same compounds as the above-mentioned compounds D-1 to D-25, respectively.

[Synthesis Example 1: Synthesis of Compound D-1]
A synthesis scheme of D-1 is shown below.

Compound 1 (20 parts) and compound 2 (32.2 parts) were placed in an eggplant flask and stirred at 100 ° C. for 1 hour. The reaction mixture was concentrated, 1,4-butanediol (10.1 parts) was added, and the mixture was stirred at 220 ° C. for 2 days. The resulting reaction solution was purified by silica gel column chromatography to obtain 20 parts of compound 3.
Compound 3 (0.3 parts) and iodoethane (9.8 parts) were placed in an eggplant flask and stirred at 60 ° C. for 5 hours. The reaction product was reprecipitated with acetone to obtain 0.2 part of Compound 4.
Compound 4 (0.05 parts), compound 5 (0.023 parts), 2-propanol (3.1 parts), acetic anhydride (0.034 parts), triethylamine (0.034 parts) were placed in an eggplant flask. Stir at 25 ° C. for 5 hours. The reaction solution was reprecipitated with a 5% by mass aqueous potassium hexafluorophosphate solution to obtain 0.04 part of Compound 6.
Lithium chloride (42.4 parts) and tetrahydrofuran (647 parts) were placed in a three-necked flask and cooled to −10 ° C. in a nitrogen atmosphere. 159 parts of t-butylmagnesium chloride (2M (mol / L), tetrahydrofuran solution) as a solid content was added dropwise with the internal temperature kept at -5 ° C or lower, and then stirred at -10 ° C for 30 minutes. Separately, 4-pyridinecarboxaldehyde (79.3 parts) and tetrahydrofuran (79.3 parts) were mixed and added dropwise to the above reaction solution with the internal temperature kept at -5 ° C or lower, and then at 0 ° C or lower for 2 hours. Stir. Distilled water (72 parts) was added dropwise so that the internal temperature did not exceed 25 ° C., a 2M aqueous hydrochloric acid solution (531 parts) was added, and the mixture was stirred for 30 minutes. Ethyl acetate (200 parts) was added, the reaction solution was transferred to a separatory funnel, and the aqueous layer was removed. The organic layer was washed with saturated brine (240 parts), and the solvent was evaporated under reduced pressure. Ethyl acetate (35 parts) was added to the obtained solid, heated and stirred at 60 ° C. to dissolve the solid, cooled to 0 ° C., and allowed to stand for 5 hours. The obtained crystals were collected by filtration, washed twice with toluene (86.7 parts), and dried under reduced pressure to obtain 37 parts of 4- (t-butylhydroxymethyl) pyridine.
In an eggplant flask, compound 6 (0.12 parts), 4- (t-butylhydroxymethyl) pyridine (0.03 parts), catechol (0.01 parts), potassium carbonate (0.02 parts), N, N -Dimethylformamide (4.7 parts) was added, stirred at 25 ° C for 24 hours, and then acetone (3.9 parts) was added. Separately, a 5 mass% potassium hexafluorophosphate aqueous solution (22 parts) was placed in a stainless beaker, and the reaction solution was added dropwise while stirring. The obtained precipitate was filtered, washed with distilled water, and dried by blowing to obtain 0.09 part of Compound 7.
Compound 7 (0.03 parts), methyl paratoluenesulfonate (0.03 parts), and acetone (3.9 parts) were placed in an eggplant flask and stirred at 25 ° C. for 24 hours. A 5% by mass aqueous potassium hexafluorophosphate solution was added dropwise to the reaction solution, and the precipitate was collected by filtration. 0.01 parts of was obtained.

[Synthesis Example 2: Synthesis of Compound D-25]
Synthesis of Compound D-1, is precipitated by dropwise addition of distilled water instead of 5 wt% potassium hexafluorophosphate aqueous solution, TsO dicationic in Compound D-1 ^- was obtained salt compound (D-25) .

[Examples 1 to 13 and Comparative Examples 1 to 4]
<Production of support>
In order to remove the rolling oil on the surface of an aluminum plate (material JIS A 1050) having a thickness of 0.3 mm, a degreasing treatment was performed at 50 ° C. for 30 seconds using a 10 mass% sodium aluminate aqueous solution, and then the bristle diameter was set to 0.00. The surface of the aluminum plate was grained using three 3 mm bundle-planted nylon brushes and a pumice-water suspension (specific gravity 1.1 g / cm ³ ) having a median diameter of 25 μm and washed thoroughly with water. Etching was performed by immersing the aluminum plate in a 25 mass% sodium hydroxide aqueous solution at 45 ° C for 9 seconds, washing with water, and further immersed in a 20 mass% nitric acid aqueous solution at 60 ° C for 20 seconds, followed by washing with water. The etching amount of the grained surface was about 3 g / m ² .

Next, an electrochemical roughening treatment was performed continuously using an alternating voltage of 60 Hz. The electrolytic solution was a 1% by mass aqueous nitric acid solution (containing 0.5% by mass aluminum ions), and the liquid temperature was 50 ° C. The AC power source waveform is electrochemical roughening treatment using a trapezoidal rectangular wave alternating current with a time ratio TP of 0.8 msec until the current value reaches a peak from zero, a duty ratio of 1: 1, and a trapezoidal rectangular wave alternating current. Went. Ferrite was used for the auxiliary anode. The current density was 30 A / dm ² at the peak current value, and 5% of the current flowing from the power source was shunted to the auxiliary anode. The amount of electricity in nitric acid electrolysis was 175 C / dm ² when the aluminum plate was the anode. Then, water washing by spraying was performed.

Subsequently, nitric acid electrolysis was performed with an aqueous solution of 0.5% by mass of hydrochloric acid (containing 0.5% by mass of aluminum ions) and an electrolytic solution having a liquid temperature of 50 ° C. under the condition of an electric quantity of 50 C / dm ² when the aluminum plate was the anode. Electrochemical surface roughening treatment was carried out in the same manner as above, followed by washing with water by spraying.
Next, a 2.5 g / m ² direct current anodic oxide film having a current density of 15 A / dm ² is formed on an aluminum plate as an electrolyte using a 15 mass% aqueous sulfuric acid solution (containing 0.5 mass% of aluminum ions), and then washed with water. The support A was prepared by drying. The average pore diameter (surface average pore diameter) in the surface layer of the anodized film was 10 nm.
The pore diameter in the surface layer of the anodized film is measured using an ultra-high resolution SEM (S-900, manufactured by Hitachi, Ltd.), with a deposition process that imparts conductivity at a relatively low acceleration voltage of 12V. Without applying, the surface was observed at a magnification of 150,000 times, and 50 pores were randomly extracted to obtain an average value. The standard deviation error was ± 10% or less.

Thereafter, in order to ensure the hydrophilicity of the non-image area, the support A was subjected to silicate treatment at 60 ° C. for 10 seconds using a 2.5 mass% No. 3 sodium silicate aqueous solution, and then washed with water to obtain the support B. Produced. The adhesion amount of Si was 10 mg / m ² . When the center line average roughness (Ra) of the support B was measured using a needle having a diameter of 2 μm, it was 0.51 μm.

Support C was prepared in the same manner as the support A, except that the electrolyte for forming the direct current anodized film was changed to a 22% by mass phosphoric acid aqueous solution. The average pore diameter (surface average pore diameter) in the surface layer of the anodized film was 25 nm as measured by the same method as described above.

Thereafter, in order to ensure the hydrophilicity of the non-image area, the support C was subjected to a silicate treatment at 60 ° C. for 10 seconds using a 2.5 mass% No. 3 sodium silicate aqueous solution, and then washed with water to obtain the support D. Produced. The adhesion amount of Si was 10 mg / m ² . When the center line average roughness (Ra) of the support D was measured using a needle having a diameter of 2 μm, it was 0.52 μm.

1. Preparation of lithographic printing plate precursor A <Formation of undercoat layer>
On the support, an undercoat layer coating solution (1) having the following composition was applied so that the dry coating amount was 20 mg / m ² to form an undercoat layer.

<Undercoat layer coating solution (1)>
Polymer (P-1) [Structure below]: 0.18 part Hydroxyethyliminodiacetic acid: 0.10 part Water: 61.4 parts

<Synthesis of polymer P-1>
The synthesis method of polymer P-1 is described below.

(Synthesis of Monomer M-1)
To a three-necked flask, 200 parts of Ancamine 1922A (diethylene glycol di (aminopropyl) ether, manufactured by Air Products), 435 parts of distilled water and 410 parts of methanol were added and cooled to 5 ° C. Next, 222.5 parts of benzoic acid and 0.025 part of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (4-OH-TEMPO) were added, and 280 parts of methacrylic anhydride were added. The reaction solution was added dropwise so that the internal temperature was 10 ° C. or lower. The reaction solution was stirred at 5 ° C. for 6 hours and then stirred at 25 ° C. for 12 hours, and then 70 parts of phosphoric acid was added to adjust the pH to 3.3. The reaction solution was transferred to a stainless beaker, 3,320 parts of ethyl acetate, 1,120 parts of methyl-tertbutyl ether (MTBE) and 650 parts of distilled water were added, and the mixture was stirred vigorously and allowed to stand. After discarding the upper layer (organic layer), 1,610 parts of ethyl acetate (1.8 L) was added, stirred vigorously and allowed to stand, and the upper layer was discarded. Furthermore, 1,350 parts of ethyl acetate was added, stirred vigorously and allowed to stand, and the upper layer was discarded. Next, 1,190 parts of MTBE was added, and after vigorous stirring, the mixture was allowed to stand and the upper layer was discarded. To the obtained aqueous solution, 0.063 parts of 4-OH-TEMPO was added to obtain 12,000 parts of an aqueous solution of monomer M-1 (20.1% by mass in terms of solid content).

(Purification of monomer M-2)
After adding 420 parts of light ester P-1M (2-methacryloylethyl acid phosphate, manufactured by Kyoeisha Chemical Co., Ltd.), 1,050 parts of diethylene glycol dibutyl ether and 1,050 parts of distilled water to a separating funnel, and vigorously stirring Left to stand. After discarding the upper layer, 1,050 parts of diethylene glycol dibutyl ether was added, and the mixture was vigorously stirred and allowed to stand. The upper layer was discarded to obtain 13,000 parts of an aqueous solution of monomer M-2 (10.5% by mass in terms of solid content).

(Synthesis of polymer P-1)
In a three-necked flask, 600.6 parts of distilled water, 33.1 parts of an aqueous monomer M-1 solution and 46.1 parts of the following monomer M-3 were added, and the temperature was raised to 55 ° C. in a nitrogen atmosphere. Next, the dropping solution 1 shown below was dropped over 2 hours and stirred for 30 minutes, then 3.9 parts of VA-046B (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the temperature was raised to 80 ° C., Stir for 1.5 hours. After returning the reaction solution to room temperature (25 ° C., the same applies hereinafter), 175 parts of a 30% by mass aqueous sodium hydroxide solution was added to adjust the pH to 8.3. Next, 0.152 part of 4-OH-TEMPO was added, and the temperature was raised to 53 ° C. 66.0 parts of methacrylic anhydride were added and stirred at 53 ° C. for 3 hours. After returning to room temperature, the reaction solution was transferred to a stainless beaker, 1,800 parts of MTBE was added, the mixture was vigorously stirred and allowed to stand, and the upper layer was discarded. Similarly, the washing operation with 1,800 parts of MTBE was further repeated twice, and then 1,700 parts of distilled water and 0.212 parts of 4-OH-TEMPO were added to the obtained aqueous layer to obtain a polymer P-1 as a homogeneous solution. 41,000 parts (11.0% by mass in terms of solid content) were obtained. The weight average molecular weight (Mw) in terms of polyethylene glycol by a gel permeation chromatography (GPC) method was 200,000.

<Drip liquid 1>
Monomer M-1 aqueous solution: 132.4 parts Monomer M-2 aqueous solution: 376.9 parts Monomer M-3 [structure shown below] 184.3 parts Bremer PME-4000 (manufactured by NOF Corporation) ): 15.3 parts · VA-046B (manufactured by Wako Pure Chemical Industries, Ltd.): 3.9 parts · Distilled water: 717.4 parts

BLEMMER PME-4000: Methoxypolyethylene glycol methacrylate (Repeating number of oxyethylene units: 90)
VA-046B: 2,2′-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate

<Formation of image recording layer>
On the undercoat layer, an image recording layer coating solution (1) having the following composition was coated with a bar and oven-dried at 100 ° C. for 60 seconds to form an image recording layer having a dry coating amount of 1.0 g / m ² .
The image recording layer coating solution (1) was prepared by mixing and stirring the following photosensitive solution (1) and microgel solution immediately before coating.

<Photosensitive solution (1)>
-Binder polymer (1) [following structure]: 0.240 parts-Polymerization initiator (1) [following structure]: 0.245 parts-Compound D listed in Table 1 or comparative compound: 0.046 parts-borate Compound TPB [following structure]: 0.010 parts Polymerizable compound Tris (acryloyloxyethyl) isocyanurate (NK ester A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.): 0.192 parts Low molecular weight hydrophilic compound Tris (2-hydroxyethyl) isocyanurate: 0.062 parts, low molecular weight hydrophilic compound (1) [following structure]: 0.050 part, sensitizer Phosphonium compound (1) [following structure]: 0.055 Part
Sensitizing agent benzyl-dimethyl-octylammonium / PF ₆ salt: 0.018 part
-Sensitizing agent Ammonium group-containing polymer (1) [the following structure, reduced specific viscosity 44 ml / g]: 0.035 parts-Fluorosurfactant (1) [following structure]: 0.008 parts-2-butanone : 1.091 parts · 1-methoxy-2-propanol: 8.609 parts

<Microgel solution>
-Microgel (1): 2.640 parts-Distilled water: 2.425 parts

Binder polymer (1), polymerization initiator (1), TPB, low molecular weight hydrophilic compound (1), phosphonium compound (1), ammonium group-containing polymer (1) and fluorine-based interface used in the photosensitive solution (1) The structure of the active agent (1) is shown below. In addition, Me represents a methyl group, and the number on the lower right of the parenthesis of each structural unit of the following polymer represents a molar ratio.

The structure of comparative compound d-1 is shown below.

The method for preparing the microgel (1) used in the microgel solution is shown below.

<Preparation of polyvalent isocyanate compound (1)>
In a suspension of 17.78 parts of isophorone diisocyanate and 7.35 parts of the following polyphenol compound (1) in ethyl acetate (25.31 parts), bismuth tris (2-ethylhexanoate) (Neostan U-600, 0.043 parts of Nitto Kasei Co., Ltd.) was added and stirred. When the exotherm had subsided, the reaction temperature was set to 50 ° C., and the mixture was stirred for 3 hours to obtain an ethyl acetate solution (50 mass%) of the polyvalent isocyanate compound (1).

<Preparation of microgel (1)>
The following oil phase component and aqueous phase component were mixed and emulsified for 10 minutes at 12,000 rpm using a homogenizer. After the resulting emulsion was stirred at 45 ° C. for 4 hours, 10 mass of 1,8-diazabicyclo [5.4.0] undec-7-ene-octylate (U-CAT SA102, manufactured by San Apro Co., Ltd.) % Aqueous solution (5.20 parts) was added, the mixture was stirred at room temperature for 30 minutes, and allowed to stand at 45 ° C. for 24 hours. Distilled water was used to adjust the solid content concentration to 20% by mass, and an aqueous dispersion of microgel (1) was obtained. When an average particle diameter was measured by a light scattering method, it was 0.28 μm.

(Oil phase component)
(Component 1) Ethyl acetate: 12.0 parts (Component 2) Trimethylolpropane (6 molar equivalents) and xylene diisocyanate (18 molar equivalents) were added to this, and methyl-terminated polyoxyethylene (1 molar equivalent, oxy Adduct with addition of ethylene unit repeat number: 90) (50 mass% ethyl acetate solution, manufactured by Mitsui Chemicals): 3.76 parts (component 3) polyvalent isocyanate compound (1) (50 mass% acetic acid) (As ethyl solution): 15.0 parts (component 4) 65% by weight ethyl acetate solution of dipentaerythritol pentaacrylate (SR-399, manufactured by Sartomer): 11.54 parts (component 5) sulfonate type surfactant (Pionine A-41-C, Takemoto Yushi Co., Ltd.) 10% ethyl acetate solution: 4.42 parts

(Water phase component)
Distilled water: 46.87 parts

<Formation of protective layer>
A protective layer coating solution having the following composition is bar-coated on the image recording layer and oven-dried at 120 ° C. for 60 seconds to form a protective layer having a dry coating amount of 0.15 g / m ^2. Was made. Table 1 summarizes the support used in the preparation of each lithographic printing plate precursor, the compound A or the comparative compound in the image recording layer coating solution (1).

<Protective layer coating solution>
-Inorganic layered compound dispersion (1) [below]: 1.5 parts-Polyvinyl alcohol (CKS50, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., sulfonic acid modification, saponification degree 99 mol% or more, polymerization degree 300) 6% by mass Aqueous solution: 0.55 parts, polyvinyl alcohol (PVA-405, manufactured by Kuraray Co., Ltd., saponification degree: 81.5 mol%, polymerization degree: 500) 6% by weight Aqueous solution: 0.03 parts, surfactant (polyoxyethylene lauryl) Ether, Emalex 710, manufactured by Nippon Emulsion Co., Ltd.) 1% by weight aqueous solution: 0.86 parts, ion-exchanged water: 6.0 parts

The method for preparing the inorganic layered compound dispersion (1) used in the protective layer coating solution is shown below.

<Preparation of inorganic layered compound dispersion (1)>
6.4 parts of synthetic mica (Somasif ME-100, manufactured by Coop Chemical Co., Ltd.) was added to 193.6 parts of ion-exchanged water, and dispersed using an homogenizer until the average particle size (laser scattering method) became 3 μm. . The aspect ratio of the obtained dispersed particles was 100 or more.

2. Preparation of lithographic printing plate precursor B In preparation of the lithographic printing plate precursor A, the following lithographic printing plate precursor A is used in place of the image recording layer coating liquid (1) except that the following image recording layer coating liquid (2) is used. A lithographic printing plate precursor B was prepared in the same manner as the preparation. The image recording layer coating solution (2) was prepared by mixing and stirring the following photosensitive solution (2) and microgel solution immediately before coating. Table 1 summarizes the support used in the preparation of each lithographic printing plate precursor, the compound D in the image recording layer coating solution (2) or the comparative compound.

<Photosensitive solution (2)>
-Binder polymer (1) [above]: 0.240 parts-Chain transfer agent (S-1) [following structure]: 0.060 parts-Compound D listed in Table 1 or comparative compound: 0.038 parts-Borate Compound TPB [above]: 0.010 parts Polymerizable compound Tris (acryloyloxyethyl) isocyanurate (NK ester A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.): 0.192 parts Low molecular weight hydrophilic compound Tris (2-Hydroxyethyl) isocyanurate: 0.062 parts. Low molecular weight hydrophilic compound (1) [above]: 0.050 part. Sensitizer Phosphonium compound (1) [above]: 0.055 parts. Aburakazai benzyl - dimethyl - octylammonium, PF ₆ salt: 0.018 parts Oil-sensitizing agent ammonium group-containing polymer (1) [the]: 0.035 parts fluorine-containing surfactant (1) [the]: 0.008 parts 2-Butanone 1.091 parts 1-Methoxy-2-propanol: 8.609 parts

<Microgel solution>
Microgel (1) [above]: 2.640 parts Distilled water: 2.425 parts

The structure of the chain transfer agent (S-1) used in the photosensitive solution (2) is shown below.

3. Preparation of lithographic printing plate precursor C In preparation of the lithographic printing plate precursor A, an image recording layer coating liquid (3) having the following composition was bar-coated instead of the image recording layer coating liquid (1), and 60 ° C. at 60 ° C. The plate was subjected to oven drying for 2 seconds to form an image recording layer having a dry coating amount of 0.6 g / m ² to prepare a lithographic printing plate precursor C. The lithographic printing plate precursor C is a lithographic printing plate precursor having no protective layer. Table 1 summarizes the support used in the preparation of each lithographic printing plate precursor, the compound D or the comparative compound in the image recording layer coating solution (3).

<Image recording layer coating solution (3)>
Compound D or comparative compound described in Table 1: 0.046 part Polymerization initiator (1) [above]: 0.245 part Borate compound TPB [above]: 0.010 part Polymer particle aqueous dispersion ( 1) (22% by mass) [below]: 10.0 parts, polymerizable compound SR-399 (manufactured by Sartomer): 1.50 parts, mercapto-3-triazole: 0.2 parts, Byk 336 (Byk Chemie) 0.4 parts) Klucel M (Hercules): 4.8 parts ELVACITE 4026 (Ineos Acrylics): 2.5 parts n-propanol: 55.0 parts 2-butanone: 17. 0 copies

The compounds described by trade names used in the image recording layer coating solution (3) are as follows.
SR-399: Dipentaerythritol pentaacrylate Byk 336: Modified dimethylpolysiloxane copolymer (25% by mass xylene / methoxypropyl acetate solution)
・ Klucel M: Hydroxypropyl cellulose (2% by mass aqueous solution)
ELVACITE 4026: Hyperbranched polymethyl methacrylate (10% by mass 2-butanone solution)

The preparation method of the polymer particle aqueous dispersion (1) used in the image recording layer coating liquid (3) is shown below.

<Preparation of polymer particle aqueous dispersion (1)>
A four-necked flask is equipped with a stirrer, thermometer, dropping funnel, nitrogen inlet tube, reflux condenser, and introduced with nitrogen gas, deoxygenated, and polyethylene glycol methyl ether methacrylate (PEGMA, average repeating unit of ethylene glycol) Number: 50) 10 parts, 200 parts of distilled water and 200 parts of n-propanol were added and heated until the internal temperature reached 70 ° C. Next, a premixed mixture of 10 parts of styrene (St), 80 parts of acrylonitrile (AN) and 0.8 part of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour. After the completion of the dropwise addition, the reaction was continued as it was for 5 hours, and then 0.4 part of 2,2′-azobisisobutyronitrile was added and the internal temperature was raised to 80 ° C. Subsequently, 0.5 part of 2,2′-azobisisobutyronitrile was added over 6 hours. Polymerization progressed 98% or more at the stage of reaction for a total of 20 hours, and an aqueous polymer particle dispersion (1) having a mass ratio of PEGMA / St / AN = 10/10/80 was prepared. The particle size distribution of the polymer particles had a maximum value at a particle size of 150 nm.

The particle size distribution is obtained by taking an electron micrograph of polymer particles, measuring the total particle size of 5,000 particles on the photo, and using a logarithmic scale between the maximum value of the obtained particle size measurement value and zero. The frequency of appearance of each particle size was plotted by dividing it into 50 and determined. For non-spherical particles, the particle size of spherical particles having the same particle area as that on the photograph was used as the particle size.

4). Preparation of lithographic printing plate precursor D In preparation of the lithographic printing plate precursor A, an image recording layer coating aqueous solution (4) having the following composition after coating was applied by bar instead of the image recording layer coating liquid (1). Then, it was oven dried at 50 ° C. for 60 seconds to form an image recording layer having a dry coating amount of 0.93 g / m ² to prepare a lithographic printing plate precursor D. The lithographic printing plate precursor D is a lithographic printing plate precursor having no protective layer. The support used in the preparation of each lithographic printing plate precursor, the compound D or the comparative compound in the image recording layer coating solution (4) are collectively shown in Table 1.

<Image recording layer coating solution (4)>
Compound D shown in Table 1 or comparative compound: 0.038 g / m ²
Borate compound TPB [above]: 0.01 g / m ²
-Polymer particle aqueous dispersion (2): 0.693 g / m ²
-Glascol E15 (manufactured by Allied Colloids Manufacturing): 0.09 g / m ²
・ ERKOL WX48 / 20 (manufactured by ERKOL): 0.09 g / m ²
・ Zonyl FSO100 (manufactured by DuPont): 0.0075 g / m ²

The compound described in the trade name and the polymer particle aqueous dispersion (2) used in the image recording layer coating aqueous solution (4) are as follows.
-Glascol E15: Polyacrylic acid-ERKOL WX48 / 20: Polyvinyl alcohol / polyvinyl acetate copolymer-Zonyl FSO100: Surfactant-Polymer particle water dispersion (2): Styrene stabilized with an anionic wetting agent / Acrylonitrile copolymer (molar ratio 50/50, average particle size 61 nm, solid content about 20% by mass)

5). Evaluation of lithographic printing plate precursor Each of the above lithographic printing plate precursors was evaluated for color developability, on-press developability, and printing durability as follows. The evaluation results are shown in Table 1.

(1) Color developability The lithographic printing plate precursor was output by a Trend setter 3244VX manufactured by Creo with a water-cooled 40 W infrared semiconductor laser. The output was 11.7 W, the outer drum rotation speed was 250 rpm, the resolution was 2,400 dpi (dot per inch, 1 inch = 25.4 mm ). The exposure was performed in an environment of 25 ° C. and 50% RH.
The color development of the lithographic printing plate precursor was measured immediately after exposure and after storage for 2 hours in a dark place (25 ° C.) after exposure. The measurement was performed by the SCE (regular reflection light removal) method using a spectrocolorimeter CM2600d manufactured by Konica Minolta Co., Ltd. and operation software CM-S100W. The color developability was evaluated by the difference ΔL between the L ^* value of the exposed area and the L ^* value of the unexposed area using the L ^* value (brightness) of the L ^* a ^* b ^* color system. The larger the value of ΔL, the better the color developability.

(2) On-machine developability The lithographic printing plate precursor was subjected to an external drum rotation speed of 1,000 rpm, a laser output of 70%, and a resolution of 2,400 dpi using a Luxel PLANETTER T-6000III equipped with an infrared semiconductor laser. Exposed. The exposure image included a solid image and a 50% halftone dot chart of a 20 μm dot FM screen.
The exposed lithographic printing plate precursor was mounted on the plate cylinder of a printing machine LITHRONE 26 manufactured by Komori Corporation without developing. Using liter-2 (made by Fujifilm Co., Ltd.) / Tap water = 2/98 (volume ratio) dampening water and Values-G (N) ink (made by DIC Graphics Co., Ltd.) Dampening water and ink are supplied by the standard automatic printing start method, and 100 sheets are printed on Tokishi Art Paper (basis weight 76.5kg) (Mitsubishi Paper Co., Ltd.) at a printing speed of 10,000 sheets per hour. went.
The on-machine development of the unexposed part of the image recording layer on the printing machine was completed, and the number of printing sheets required until the ink was not transferred to the non-image part was measured and evaluated as on-machine developability. The smaller the number, the better the on-press developability.

(3) Printing durability After the on-press developability was evaluated, printing was further continued. As the number of printed sheets increased, the image recording layer gradually worn out, so that the ink density on the printed material decreased. The number of printed sheets was measured until the value obtained by measuring the dot area ratio of the 50% halftone dot of the FM screen in the printed matter with a Gretag densitometer was 5% lower than the measured value of the 100th printed sheet. Evaluation was made based on the relative printing durability when the number of printed sheets was 50,000. The larger the value, the better the printing durability.
Relative printing durability = (number of lithographic printing plates produced from the target lithographic printing plate precursor) / 50,000 × 100

From the results shown in Table 1, the lithographic printing plate precursor having the image recording layer containing the compound according to the present disclosure is superior in color developability as compared with the lithographic printing plate precursor of the comparative example containing the comparative compound. It is clear. Furthermore, it can be seen that the lithographic printing plate precursor having the image recording layer containing the compound according to the present disclosure has good on-press developability and printing durability.

The disclosure of Japanese Patent Application No. 2016-166950 filed on August 29, 2016 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards described in this specification are the same as if each document, patent application, and technical standard were specifically and individually stated to be incorporated by reference. Which is incorporated herein by reference.

Claims

A coloring composition comprising a compound represented by the following formula 1.

In Formula 1, A represents a ring structure containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, A + represents a ring structure containing N + , O + or S + , Each X independently represents a carbon atom or a nitrogen atom, and at least one of X is a nitrogen atom, and when X is a nitrogen atom, R 1 , R 2 or R 3 bonded to the nitrogen atom is present R 1 , R 2 and R 3 are each independently a hydrogen atom, halogen atom, hydrocarbon group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, hydroxy group, alkoxycarbonyl group, acyloxy group, an amino group, a urethane group, a urea group, an amide group, a nitrile group or an imino group, the 2 or more of R 1 ~ R 3 may form a ring structure, one or more of R 1 R 3 and A or A + and may form a ring structure, n is an integer of 1 ~ 6, Z represents a counter ion for neutralizing a charge.
The coloring composition according to claim 1, wherein the compound represented by Formula 1 is a compound represented by Formula 2 below.

In Formula 2, A represents a ring structure containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, Ar represents a ring structure containing N + , O + or S + , and L Represents —CH 2 —, —CHR a —, —C (R a ) 2 —, —NR a —, —O— or —S—, each R a independently represents a hydrocarbon group, R 1 , R 2 and R 3 are each independently a hydrogen atom, halogen atom, hydrocarbon group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, hydroxy group, alkoxycarbonyl group, acyloxy group, amino group, urethane Represents a group, a urea group, an amide group, a nitrile group or an imino group, and two or more R 1 to R 3 may combine to form a ring structure and one or more R 1 to R 3 and A, L or Combines with Ar to form a ring structure N represents an integer of 1 to 6, and Z represents a counter ion for neutralizing the electric charge.
The coloring composition according to claim 1 or 2, wherein the compound represented by Formula 1 is a compound represented by Formula 3 below.

In Formula 3, A represents a ring structure containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, one of the two A 1 represents N + , and the other represents a carbon atom. L represents —CH 2 —, —CHR a —, —C (R a ) 2 —, —NR a —, —O— or —S—, and each R a independently represents a hydrocarbon group. , R 1 , R 2 and R 3 are each independently a hydrogen atom, halogen atom, hydrocarbon group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, hydroxy group, alkoxycarbonyl group, acyloxy group, amino group Represents a group, a urethane group, a urea group, an amide group, a nitrile group or an imino group, and two or more R 1 to R 3 may combine to form a ring structure, and one or more of R 1 to R 3 and A , L or one or more R 4 to R 7 may combine with each other to form a ring structure, and R 4 to R 7 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, Represents a hydroxy group, an alkoxycarbonyl group, an acyloxy group, an amino group, a urethane group, a urea group, an amide group, a nitrile group, an imino group, a carboxylic acid group, a sulfonic acid group or a phosphoric acid group, and two or more R 4 to R 7 May combine to form a ring structure, n represents an integer of 1 to 6, and Z represents a counter ion for neutralizing the charge.
The coloring composition according to any one of claims 1 to 3, wherein the compound represented by the formula 1 is a compound represented by the following formula 4.

In Formula 4, A represents a ring structure containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, one of the two A 1 represents N + , and the other represents a carbon atom. L represents —CH 2 —, —CHR a —, —C (R a ) 2 —, —NR a —, —O— or —S—, and each R a independently represents a hydrocarbon group. R 4 to R 14 are each independently a hydrogen atom, halogen atom, hydrocarbon group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, hydroxy group, alkoxycarbonyl group, acyloxy group, amino group, urethane Group, urea group, amide group, nitrile group, imino group, carboxylic acid group, sulfonic acid group or phosphoric acid group, and two or more R 4 to R 14 may be bonded to form a ring structure. or more of R 4 ~ 14 and the A or L may form a ring structure, Z is a counter ion for neutralizing a charge.
The color forming composition according to claim 4, wherein R 10 and R 12 are bonded to form a ring structure.
The coloring composition according to any one of claims 1 to 3 , wherein at least one of R 1 to R 3 is a group represented by the following formula 5.

In Formula 5, R 15 represents a hydrocarbon group, and R 16 each independently represents a group represented by the following Formula 6, a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group Represents an acyl group, a hydroxy group, an alkoxycarbonyl group, an acyloxy group, an amino group, a urethane group, a urea group, an amide group, a nitrile group, or an imino group, and at least one of R 16 is represented by the following formula 6. Group.

In Formula 6, * represents a connecting position with the pyridinium ring in Formula 5, ** represents a connecting position with the polymethine chain in Formula 1 to Formula 4, and L 1 is a single bond or a carbon number of 1 to 10 Represents a divalent hydrocarbon group, and the methylene group in the divalent hydrocarbon group is partly an ether bond, thioether bond, carbonyl bond, ester bond, amino bond, urethane bond, urea bond, amide bond, and imino. It may be replaced with at least one structure selected from the group consisting of bonds.
The color forming composition according to claim 4, wherein R 11 is a group represented by the following formula 5.

In Formula 5, R 15 represents a hydrocarbon group, and R 16 each independently represents a group represented by the following Formula 6, a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group Represents an acyl group, a hydroxy group, an alkoxycarbonyl group, an acyloxy group, an amino group, a urethane group, a urea group, an amide group, a nitrile group, or an imino group, and at least one of R 16 is represented by the following formula 6. Group.

In Formula 6, * represents a connecting position with the pyridinium ring in Formula 5, ** represents a connecting position with the polymethine chain in Formula 1 to Formula 4, and L 1 is a single bond or a carbon number of 1 to 10 Represents a divalent hydrocarbon group, and the methylene group in the divalent hydrocarbon group is partly an ether bond, thioether bond, carbonyl bond, ester bond, amino bond, urethane bond, urea bond, amide bond, and imino. It may be replaced with at least one structure selected from the group consisting of bonds.
The coloring composition according to any one of claims 1 to 7, further comprising a polymer.
The coloring composition according to any one of claims 1 to 8, further comprising a polymerization initiator and a polymerizable compound.
The coloring composition according to claim 8 or 9, which is a curable composition cured by infrared irradiation.
A lithographic printing plate precursor having at least one layer containing the color forming composition according to any one of claims 1 to 10 on a support.
Irradiating the planographic printing plate precursor according to claim 11 with infrared rays;
Supplying the at least one selected from the group consisting of printing ink and fountain solution on a printing press to develop the lithographic printing plate irradiated with infrared rays on the press;
A method for producing a lithographic printing plate comprising
A compound represented by the following formula 1.

In Formula 1, A represents a ring structure containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, A + represents a ring structure containing N + , O + or S + , Each X independently represents a carbon atom or a nitrogen atom, and at least one of X is a nitrogen atom, and when X is a nitrogen atom, R 1 , R 2 or R 3 bonded to the nitrogen atom is present R 1 , R 2 and R 3 are each independently a hydrogen atom, halogen atom, hydrocarbon group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, hydroxy group, alkoxycarbonyl group, acyloxy group, an amino group, a urethane group, a urea group, an amide group, a nitrile group or an imino group, the 2 or more of R 1 ~ R 3 may form a ring structure, one or more of R 1 R 3 and A or A + and may form a ring structure, n is an integer of 1 ~ 6, Z represents a counter ion for neutralizing a charge.