JP2018058980A - Salt-forming compound, image forming material using the same and use of the material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a salt-forming compound having high invisibility, that is, small in absorption in a visible range (400 nm to 750 nm), having excellent near-infrared ray absorptivity and high light fastness, and less causing aggregation, and an image forming material comprising the salt-forming compound having the above characteristics.SOLUTION: The salt-forming compound comprises a specific squalirium compound [A] represented by general formula and a resin [B] having a cationic group in a side chain; and the image forming material comprises the above salt-forming compound.SELECTED DRAWING: None

Description

  The present invention relates to a specific salt-forming compound and an image forming material containing the salt-forming compound.

  In recent years, there has been a technology for recording invisible information that is not visible under normal visual conditions on documents, stock certificates, bonds, checks, gift certificates, lottery tickets, commuter passes, and optically reading the information. Attention has been paid. Such a technique is very useful in security management and the like, and is effective in improving the added value of documents and the like and strengthening measures for preventing forgery of securities and the like.

  As a method for recording invisible information, there is a method of using an image forming material using a dye having absorption in the near infrared region of 750 nm to 1000 nm that cannot be visually recognized by human eyes. Such invisibility information can be detected by a light receiving element (CCD, CMOS, etc.) made of silicon, etc. even if it cannot be visually recognized by human eyes.

  As typical dyes having absorption in the near infrared region of 750 nm or more and 1000 nm or less, phthalocyanine dyes, cyanine dyes, diimonium dyes, squarylium dyes, croconium dyes and the like are known.

  Examples of phthalocyanine dyes include phthalocyanine compounds having an amino group (for example, see Patent Document 1), phthalocyanine compounds having an aryloxy group (for example, see Patent Document 2), fluorine-containing phthalocyanine compounds (for example, see Patent Document 3), and the like. Are known. However, since there is an absorption band peculiar to phthalocyanine in the visible light region (400 nm to 750 nm), the transparency in the visible region is insufficient. Also, heat resistance and light resistance are not always satisfactory.

  On the other hand, cyanine dyes, diimonium dyes, squarylium dyes, croconium dyes, and the like are materials having excellent near-infrared absorption ability and relatively good transparency in the visible region, and various types are known (for example, And Patent Documents 4 to 8). Furthermore, these dyes also have high solubility and resin compatibility. However, the stability as a pigment is extremely low, and the heat resistance and light resistance are not satisfied.

  Among squarylium dyes, dyes having a perimidine skeleton are known, and are particularly excellent in light resistance (see, for example, Patent Document 9). However, since the structure tends to aggregate, there are problems in dispersibility, viscosity, storage stability with time, etc., and performance for practical use cannot be satisfied.

JP 2004-18561 A JP 2013-241563 A JP 05-078364 A JP 2008-088426 A JP 2009-108267 A Japanese Patent Laid-Open No. 05-247437 Japanese Patent Laid-Open No. 10-036695 JP 2001-294785 A JP 2009-209297 A

  The problem to be solved by the present invention is a salt-forming compound having high invisibility, that is, low absorption in the visible region (400 nm to 750 nm), excellent near infrared absorption ability, high light resistance, and hardly agglomerating, The present invention also provides an image forming material containing a salt-forming compound having the above-mentioned characteristics.

As a result of intensive studies to solve the above problems, the present inventors have reached the present invention.
That is, the present invention relates to a salt-forming compound of squarylium [A] represented by the following general formula and a resin [B] having a cationic group in the side chain.

General formula (1)

In General Formula (1), X _{1 to} X ₁₀ may each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. A good aryl group, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an amino group, a substituted amino group, —SO ₂ NR ₁ R ₂ , —COOR ₃ , —CONR ₄ R ₅ , a nitro group, a cyano group, or a halogen atom may be represented, and adjacent groups may form a ring. R _{1 to} R ₅ each independently represents a hydrogen atom or an alkyl group which may have a substituent. n represents an integer of 1 to 4. Z ⁺ represents a hydrogen ion or an inorganic or organic cation.

  Moreover, it is related with the said salt-forming compound whose resin [B] which has a cationic group in a side chain is a vinyl resin containing the structural unit represented by following General formula (2).

General formula (2)

In general formula (2), R ₆ represents a hydrogen atom or an alkyl group which may have a substituent. R _{7 to} R ₉ each independently represent a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent; Two of _{7 to} R ₉ may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ₁₀ — or —COO—R ₁₁ —, and R ₁₀ and R ₁₁ represent an alkylene group. Y ⁻ represents an inorganic or organic anion.

  The present invention also relates to an image forming material containing the salt-forming compound.

  Furthermore, the present invention relates to the image forming material which is an electrophotographic toner, an ink for an ink jet printer, or an ink for letterpress, offset, flexo, gravure or silk printing.

  According to the present invention, it is possible to provide a salt-forming compound and an image forming material which are excellent in spectral characteristics and light resistance and hardly aggregate, that is, are easily dispersed and excellent in storage stability.

<Squarylium [A]>
The squarylium [A] represented by the general formula (1) of the present invention will be described in detail.

General formula (1)

In General Formula (1), X _{1 to} X ₁₀ may each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. A good aryl group, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an amino group, a substituted amino group, —SO ₂ NR ₁ R ₂ , —COOR ₃ , —CONR ₄ R ₅ , a nitro group, a cyano group, or a halogen atom may be represented, and adjacent groups may form a ring. R _{1 to} R ₅ each independently represents a hydrogen atom or an alkyl group which may have a substituent. n represents an integer of 1 to 4. Z ⁺ represents a hydrogen ion or an inorganic or organic cation.

Examples of the “alkyl group which may have a substituent” in X _{1 to} X ₁₀ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, a tert-amyl group, a 2-ethylhexyl group, Stearyl group, chloromethyl group, trichloromethyl group, trifluoromethyl group, 2-methoxyethyl group, 2-chloroethyl group, 2-nitroethyl group, cyclopentyl group, cyclohexyl group, dimethylcyclohexyl group, etc. Among them, a methyl group, an ethyl group, and an n-propyl group are preferable from the viewpoint of imparting durability and difficulty in synthesis, and a methyl group is particularly preferable.

As the “alkenyl group which may have a substituent” in X _{1 to} X ₁₀ , a vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1 -Pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, etc. Among these, a vinyl group and an allyl group are preferable from the viewpoint of imparting durability and difficulty in synthesis.

In X _{1 to} X ₁₀ , as the “aryl group optionally having substituent (s)”, phenyl group, naphthyl group, 4-methylphenyl group, 3,5-dimethylphenyl group, pentafluorophenyl group, 4-bromophenyl Group, 2-methoxyphenyl group, 4-diethylaminophenyl group, 3-nitrophenyl group, 4-cyanophenyl group and the like, among which phenyl group and 4-methylphenyl group are used for durability and synthesis. It is preferable from the viewpoint of difficulty.

Examples of the “aralkyl group which may have a substituent” in X _{1 to} X ₁₀ include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group and the like. Among these, a benzyl group is a durable group. It is preferable from the viewpoint of imparting and synthesis difficulty.

In X _{1 to} X ₁₀ , the “alkoxy group having a substituent” includes a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an n-octyloxy group, and 2-ethylhexyloxy. Group, trifluoromethoxy group, cyclohexyloxy group, stearyloxy group and the like. Among these, a methoxy group, an ethoxy group, and a trifluoromethoxy group are preferable from the viewpoint of imparting durability and difficulty in synthesis.

As the “aryloxy group which may have a substituent” in X _{1 to} X ₁₀ , phenoxy group, naphthyloxy group, 4-methylphenyloxy group, 3,5-chlorophenyloxy group, 4-chloro-2- Examples thereof include methylphenyloxy group, 4-tert-butylphenyloxy group, 4-methoxyphenyloxy group, 4-diethylaminophenyloxy group, 4-nitrophenyloxy group, and among these, phenoxy group, naphthyloxy group Is preferable from the viewpoint of imparting durability and difficulty in synthesis.

As the “substituted amino group” in X _{1 to} X ₁₀ , the methylamino group, ethylamino group, isopropylamino group, n-butylamino group, cyclohexylamino group, stearylamino group, dimethylamino group, diethylamino group, dibutylamino group N, N-di (2-hydroxyethyl) amino group, phenylamino group, naphthylamino group, 4-tert-butylphenylamino group, diphenylamino group, N-phenyl-N-ethylamino group, and the like. Among these, a dimethylamino group and a diethylamino group are preferable from the viewpoint of imparting durability and difficulty in synthesis.

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

In X _{1 to} X ₁₀ , adjacent groups may form a ring, and examples thereof include the following structures, but are not limited thereto.

In R _{1 to} R ₅ , the “alkyl group optionally having substituent (s)” has the same meaning as X _{1 to} X ₁₀ .

X _{1 to} X ₁₀ preferably contain an unsubstituted alkyl group, more preferably at least one of X ₃ , X ₄ , X ₇ and X ₈ is an unsubstituted alkyl group, and X ₃ and X ₇ Is particularly preferably an unsubstituted alkyl group. The unsubstituted alkyl group is preferably a methyl group.

As the “inorganic or organic cation” of Z ⁺ , known ones can be used without limitation, and specific examples include metal atoms, ammonium compounds, pyridinium compounds, imidazolium compounds, phosphonium compounds, sulfonium compounds and the like. it can. As Z ⁺ , a hydrogen atom, a metal atom, or an ammonium compound is preferable from the viewpoint of synthesis difficulty.

  N in the general formula (1) is preferably 1 or 2 from the viewpoint of light resistance, and n = 2 is particularly preferable from the viewpoint of difficulty in synthesis.

<Method for producing squarylium [A]>
Although the following method can be considered as a manufacturing method of squarylium [A], squarylium [A] used for this invention is not limited by this following manufacturing method. The 1,8-diaminonaphthalene represented by the following formula (3) and the cyclohexanone represented by the following general formula (4) were condensed with heating in a solvent together with a catalyst, and then the following formula (5) was obtained. The indicated 3,4-dihydroxy-3-cyclobutene-1,2-dione is added and further heated to reflux for condensation to obtain a squarylium [A] precursor represented by the general formula (6). Furthermore, squarylium [A] (Z ⁺ = hydrogen ion) represented by the general formula (7) can be obtained by sulfonating the squarylium [A] precursor in an appropriate concentration of sulfuric acid. The general formula (7) squarylium indicated [A] (Z + ⁼ hydrogen ion) to be to any ionic compound and salt exchange reaction, to convert Z ⁺ to any inorganic or organic cation it can.

<Resin having cationic group in side chain [B]>
The resin [B] having a cationic group in the side chain represented by the general formula (2) of the present invention will be described in detail.

General formula (2)

In general formula (2), R ₆ represents a hydrogen atom or an alkyl group which may have a substituent. R _{7 to} R ₉ each independently represent a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent; Two of _{7 to} R ₉ may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ₁₀ — or —COO—R ₁₁ —, and R ₁₀ and R ₁₁ represent an alkylene group. Y ⁻ represents an inorganic or organic anion.

Examples of the “alkyl group which may have a substituent” in R ₆ include a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-hexyl group, and a cyclohexyl group. Can be mentioned. As this alkyl group, a C1-C12 alkyl group is preferable, a C1-C8 alkyl group is more preferable, and a C1-C4 alkyl group is especially preferable.

When the alkyl group represented by R ₆ has a substituent, examples of the substituent include a hydroxyl group,
An alkoxyl group etc. are mentioned.

Among the above, R ₆ is most preferably a hydrogen atom or a methyl group.

As the “alkyl group optionally having substituent (s)” in R _{7 to} R ₉ , a linear alkyl group (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, etc.), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl and 1, 1,3,3-tetramethylbutyl, etc.), cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.) and bridged cyclic alkyl groups (norbornyl, adamantyl, pinanyl, etc.). As this alkyl group, a C1-C18 alkyl group is preferable, More preferably, it is a C1-C8 alkyl group.

In R _{7 to} R ₉ , the “optionally substituted alkenyl group” may be a linear or branched alkenyl group (vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3 -Butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, etc.), cycloalkenyl groups (2-cyclohexenyl and 3- Cyclohexenyl etc.). As this alkenyl group, a C2-C18 alkenyl group is preferable, More preferably, it is a C2-C8 alkenyl group.

In R _{7 to} R ₉ , the “aryl group which may have a substituent” includes a monocyclic aryl group (such as phenyl), a condensed polycyclic aryl group (naphthyl, anthracenyl, phenanthrenyl, anthraquinolyl, fluorenyl and naphthoquinolyl). Etc.) and aromatic heterocyclic hydrocarbon groups (thienyl (group derived from thiophene)), furyl (group derived from furan), pyranyl (group derived from pyran), pyridyl (group derived from pyridine) ), 9-oxoxanthenyl (a group derived from xanthone), 9-oxothioxanthenyl (a group derived from thioxanthone), and the like.

When the alkyl group, alkenyl group and aryl group represented by R _{7 to} R ₉ have a substituent, examples of the substituent include a halogen atom, a hydroxyl group, an alkoxyl group, an aryloxy group, an alkenyl group, an acyl group, Examples include a substituent selected from an alkoxycarbonyl group, a carboxyl group, a phenyl group, and the like. Among these substituents, a halogen atom, a hydroxyl group, an alkoxyl group, and a phenyl group are particularly preferable.

As R < ₇ > -R < ₉ >, the alkyl group which may have a substituent from a stability viewpoint is preferable, and an unsubstituted alkyl group is still more preferable.

Two of R _{7 to} R ₉ may be bonded to each other to form a ring.

In the general formula (2), components of the Q connecting the acrylic sites and ammonium base is an alkylene group, an arylene _{group, -CONH-R 10 -, -} COO-R 11 - _{represents, R 10} and _{R 11} represents an alkylene group Among them, -CONH-R ₁₀ -and -COO-R ₁₁ -are preferable because of polymerizability and availability. Examples of the “alkylene group” in R ₁₀ and R ₁₁ include a methylene group, an ethylene group, a propylene group, and a butylene group, and among these, an ethylene group is particularly preferable.

The component of Y ⁻ in the general formula (2) constituting the counter anion of the resin [B] may be an inorganic or organic anion. As the counter anion, known ones can be used without limitation. Specifically, hydroxide ions; halogen ions such as chloride ions, bromide ions, and iodide ions; carboxylate ions such as formate ions and acetate ions; Carbonate ions, bicarbonate ions, nitrate ions, sulfate ions, sulfite ions, chromate ions, dichromate ions, phosphate ions, cyanide ions, permanganate ions, and even hexacyanoferrate (III) ions And complex ions. From the viewpoint of synthesis suitability and stability, halogen ions and carboxylate ions are preferable, and halogen ions are most preferable. When the counter anion is an organic acid ion such as a carboxylate ion, the organic acid ion may be covalently bonded in the resin to form an inner salt.

  In order to obtain a vinyl resin containing a structural unit represented by the general formula (2) which is a preferred embodiment of the present invention, only a method of copolymerizing an ethylenically unsaturated monomer having an ammonium base as a monomer component is used. Alternatively, after obtaining a vinyl resin having an amino group obtained by copolymerizing an ethylenically unsaturated monomer having an amino group as a monomer component, it may be obtained by a method in which an onium chlorinating agent is reacted and ammonium salified. good.

  Below, the specific example of the ethylenically unsaturated monomer which can be used in order to obtain the vinyl resin containing the structural unit represented by General formula (2) which is a preferable aspect of this invention is shown. In addition, in this specification, when showing either or both of "acryl, methacryl", it may describe as "(meth) acryl". Similarly, when one or both of “acryloyl and methacryloyl” are indicated, it may be described as “(meth) acryloyl”.

  Examples of the ethylenically unsaturated monomer having a quaternary ammonium base include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meta ) Alkyl (meth) acrylate quaternary ammonium salts such as acryloyloxyethylmethylmorpholino ammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloylaminoethyltriethylammonium chloride, (meth) acryloylaminoethyldimethylbenzyl Alkyl (meth) acryloylamide quaternary ammonium salts such as ammonium chloride, dimethyl Luzia Lil ammonium methyl sulfate, trimethyl vinyl phenyl ammonium chloride.

  Examples of the ethylenically unsaturated monomer having an amino group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, diisopropylaminoethyl (meth) acrylate, and dibutylamino. Ethyl (meth) acrylate, diisobutylaminoethyl (meth) acrylate, di-t-butylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) acrylamide, diisopropyl Aminopropyl (meth) acrylamide, dibutylaminopropyl (meth) acrylamide, diisobutylaminopropyl (meth) acrylamide, di-t-butyl Examples include (meth) acrylic acid esters having a dialkylamino group such as minopropyl (meth) acrylamide or (meth) acrylamide, and styrenes having a dialkylamino group such as dimethylaminostyrene and dimethylaminomethylstyrene, diallylmethylamine, diallylamine And amino group-containing aromatic vinyl monomers such as N-vinylpyrrolidine, N-vinylpyrrolidone and N-vinylcarbazole.

  Examples of the onium chloride agent include alkyl sulfates such as dimethyl sulfate, diethyl sulfate, or dipropyl sulfate, sulfonate esters such as methyl p-toluenesulfonate, or methyl benzenesulfonate, methyl chloride, ethyl chloride, propyl chloride, or Examples thereof include alkyl chlorides such as octyl chloride, alkyl bromides such as methyl bromide, ethyl bromide, propyl bromide, and octyl chlorobromide, benzyl chloride, and benzyl bromide.

  The reaction between the ethylenically unsaturated monomer having an amino group and the onium chlorinating agent is usually performed by dropping an equimolar amount or less of the onium chlorinating agent into the amino group-containing ethylenically unsaturated monomer solution. Can be done. The temperature during the ammonium chlorination reaction is about 90 ° C. or less, and particularly when the vinyl monomer is ammonium chlorinated, it is preferably about 30 ° C. or less, and the reaction time is about 1 to 4 hours.

Alternatively, an alkoxycarbonylalkyl halide can also be used as the onium chlorinating agent. The alkoxycarbonylalkyl halide is represented by the following general formula (8).
_D-R 12 -COOR ₁₃ formula (8)
(In General Formula (8), D is a halogen such as chlorine or bromine, preferably bromine, and R ₁₂ is an alkylene group having 1 to 6 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. And R ₁₃ is a lower alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.)

Reaction of the ethylenically unsaturated monomer and alkoxycarbonylalkyl halide with an amino group, after equimolar following alkoxycarbonylalkyl halide was reacted in the same manner as in the above onium chloride agent to an amino group, a -COOR ₁₃ It is obtained by hydrolysis and conversion to carboxylate ions (—COO—). Thereby, the ethylenically unsaturated monomer which has a carboxybetaine structure shown by General formula (8) Formula, and has an ammonium base can be obtained.

  Other examples of the ethylenically unsaturated monomer that can be used other than the structural unit represented by the general formula (2) include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, and maleic acid. Diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, vinyl alcohol esters, styrenes, (meth) acrylonitrile and the like are preferable.

  Specific examples of such vinyl monomers include the following compounds.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2- Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth) acrylic acid Diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, ( Β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo (meth) acrylate Pentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate And (meth) acrylic acid tribromophenyloxyethyl.

  Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.

  Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like. Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

  Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

  Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

Examples of (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn -Butyl acryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N , N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide and the like.

  Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether. Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

  In addition, the ethylenically unsaturated monomer that can be used other than the structural unit represented by the general formula (2) may further include a copolymer unit derived from a monomer having an acid group.

  As monomers having an acid group, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, anhydrous Unsaturated dicarboxylic acids such as itaconic acid, citraconic acid, citraconic anhydride and mesaconic acid or their anhydrides; trivalent or higher unsaturated polycarboxylic acids or their anhydrides; succinic acid mono (2-acryloyloxyethyl) ), Succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl) monovalent polyvalent carboxylic acid mono [ (Meth) acryloyloxyalkyl] esters; ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolacto Include mono (meth) acrylates such as both terminal carboxy polymers such monomethacrylate.

  Examples of a method for obtaining a vinyl resin containing the structural unit represented by the general formula (2) suitable for the present invention include anionic polymerization, living anionic polymerization, cationic polymerization, living cationic polymerization, free radical polymerization, and living radical polymerization. Any known method can be used. Of these, free radical polymerization or living radical polymerization is preferred.

  In the case of the free radical polymerization method, it is preferable to use a polymerization initiator. As the polymerization initiator, for example, an azo compound and an organic peroxide can be used. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), or 2,2′-azobis [2- (2-imidazolin-2-yl ) Propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples thereof include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more. The reaction temperature is preferably 40 to 150 ° C., more preferably 50 to 110 ° C., and the reaction time is preferably 3 to 30 hours, more preferably 5 to 20 hours.

  In the living radical polymerization method, side reactions that occur in general radical polymerization are suppressed, and further, since the growth of polymerization occurs uniformly, it is possible to easily synthesize block polymers and resins with uniform molecular weight.

Among them, the atom transfer radical polymerization method using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is applicable to a wide range of monomers, and has a polymerization temperature applicable to existing equipment. It is preferable in that it can be adopted. The atom transfer radical polymerization method can be performed by the method described in the following references 10 to 17 and the like.
(Reference 10) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329
(Reference 11) Matyjaszewski et al., Chem. Rev. 2001, 101, 2921
(Reference 12) Matyjaszewski et al. Am. Chem. Soc. 1995, 117, 5614
(Reference 13) Macromolecules 1995, 28, 7901, Science, 1996, 272, 866
(Reference 14) Pamphlet of International Publication No. 96/030421 (Reference 15) Pamphlet of International Publication No. 97/018247 (Reference 16) JP-A-9-208616 (Reference 17) JP-A-8-411117 It is preferable to use an organic solvent for the polymerization. The organic solvent is not particularly limited, but for example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether Acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, or the like is used. Two or more kinds of these polymerization solvents may be mixed and used.

  The amount of the ammonium base present in the vinyl-based resin containing the structural unit represented by the general formula (2) suitable for the present invention is not particularly limited, but the ammonium salt value of the resin is 10 to 200 mgKOH / It is preferable that it is g, and it is more preferable that it is 20-130 mgKOH / g.

  In order for the ammonium salt value of the resin to satisfy the above range, the preferred content of the structural unit having a quaternary ammonium base is 4 to 74% by weight in a total of 100% by weight of the structural units constituting the resin, A more preferred range is 8 to 48% by weight.

  Although the molecular weight of the vinyl resin containing the structural unit represented by the general formula (2) used in the present invention is not particularly limited, the converted weight average molecular weight measured by gel permeation chromatography (GPC). Is preferably 1,000 to 500,000, and more preferably 3,000 to 15,000.

  In the resin [B] having a cationic group in the side chain, the total content of the structural unit represented by the general formula (2) is not particularly limited, but the resin [B] having a cationic group in the side chain. From the viewpoint of solvent solubility and coloring power of the salt-forming compound, the total content of the structural unit represented by the general formula (2) is 5% by weight, assuming that the total structural unit contained in 100% by mass. % Or more, and more preferably 10 to 50% by mass.

<Method for producing salt-forming compound>
The salt-forming compound of the present invention is prepared by stirring or vibrating an aqueous solution in which squarylium [A] and a resin [B] having a cationic group are dissolved in the side chain, or in an aqueous solution and side chain of squarylium [A]. It can be easily obtained by mixing an aqueous solution of the resin [B] having a functional group with stirring or vibration. In the aqueous solution, the anionic group of squarylium [A] and the cationic group of resin [B] are ionized and these are ionically bonded, and the ion-bonded portion becomes water-insoluble and precipitates. On the contrary, a salt composed of a counter cation of squarylium [A] and a counter anion of resin [B] is water-soluble and can be removed by washing or the like. The squarylium [A] and the resin [B] having a cationic group in the side chain may be used alone or in a plurality of types having different structures.

  In order to dissolve squarylium [A] and the resin [B] having a cationic group in the side chain as an aqueous solution used at the time of salt formation, a mixed solution of water and a water-soluble organic solvent may be used. Examples of the water-soluble organic solvent include methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol, 2- (methoxymethoxy) ethanol, 2- Butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol, propylene glycolic monomethyl ether acetate, dipropylene glycol, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, acetone, diacetone alcohol, aniline, pyridine, ethyl acetate, isopropyl acetate, methyl ethyl ketone , N, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran (THF), dioxane, 2-pyrrolidone, 2-methylpyrrolidone, N-methyl-2-pyrrolidone, 1,2-hexanediol, 2,4,6-hexanetriol , Tetrafurfuryl alcohol, 4-methoxy-4-methylpentanone and the like. These water-soluble organic solvents are preferably used in an amount of 5 to 50% by weight, and most preferably 5 to 20% by weight, based on the total weight of the aqueous solution (100% by weight).

  The ratio of the squarylium [A] and the resin [B] having a cationic group in the side chain is such that the molar ratio of the total cation unit of the resin [B] to the total anionic group of the squarylium [A] is 10/1. If it is in the range of 1/10, the salt-forming compound of the present invention can be suitably adjusted, preferably in the range of 4/1 to 1/4, and particularly preferably in the range of 2/1 to 1/2.

When n in the squarylium [A] represented by the general formula (1) is 2 or more and a plurality of sulfo groups are present, all the sulfo groups may form a salt with the resin [B]. The sulfo group may form a salt with the resin [B], and the remaining counter cation of the sulfo group may remain in the Z ⁺ state. By changing the molar ratio in the production, the ratio of the resin [B] and Z ⁺ can be controlled.

<Image forming material>
The image forming material of the present invention will be described in detail.
In the image forming material of the present invention, the salt-forming compound of the present invention can be used in either a dispersed state or a dissolved state. The salt-forming compound in the image-forming material of the present invention can be adjusted as necessary, but it is preferably contained in the image-forming material in an amount of 0.05 to 50% by mass, and 0.1 to 30% by mass. It is more preferable. In the image forming material of the present invention, the salt-forming compounds can be used alone or in combination of two or more at any ratio as required.

  The application of the image forming material of the present invention is not particularly limited, and examples thereof include applications such as toner for electrophotography, ink for inkjet printer, or ink for letterpress printing, offset printing, flexographic printing, gravure printing, or silk printing. It is done.

  When the image forming material of the present invention is an electrophotographic toner, the image forming material may be used alone as a one-component developer or as a two-component developer combined with a carrier. As the carrier, a known carrier can be used. For example, the resin coat carrier which has a resin coating layer on a core material can be mentioned. Conductive powder or the like may be dispersed in the resin coating layer.

  In addition, when the image forming material of the present invention is an electrophotographic toner, the image forming material can contain a binder resin. Binder resins include styrenes such as styrene and chlorostyrene, monoolefins such as ethylene, propylene, butylene and isoprene, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate and vinyl butyrate, methyl acrylate, acrylic Α-methylene aliphatic monocarboxylic acid esters such as ethyl acetate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate, vinyl methyl ether And vinyl ethers such as vinyl ethyl ether and vinyl butyl ether, and homopolymers or copolymers of vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and vinyl isopropenyl ketone. Typical binder resins include polystyrene, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer. Examples thereof include coalescence, polyethylene, and polypropylene. Furthermore, polyester, polyurethane, epoxy resin, silicone resin, polyamide, modified rosin, paraffin wax and the like may be used as the binder resin.

  In addition, when the image forming material of the present invention is an electrophotographic toner, the image forming material can further contain a charge control agent, an offset preventive agent and the like as required. As the charge control agent, there are a positive charge agent and a negative charge agent. For the positive charge, there are quaternary ammonium compounds. For negative charging, alkylsalicylic acid metal complexes, resin-type charge control agents containing polar groups, and the like can be used. As the offset preventing agent, low molecular weight polyethylene, low molecular weight polypropylene or the like is used.

  In addition, when the image forming material of the present invention is an electrophotographic toner, the inorganic powder particles or the organic particles are removed for improving fluidity, powder storage stability, triboelectric charge control, transfer performance, and cleaning performance. It may be added to the toner surface as an additive. Examples of the inorganic powder particles include known ones such as silica, alumina, titania, calcium carbonate, magnesium carbonate, calcium phosphate, cerium oxide and the like. Further, a known surface treatment may be applied to the inorganic powder particles according to the purpose. Examples of the organic particles include an emulsion polymer having a constituent component such as vinylidene fluoride, methyl methacrylate, styrene-methyl methacrylate, or a soap-free polymer.

When the image forming material of the present invention is an ink for an ink jet printer, the image forming material may take the form of an aqueous ink containing water. When the image forming material is a water-based ink, it may further contain a water-soluble organic solvent in order to prevent the ink from drying and to improve the permeability.
Examples of water include ion exchange water, ultrafiltration water, and pure water.

Examples of the water-soluble organic solvent include polyhydric alcohols such as ethylene glycol, diethylene glycol, polyethylene glycol, and glycerin, esters such as N-alkylpyrrolidones, ethyl acetate, and amyl acetate, methanol, ethanol, propanol, Examples include lower alcohols such as butanol, and glycol ethers such as methanol, butanol, and phenol-ethylene oxide or propylene oxide adducts. The organic solvent used may be one type or two or more types.
The organic solvent is selected in consideration of hygroscopicity, moisture retention, solubility of squarylium dye, permeability, ink viscosity, freezing point, and the like. As content rate of the organic solvent in the ink for inkjet printers, the range of 1 weight% or more and 60 weight% or less is mentioned, for example.

  Further, when the image forming material of the present invention is an ink for an ink jet printer, the image forming material according to the present embodiment is conventionally known as an ink component in order to satisfy various conditions required for the ink jet printer system. May contain additives. Examples of such additives include pH adjusters, specific resistance adjusters, antioxidants, antiseptics, fungicides, and sequestering agents. Examples of the pH adjuster include alcohol amines, ammonium salts, metal hydroxides and the like. Examples of the specific resistance adjusting agent include organic salts and inorganic salts. Examples of the metal sequestering agent include chelating agents.

  Further, when the image forming material of the present invention is an ink for an ink jet printer, polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose, styrene-acrylic acid resin is used to such an extent that blocking of the jet nozzle part and change in the ink discharge direction do not occur. Water-soluble resins such as styrene-maleic acid resin can also be contained.

  When the image forming material of the present invention is an ink for letterpress printing, offset printing, flexographic printing, gravure printing, or silk printing, the image forming material can take the form of an oil-based ink containing a polymer or an organic solvent. Polymers generally include natural resins such as proteins, rubbers, celluloses, shellac, copal, starch, rosin; vinyl resins, acrylic resins, styrene resins, polyolefin resins, novolac phenol resins, etc. Thermoplastic resin; thermosetting resin such as resol type phenol resin urea resin, melamine resin, polyurethane resin, epoxy, unsaturated polyester, and the like. Moreover, as an organic solvent, the organic solvent illustrated in description of the said ink for inkjet printers is mentioned.

  Further, when the image forming material of the present invention is an ink for letterpress printing, offset printing, flexographic printing, gravure printing or silk printing, the image forming material is a plasticizer for improving the flexibility and strength of the printed film, It may further contain additives such as a solvent for adjusting viscosity and improving drying property, a drying agent, a viscosity adjusting agent, a dispersing agent, and various reactants.

  The image forming material of the present invention may further contain a stabilizer. The stabilizer receives energy from the excited organic near-infrared absorbing dye, and preferably has an absorption band on the longer wavelength side than the absorption band of the organic near-infrared absorbing dye. The stabilizer is preferably not easily decomposed by singlet oxygen and highly compatible with the salt-forming compound of the present invention. Examples of such stabilizers include organometallic complex compounds, and Ni complex compounds are particularly preferable.

<Method for producing image forming material>
Hereinafter, an example of the method for producing the image forming material of the present invention will be described.
For example, when used in a dispersed state, a method of mixing a salt-forming compound and a dispersant and subjecting the mixture to a pigmentation treatment can be mentioned. Examples of the dispersing agent include low molecular weight dispersing agents such as Triton X and sodium alkylbenzene sulfonate aqueous solutions, and high molecular weight dispersing agents such as Solsperse. You may adjust a density | concentration by adding water to the said liquid mixture as needed. Moreover, as an apparatus used for the pigmentation treatment, a bead mill processing apparatus is suitable.

<Evaluation method of image forming material>
The salt-forming compound of the present invention has sufficiently low absorbance in the visible light wavelength region of 400 nm or more and 750 nm or less, and sufficiently high absorbance in the near infrared light wavelength region of 750 nm or more and 1000 nm or less. The salt-forming compound of the present invention is excellent in light resistance. Therefore, the image forming material of the present invention containing the salt-forming compound of the present invention can achieve both invisibility of information and readability of invisible information, and furthermore, long-term stability in a recording medium on which invisible information is recorded. It is possible to achieve sex.

The salt-forming compound of the present invention preferably satisfies the conditions represented by the following formulas (I) and (II). By satisfying the conditions represented by the following formulas (I) and (II), it is possible to achieve both invisibility of information and readability of invisible information regardless of the color of the image forming material. Long-term reliability in a recording medium on which invisible information is recorded can be realized.
0 ≦ ΔE ≦ 15 (I)
(100-R) ≧ 75 (II)
[In the formula (II), ΔE represents the following formula (III):

Formula (III)

(In Formula (III), L ₁ , a ₁ , and b ₁ represent the L value, a value, and b value of the surface of the recording medium before image formation, respectively, and L ₂ , a ₂ , and b ₂ represent the image formation, respectively. (The L value, a value, and b value in the image area when a fixed image having an adhesion amount of 4 g / m ² is formed on the surface of the recording medium using the material are shown.
In the formula (II), R (unit:%) represents the infrared reflectance at a wavelength of 850 nm in the image portion. ]

L ₁ , a ₁ , b ₁ , L ₂ , a ₂ , and b ₂ can be obtained using a reflection spectral densitometer. L ₁ , a ₁ , b ₁ , L ₂ , a ₂ , and b ₂ in the present invention are measured by using x-rite 939 manufactured by X-Rite Co., Ltd. as a reflection spectral densitometer.

  The invisible information recorded using the image forming material of the present invention is, for example, a semiconductor laser or a light emitting diode that emits light at any wavelength of 750 nm to 1000 nm as a light source for optical reading, and has a high spectral intensity in near infrared light. By using a general-purpose light receiving element having sensitivity, it is possible to read out very easily and with high sensitivity. An example of the light receiving element is a light receiving element (CCD or the like) made of silicon.

  Further, the salt-forming compound of the present invention is not limited to the image forming material, but for example, a near-infrared absorbing film or a near-infrared absorbing plate that blocks heat rays for energy saving, and agricultural use for selective use of sunlight. Near-infrared absorbing film, recording medium using near-infrared absorption heat, near-infrared cut filter for electronic equipment, near-infrared filter for photography, protective glasses, sunglasses, heat ray blocking film, laser resin welding, etc. is there.

  EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In Examples and Comparative Examples, “part” and “%” mean “part by mass” and “% by mass”, respectively.

(Identification method of squarylium [A])
Elemental analysis and MALDI TOF-MS spectrum were used for identification of squarylium [A] used in the present invention. Elemental analysis was performed using a Perkin Elmer 2400 CHN Elegant Analyzer. The MALDI TOF-MS spectrum uses the MALDI mass spectrometer “autoflex III” manufactured by Bruker Daltonics, Inc. to identify the obtained compound with the coincidence between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. It was.

(Weight average molecular weight (Mw) of resin [B] having a cationic group in the side chain)
The weight average molecular weight (Mw) of the resin [B] having a cationic group in the side chain used in the present invention is a GPC (manufactured by Tosoh Corp., HLC-) equipped with an RI detector using a TSKgel column (Tosoh Corp.). 8120 GPC), and a polystyrene-reduced weight average molecular weight (Mw) measured using THF as a developing solvent.

(Quaternary ammonium salt value of resin [B] having a cationic group in the side chain)
The quaternary ammonium salt value of the resin [B] having a cationic group in the side chain used in the present invention was determined by titrating with a 0.1N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator. Converted to the equivalent of potassium oxide. The quaternary ammonium salt value of the following resin [B] indicates the quaternary ammonium salt value of the solid content.

<Method for producing squarylium [A]>
(Manufacture of squarylium [A-1])
To 400 parts of toluene, 40.0 parts of 1,8-diaminonaphthalene, 25.1 parts of cyclohexanone, and 0.087 part of p-toluenesulfonic acid monohydrate are mixed, heated and stirred in an atmosphere of nitrogen gas, 3 Reflux for hours. Water generated during the reaction was removed from the system by azeotropic distillation. After completion of the reaction, the dark brown solid obtained by distilling toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The obtained brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added, and an atmosphere of nitrogen gas was added. The mixture was heated and stirred in, and refluxed for 8 hours. Water generated during the reaction was removed from the system by azeotropic distillation. After completion of the reaction, the solvent was distilled off, and 200 parts of hexane was added while stirring the obtained reaction mixture. The resulting black-brown precipitate was filtered off, washed successively with hexane, ethanol and acetone and dried under reduced pressure. The obtained black-brown solid was dissolved in 1000 parts of 90% sulfuric acid and stirred at 30 degrees for 5 hours. After completion of the reaction, the reaction solution was added dropwise to 10000 parts of water which was being stirred, and stirred at 20 degrees for 1 hour. The resulting precipitate was filtered off, washed with 0.5% hydrochloric acid and dried under reduced pressure to obtain 70.9 parts of squarylium [A-1] (yield: 92%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-1].

Squarylium [A-1]

(Manufacture of squarylium [A-2])
The same operation as the production of squarylium [A-1] was carried out except that 1000 parts of 98% sulfuric acid was used instead of 1000 parts of 90% sulfuric acid used in the production of squarylium [A-1]. 2] 79.8 parts (yield: 92%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-2].

Squarylium [A-2]

(Manufacture of squarylium [A-3])
The same operation as the production of squarylium [A-1] was performed except that 1000 parts of 101% sulfuric acid was used instead of 1000 parts of 90% sulfuric acid used in the production of squarylium [A-1]. 3] 87.8 parts (yield: 91%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-3].

Squarylium [A-3]

(Manufacture of squarylium [A-4])
The same operation as the production of squarylium [A-1] was performed except that 1000 parts of 104.5% sulfuric acid was used instead of 1000 parts of 90% sulfuric acid used in the production of squarylium [A-1]. A-4] 95.6 parts (yield: 90%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-4].

Squarylium [A-4]

(Manufacture of squarylium [A-5])
The same operation as in the production of squarylium [A-2] was performed except that 32.2 parts of 2,6-dimethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. , 89.8 parts (yield: 96%) of squarylium [A-5] were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-5].

Squarylium [A-5]

(Production of squarylium [A-6])
The same operation as in the production of squarylium [A-1] was performed except that 32.2 parts of 3,5-dimethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-1]. , 82.2 parts (yield: 98%) of squarylium [A-6] was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-6].

Squarylium [A-6]

(Manufacture of squarylium [A-7])
The same operation as in the production of squarylium [A-2] was performed except that 32.2 parts of 3,5-dimethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. , 90.8 parts of squarylium [A-7] (yield: 97%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-7].

Squarylium [A-7]

(Manufacture of squarylium [A-8])
The same operation as in the production of squarylium [A-3] was carried out except that 32.2 parts of 3,5-dimethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-3]. , 98.1 parts (yield: 95%) of squarylium [A-8] were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-8].

Squarylium [A-8]

(Manufacture of squarylium [A-9])
The same operation as in the production of squarylium [A-4] was carried out except that 32.2 parts of 3,5-dimethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-4]. , 106.2 parts (yield: 94%) of squarylium [A-9] were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-9].

Squarylium [A-9]

(Manufacture of squarylium [A-10])
The same operation as the production of squarylium [A-2] was carried out except that 28.6 parts of 4-methylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. [A-10] 85.6 parts (yield: 95%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-10].

Squarylium [A-10]

(Manufacture of squarylium [A-11])
The same operation as the production of squarylium [A-1] except that 35.8 parts of 3,3,5-trimethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-1]. To obtain 81.1 parts of squarylium [A-11] (yield: 93%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-11].

Squarylium [A-11]

(Manufacture of squarylium [A-12])
The same operation as the production of squarylium [A-2] except that 35.8 parts of 3,3,5-trimethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. To obtain 90.2 parts (yield: 93%) of squarylium [A-12]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-12].

Squarylium [A-12]

(Manufacture of squarylium [A-13])
The same operation as the production of squarylium [A-3] except that 35.8 parts of 3,3,5-trimethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-3]. To obtain 98.1 parts of squarylium [A-13] (yield: 92%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-13].

Squarylium [A-13]

(Manufacture of squarylium [A-14])
The same operation as the production of squarylium [A-4] except that 35.8 parts of 3,3,5-trimethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-4]. To obtain 104.8 parts of squarylium [A-14] (yield: 90%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-14].

Squarylium [A-14]

(Manufacture of squarylium [A-15])
The same operation as in the production of squarylium [A-1] was carried out except that 39.4 parts of 3,5-diethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-1]. , 86.1 parts (yield: 95%) of squarylium [A-15] were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-15].

Squarylium [A-15]

(Manufacture of squarylium [A-16])
The same operation as in the production of squarylium [A-2] was conducted except that 39.4 parts of 3,5-diethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. , 94.3 parts of squarylium [A-16] (yield: 94%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-16].

Squarylium [A-16]

(Manufacture of squarylium [A-17])
The same operation as in the production of squarylium [A-3] was carried out except that 39.4 parts of 3,5-diethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-3]. , 103.5 parts of squarylium [A-17] (yield: 94%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-17].

Squarylium [A-17]

(Manufacture of squarylium [A-18])
The same operation as in the production of squarylium [A-4] was carried out except that 39.4 parts of 3,5-diethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-4]. , 110.2 parts (yield: 92%) of squarylium [A-18] were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-18].

Squarylium [A-18]

(Manufacture of squarylium [A-19])
The same operation as the production of squarylium [A-2] except that 39.4 parts of 5-isopropyl-2-methylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. And 93.3 parts of squarylium [A-19] (yield: 93%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-19].

Squarylium [A-19]

(Manufacture of squarylium [A-20])
The same operation as in the production of squarylium [A-2] was conducted except that 46.0 parts of 2-cyclohexylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. [A-20] 97.1 parts (yield: 91%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-20].

Squarylium [A-20]

(Manufacture of squarylium [A-21])
Except for using 28.1 parts of 2-norbornanone instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2], the same operation as in the production of squarylium [A-2] was performed. A-21] was obtained 82.5 parts (yield: 92%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-21].

Squarylium [A-21]

(Production of squarylium [A-22])
The production of squarylium [A-2] was performed except that 42.5 parts of spiro [5.5] undecan-1-one was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. The same operation was performed to obtain 97.1 parts of squarylium [A-22] (yield: 94%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-22].

Squarylium [A-22]

(Manufacture of squarylium [A-23])
Instead of 25.1 parts of cyclohexanone used in the preparation of squarylium [A-2], 41.9 parts of 3-methyl-3,4,4a, 5,8,8a-hexahydronaphthalen-1 (2H) -one Was used in the same manner as in the production of squarylium [A-2] to obtain 93.5 parts of squarylium [A-23] (yield: 94%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-23].

Squarylium [A-23]

(Manufacture of squarylium [A-24])
The same operation as the production of squarylium [A-2] except that 41.0 parts of 3- (2-chloroethyl) cyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. To obtain 95.8 parts of squarylium [A-24] (yield: 94%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-24].

Squarylium [A-24]

(Manufacture of squarylium [A-25])
The production of squarylium [A-2] was performed except that 59.8 parts of 3,5-di (trifluoromethyl) cyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. The same operation was performed to obtain 111.4 parts of squarylium [A-25] (yield: 93%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-25].

Squarylium [A-25]

(Manufacture of squarylium [A-26])
The same operation as the production of squarylium [A-2] was carried out except that 44.5 parts of 2-phenylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. [A-26] 96.8 parts (yield: 92%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-26].

Squarylium [A-26]

(Manufacture of squarylium [A-27])
The same operation as in the production of squarylium [A-2] was carried out except that 48.1 parts of 4-p-tolylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. , 102.1 parts of squarylium [A-27] (yield: 94%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-27].

Squarylium [A-27]

(Manufacture of squarylium [A-28])
The same operation as the production of squarylium [A-2] was carried out except that 48.1 parts of 4-benzylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. [A-28] 103.2 parts (yield: 95%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-28].

Squarylium [A-28]

(Manufacture of squarylium [A-29])
The same operation as the production of squarylium [A-2] was carried out except that 36.3 parts of 4-ethoxycyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. [A-29] 88.7 parts (yield: 91%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-29].

Squarylium [A-29]

(Manufacture of squarylium [A-30])
The production of squarylium [A-2] was performed except that 68.0 parts of 2,6-di (trifluoromethoxy) cyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. The same operation was performed to obtain 118.6 parts (yield: 93%) of squarylium [A-30]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-30].

Squarylium [A-30]

(Manufacture of squarylium [A-31])
The same operation as the production of squarylium [A-2] was carried out except that 48.6 parts of 4-phenoxycyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. [A-31] 100.4 parts (yield: 92%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-31].

Squarylium [A-31]

(Manufacture of squarylium [A-32])
Production of squarylium [A-2] except that 52.4 parts of N-ethyl-3-oxocyclohexane-1-sulfoamide was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. The same operation was carried out to obtain 106.0 parts of squarylium [A-32] (yield: 94%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-32].

Squarylium [A-32]

(Manufacture of squarylium [A-33])
The same operation as in the production of squarylium [A-2] was performed except that 36.3 parts of 4-oxocyclohexanecarboxylic acid was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. , 87.7 parts (yield: 90%) of squarylium [A-33] were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-33].

Squarylium [A-33]

(Manufacture of squarylium [A-34])
The same operation as in the production of squarylium [A-2] was conducted except that 43.5 parts of ethyl 2-oxocyclohexanecarboxylate was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. And 96.9 parts of squarylium [A-34] (yield: 93%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-34].

Squarylium [A-34]

(Manufacture of squarylium [A-35])
Similar to the production of squarylium [A-2] except that 46.8 parts of 4-oxo-N-propylcyclohexanecarboxamide were used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. Then, squarylium [A-35] 102.0 (yield: 95%) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-35].

Squarylium [A-35]

(Manufacture of squarylium [A-36])
The same operation as the production of squarylium [A-2] was carried out except that 28.9 parts of 4-aminocyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. [A-36] 85.0 parts (yield: 94%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-36].

Squarylium [A-36]

(Manufacture of squarylium [A-37])
The same operation as in the production of squarylium [A-2] was conducted except that 36.1 parts of 4- (dimethylamino) cyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. And 92.3 parts (yield: 95%) of squarylium [A-37] were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-37].

Squarylium [A-37]

(Manufacture of squarylium [A-38])
The same operation as in the production of squarylium [A-2] was carried out except that 31.4 parts of 4-oxocyclohexanecarbonitrile was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. , 85.4 parts of squarylium [A-38] (yield: 92%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-38].

Squarylium [A-38]

(Manufacture of squarylium [A-39])
The same operation as the production of squarylium [A-2] was carried out except that 36.6 parts of 4-nitrocyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. [A-39] 89.9 parts (yield: 92%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-39].

Squarylium [A-39]

(Manufacture of squarylium [A-40])
The same operation as in the production of squarylium [A-2] was conducted except that 34.3 parts of 3,5-difluorocyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. , 88.8 parts of squarylium [A-40] (yield: 93%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-40].

Squarylium [A-40]

(Manufacture of squarylium [A-41])
The same operation as the production of squarylium [A-2] was carried out except that 33.9 parts of 2-chlorocyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. [A-41] 87.5 parts (yield: 92%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-41].

Squarylium [A-41]

(Manufacture of squarylium [A-42])
The same operation as in the production of squarylium [A-2] was carried out except that 65.4 parts of 3,3-dibromocyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. , 116.3 parts (yield: 93%) of squarylium [A-42] were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-42].

Squarylium [A-42]

Tables 1 and 2 show the results of mass spectrometry and elemental analysis of squarylium [A-1] to [A-42] synthesized in the production examples.

<Preparation Method of Resin [B] Having Cationic Group in Side Chain>
(Preparation of resin [B-1] having a cationic group in the side chain)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 67.3 parts of methyl ethyl ketone was charged and heated to 75 ° C. under a nitrogen stream. Separately, 33.2 parts of methyl methacrylate, 27.3 parts of n-butyl methacrylate, 27.3 parts of 2-ethylhexyl methacrylate, 12.2 parts of dimethylaminoethyl methyl chloride salt, 2,2′-azobis (2,4 -Dimethylvaleronitrile) 6.5 parts and 21.5 parts of methyl ethyl ketone were homogenized, charged into a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of dropping, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7500, and the mixture was cooled to 50 ° C. Thereafter, 72 parts of isopropyl alcohol was added to obtain a resin [B-1] having a cationic group in the side chain of 40% by weight of the resin component. The ammonium salt value of the obtained resin was 33 mgKOH / g.

(Preparation of resin [B-2] having a cationic group in the side chain)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 67.3 parts of methyl ethyl ketone was charged and heated to 75 ° C. under a nitrogen stream. Separately, 22.4 parts of methyl methacrylate, 16.7 parts of n-butyl methacrylate, 27.3 parts of 2-ethylhexyl methacrylate, 15.0 parts of hydroxyethyl methacrylate, 2.5 parts of methacrylic acid, 1.3 parts of t-butyl methacrylate 1.3 parts of isobutyl methacrylate, 1.3 parts of cyclohexyl methacrylate, 12.2 parts of dimethylaminoethyl methyl chloride salt, 6.5 parts of 2,2′-azobis (2,4-dimethylvaleronitrile), and After making 25.1 parts of methyl ethyl ketone uniform, it was charged in a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7950, and the mixture was cooled to 50 ° C. Thereafter, 72 parts of isopropyl alcohol was added to obtain a resin [B-2] having a cationic group in the side chain of 40% by weight of the resin component. The ammonium salt value of the obtained resin was 33 mgKOH / g.

(Preparation of resin [B-3] having a cationic group in the side chain)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 67.3 parts of methyl ethyl ketone was charged and heated to 75 ° C. under a nitrogen stream. Separately, 21.0 parts of methyl methacrylate, 27.3 parts of n-butyl methacrylate, 27.3 parts of 2-ethylhexyl methacrylate, 22.4 parts of dimethylaminoethyl methyl chloride salt, 2,2′-azobis (2,4 -Dimethylvaleronitrile) 6.5 parts and 21.5 parts of methyl ethyl ketone were homogenized, charged into a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7640, and the mixture was cooled to 50 ° C. Thereafter, 72 parts of isopropyl alcohol was added to obtain a resin [B-3] having a cationic group in the side chain of 40% by weight of the resin component. The ammonium salt value of the obtained resin was 66 mgKOH / g.

(Preparation of resin [B-4] having a cationic group in the side chain)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 62.4 parts of isopropyl alcohol was charged and heated to 75 ° C. under a nitrogen stream. Separately, 16.0 parts of methyl methacrylate, 17.0 parts of butyl methacrylate, 16.0 parts of styrene, 51.0 parts of dimethylaminoethyl methyl chloride salt, 2,2′-azobis (2,4-dimethylvaleronitrile) 6 parts and 25.0 parts of methyl ethyl ketone were homogenized, charged into a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropping, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7050, and the mixture was cooled to 50 ° C. Thereafter, 65 parts of isopropyl alcohol was added to obtain a resin [B-7] having a cationic group in the side chain of 40% by weight of the resin component. The ammonium salt value of the obtained resin was 138 mgKOH / g.

(Preparation of resin [B-5] having a cationic group in the side chain)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 62.4 parts of isopropyl alcohol was charged and heated to 75 ° C. under a nitrogen stream. Separately, 35.5 parts of methyl methacrylate, 30.0 parts of butyl methacrylate, 16.8 parts of 2-ethylhexyl acrylate, 17.7 parts of dimethylaminopropylmethyl chloride methacrylate, 2,2′-azobis (2,4-dimethyl) 5.7 parts of valeronitrile) and 15.6 parts of methyl ethyl ketone were homogenized, charged into a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7420, and the mixture was cooled to 50 ° C. Thereafter, 72 parts of isopropyl alcohol was added to obtain a resin [B-2] having a cationic group in the side chain of 40% by weight of the resin component. The ammonium salt value of the obtained resin was 45 mgKOH / g.

(Preparation of resin [B-6] having a cationic group in the side chain)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 67.3 parts of methyl ethyl ketone was charged and heated to 75 ° C. under a nitrogen stream. Separately, 34.7 parts of isobornyl methacrylate, 1.7 parts of n-butyl methacrylate, 30.0 parts of hydroxyethyl methacrylate, 2.5 parts of methacrylic acid, 16.3 parts of t-butyl methacrylate, 2.5 parts of isobutyl methacrylate , 2.3 parts of cyclohexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 6.5 parts of 2,2′-azobis (2,4-dimethylvaleronitrile), and 25.1 parts of methyl ethyl ketone, The mixture was placed in a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 6830, and the mixture was cooled to 50 ° C. To this, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, reacted at 50 ° C. for 2 hours, heated to 80 ° C. over 1 hour, and further reacted for 2 hours. Thus, a resin [B-6] having a cationic group in the side chain of 47% by weight of the resin component was obtained. The ammonium salt value of the obtained resin was 34 mgKOH / g.

(Preparation of resin [B-7] having a cationic group in the side chain)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 67.3 parts of methyl ethyl ketone was charged and heated to 75 ° C. under a nitrogen stream. Separately, 60.0 parts of methyl methacrylate, 10.0 parts of n-butyl methacrylate, 10.0 parts of 2-isocyanatoethyl methacrylate, 20.0 parts of N, N-dimethylaminomethylstyrene, 2,2′-azobis (2 , 4-dimethylvaleronitrile) and 25.1 parts of methyl ethyl ketone were made uniform, charged in a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropping, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 6770, and the mixture was cooled to 50 ° C. To this, 15.7 parts of benzyl chloride and 22.0 parts of ethanol were added, reacted at 50 ° C. for 2 hours, heated to 80 ° C. over 1 hour, and further reacted for 2 hours. Thus, a resin [B-7] having a cationic group in the side chain of 50% by weight of the resin component was obtained. The ammonium salt value of the obtained resin was 60 mgKOH / g.

(Preparation of resin [B-8] having a cationic group in the side chain)
A 4-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser was charged with 62.4 parts of isopropyl alcohol and heated to 75 ° C. under a nitrogen stream. Separately, 30.0 parts of methyl methacrylate, 20.0 parts of butyl methacrylate, 15.0 parts of hydroxyethyl methacrylate, 5.0 parts of methacrylic acid, 10.0 parts of styrene, 20.0 parts of N-vinylpyrrolidone, 2,2 ′ -After 4.7 parts of azobis (2,4-dimethylvaleronitrile) and 15.6 parts of isopropyl alcohol were made uniform, charged into a dropping funnel, attached to a four-necked separable flask and dropped over 2 hours. . Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7550, and the mixture was cooled to 50 ° C. To this, 9.0 parts of methyl chloride and 22.0 parts of isopropyl alcohol were added, reacted at 50 ° C. for 2 hours, heated to 80 ° C. over 1 hour, and further reacted for 2 hours. Thereafter, 50 parts of isopropyl alcohol was added to obtain a resin [B-8] having a cationic group in the side chain of 44% by weight of the resin component. The ammonium salt value of the obtained resin was 92 mgKOH / g.

The composition, ammonium salt value, and weight average molecular weight of the resins [B-1] to [B-8] synthesized in the production examples are separately shown in Table 3.

Abbreviations in Table 3 are shown below.
MMA: methyl methacrylate n-BMA: n-butyl methacrylate 2-EHMA: 2-ethylhexyl methacrylate 2-EHA: 2-ethylhexyl acrylate HEMA: hydroxyethyl methacrylate MAA: methacrylic acid tBMA: t-butyl methacrylate IBMA: isobutyl methacrylate CHMA: cyclohexyl Methacrylate IBX: Isobornyl methacrylate St: Styrene MOI: 2-Isocyanatoethyl methacrylate

<Method for producing salt-forming compound>
[Example 1]
(Production of salt-forming compound 1)
A salt-forming compound 1 composed of squarylium [A-1] and a resin [B-2] having a cationic group was produced by the following procedure. The resin [B-2] having a cationic group in the side chain of 51 parts is added to 2000 parts of water, sufficiently stirred and mixed, and then heated to 60 ° C. On the other hand, an aqueous solution in which 6.03 parts of squarylium [A-1] and 0.85 parts of sodium hydroxide are dissolved in 90 parts of water is prepared and added dropwise to the above resin solution little by little. After dropping, the mixture is stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer, and 21 parts of squarylium [A-1] and a cation are obtained. The salt-forming compound 1 consisting of the resin [B-2] having a functional group was obtained.

[Examples 2 to 42]
(Production of salt-forming compounds 2 to 42)
Hereinafter, the salt-forming compounds 2 to 42 are the same as the salt-forming compound 1 except that the squarylium [A] and the resin [B] used in the production of the salt-forming compound 1 are changed to the compounds and amounts shown in Table 4. Got.

[Comparative Example 1]
(Manufacture of squarylium [C-1])
The following squarylium [C-1] was synthesized with reference to Japanese Patent No. 3590694.

Squarylium [C-1]

[Comparative Example 2]
(Squarylium [C-2])
The following squarylium [C-2] was synthesized with reference to Japanese Patent Application Laid-Open No. 2009-209297.

Squarylium [C-2]

<Manufacture of image forming materials>
Hereinafter, as an image forming material used in the present invention, a method for producing toner and ink-jet ink will be described, but the present invention is not limited to these.

<Manufacture of toner>
[Example 43]
(Manufacture of toner T1)
Using the salt-forming compound 1 produced in Example 1, an aggregation method toner T1 was obtained by the following method.
(1) Preparation of dispersion liquid To 20 parts of the salt-forming compound (1), 70 parts of ion-exchanged water and 3 parts of sodium dodecylbenzenesulfonate (Neopelex G-15, manufactured by Kao Corporation) were added and dispersed for 4 hours with an Eiger mill. The pigment dispersion was obtained by processing.
(2) Preparation of polymer emulsion In a reactor, 320 parts of ester wax emulsion (as solids (SELOSOL R-586, manufactured by Chukyo Yushi Co., Ltd.)) and 14000 parts of ion-exchanged water were heated to 90 ° C., and alkylbenzene 3 parts of sulfonate, 2500 parts of styrene, 650 parts of n-butyl acrylate, 170 parts of methacrylic acid, 330 parts of 8% aqueous hydrogen peroxide solution, and 330 parts of 8% ascorbic acid aqueous solution were added. The reaction was continued at 90 ° C. for 7 hours to obtain a polymer emulsion.
(3) Manufacture of toner 9.5 parts of the dispersion was poured into 150 parts of the polymer emulsion and mixed and stirred. Into this, 40 parts of 0.5% aluminum sulfate solution was poured while stirring. The temperature was raised to 60 ° C., and stirring was continued for 2 hours, followed by filtration, washing and drying to obtain the toner of the present invention.

[Examples 44 to 84, Comparative Examples 3 and 4]
(Manufacture of toners T2 to T44)
Aggregation method toners T2 to T44 were obtained in the same manner as toner T1, except that salt formation compound 1 was changed to the salt formation compounds or squarylium dyes shown in Table 5.

<Manufacture of inkjet ink>
[Example 85]
(Inkjet ink J1)
Ink jet ink J1 was obtained by the following method using salt-forming compound 1 produced in Example 1.
(1) Preparation of dispersion To 20 parts of the salt-forming compound, 200 parts of ion-exchanged water and 2 parts of a sodium salt of special aromatic sulfonic acid formalin condensate (Demol SN-B, manufactured by Kao Corporation) are added, and 3 parts with an Eiger mill. A time dispersion treatment was performed to obtain a pigment dispersion.
(2) Manufacture of ink In each of the above dispersions (40.3 parts), 10 parts of glycerin, 10 parts of triethylene glycol, 10 parts of triethylene glycol monobutyl ether, 0.2 part of triethanolamine, an acetylene glycol surfactant (Orphine) 1 part of E1010 (manufactured by Nissin Chemical Co., Ltd.) was mixed and stirred at 35 ° C. for 1 hour. Then, it filtered with a 1.0 micrometer filter, and obtained the inkjet ink of this invention. The remainder was prepared so that ultrapure water (specific resistance value of 18 MΩ · cm or more) was added and the total amount was 100 parts.

[Examples 86 to 126, Comparative Examples 5 and 6]
(Inkjet inks J2 to J44)
Ink jet inks J2 to J44 were obtained in the same manner as the ink jet ink J1, except that the salt forming compound 1 was changed to the salt forming compound or squarylium pigment shown in Table 5.

<Evaluation of image forming material>
[Evaluation of toner]
The following evaluations were performed using the obtained toners T1 to T44. The results are shown in Table 5.
(Dispersibility)
The obtained toners T1 to T44 were sliced to a thickness of 0.9 μm with a microtome, and the pigment dispersion state was observed with a transmission electron microscope. ○ when the pigment is uniformly distributed in the colored resin composition, △ when the pigment aggregate is present and not uniformly distributed, × when the pigment aggregate is many and not uniformly distributed It was.

(Invisibility and near infrared absorption ability)
About 50 parts of the obtained toners T1 to T44, 0.3 part of hydrophobic silica was externally added, and a solid image was printed on high-quality paper with an electrophotographic printer, and evaluated by the following method. An image obtained by printing a solid image on fine paper is measured using a reflection spectral densitometer (x-rite 939, manufactured by X-Rite Co., Ltd.), and in the above-mentioned <Method for evaluating image forming material> ΔE in formula (II) and R in formula (III) were determined. In addition, (double-circle) is a very good level, (circle) is a favorable level, and x is a level unsuitable for practical use. The evaluation criteria are as follows.

<Invisibility>
◎: Less than ΔE 10 ○: ΔE 10 or more, less than 15 ×: ΔE 15 or more <Near-infrared absorbing ability>
◎: (100-R) 80 or more ○: (100-R) 75 or more, less than 80 ×: (100-R) 75 or less

(Light resistance)
A test piece obtained in the same manner as that prepared when evaluating the invisibility and near infrared absorption ability was placed in a light resistance tester (“SUNTEST CPS +” manufactured by TOYOSEIKI) and allowed to stand for 24 hours. About the image before and after a light resistance test, it measured using the reflection spectral densitometer (The X-lite KK make, x-rite939), and calculated | required R in Formula (III). The residual rate relative to that before light irradiation was determined, and the light resistance was evaluated according to the following criteria. The residual rate was calculated using the following formula.

  Residual rate = <(100-R) after irradiation> / ((100-R) before irradiation) × 100

◎: Residual rate is 95% or more ○: Residual rate is 92.5% or more and less than 95% △: Residual rate is 90% or more and less than 92.5% ×: Residual rate is less than 90%

The image forming material containing the salt-forming compound of the present invention has been shown to have very high dispersibility, invisibility, near infrared absorption ability, and light resistance. In particular, the image forming material containing the salt-forming compounds 6 to 9 and 11 to 14 in which X ₃ , X ₄ , X ₇ and X _{8 in} the cyclo ring of squarylium [A] were substituted with a methyl group was a good result. . Among them, the salt-forming compounds 6, 7, 11, and 12 having a sulfo group substitution number n = 1 or 2 gave particularly good results. On the other hand, the salt-forming compound in which n = 3 or 4 was slightly inferior in light resistance. In addition, the salt-forming compounds 20, 28, and 36 using the resin [B-4] having an ammonium salt value of 130 mgKOH / g or more were slightly inferior in dispersibility. On the other hand, the image forming material containing squarylium [C-1] which is not the present invention has deteriorated invisibility and light resistance. Further, the image forming material containing squarylium [C-2] which is not the present invention has good invisibility, near-infrared absorption ability, and light resistance, but is not suitable for practical use because its dispersibility is remarkably deteriorated. It is.

[Evaluation of ink for inkjet]
The following evaluation was performed using the obtained inkjet inks J1 to J44. The results are shown in Table 6.
(Storage stability)
The obtained inkjet inks J1 to J44 were stored in a thermostat at 70 ° C. for 1 week and allowed to accelerate with time, and the viscosity change of the ink before and after aging was measured. The viscosity of the ink was measured using an E-type viscometer (“ELD type viscometer” manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. and a rotation speed of 50 rpm.
◎: Change rate is less than ± 3% ○: Change rate is ± 3% or more and less than ± 5% △: Change rate is ± 5% or more and less than ± 15% ×: Change rate is ± 15% or more

(Invisibility and near infrared absorption ability)
The obtained ink-jet inks J1 to J44 are packed in a black ink ink cartridge for an ink jet printer PM-A700 (trade name, manufactured by EPSON) and photo glossy paper (PM photo paper manufactured by EPSON <gloss> (KA420PSK) , EPSON (trade name), a solid image was printed with a color setting of “black” and evaluated by the following method: For an image obtained by printing a solid image on photo glossy paper, Measurement was performed using a reflection spectral densitometer (x-rite 939, manufactured by X-Rite Co., Ltd.), and ΔE in formula (II) and R in formula (III) were determined. , O is a good level, x is a level not suitable for practical use, and evaluation criteria are as follows.

<Invisibility>
◎: Less than ΔE 10 ○: ΔE 10 or more, less than 15 ×: ΔE 15 or more <Near-infrared absorbing ability>
◎: (100-R) 80 or more ○: (100-R) 75 or more, less than 80 ×: (100-R) 75 or less

(Light resistance)
A test piece obtained in the same manner as that prepared when evaluating the invisibility and near infrared absorption ability was placed in a light resistance tester (“SUNTEST CPS +” manufactured by TOYOSEIKI) and allowed to stand for 24 hours. About the image before and after a light resistance test, it measured using the reflection spectral densitometer (The X-lite KK make, x-rite939), and calculated | required R in Formula (III). The residual rate relative to that before light irradiation was determined, and the light resistance was evaluated according to the following criteria. The residual rate was calculated using the following formula.
Residual rate = <(100-R) after irradiation> / ((100-R) before irradiation) × 100
◎: Residual rate is 95% or more ○: Residual rate is 92.5% or more and less than 95% △: Residual rate is 90% or more and less than 92.5% ×: Residual rate is less than 90%

The image forming material containing the salt-forming compound of the present invention has been shown to have very high invisibility, near infrared absorption ability, light resistance and storage stability. In particular, the image forming material containing the salt-forming compounds 6-9 and 11-14 in which X ₃ , X ₄ , X ₇ and X ₈ of the cyclo ring of squarylium [A] are substituted with a methyl group was an excellent result. It was. Among them, the salt-forming compounds 6, 7, 11, and 12 having a sulfo group substitution number n = 1 or 2 gave particularly good results. On the other hand, the salt-forming compound in which n = 3 or 4 was slightly inferior in light resistance. In addition, the salt-forming compounds 20, 28, and 36 using the resin [B-4] having an ammonium salt value of 130 mgKOH / g or more were slightly inferior in dispersibility.
The image forming material containing squarylium [C-1] which is not the present invention has deteriorated invisibility and light resistance. Further, the image forming material containing squarylium [C-2] which is not the present invention has good invisibility, near-infrared absorption ability, and light resistance, but storage stability is remarkably deteriorated and stable as an inkjet ink. Cannot be used.

  The image forming material thus prepared has very little absorption in the visible region (400 nm to 750 nm) and is excellent in near infrared absorption ability, and therefore can be said to have excellent spectral characteristics. Furthermore, since it is excellent in light resistance and hardly aggregates, it is excellent in dispersibility as a toner and storage stability as an inkjet ink. Therefore, it can be said that it has excellent performance as an image forming material for recording invisible information.

Claims (4)

A salt-forming compound of squarylium [A] represented by the following general formula and resin [B] having a cationic group in the side chain.
General formula (1)

[In General Formula (1), X _{1 to} X ₁₀ each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. An aryl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an amino group, a substituted amino group, —SO ₂ NR ₁ R ₂ , —COOR ₃ , —CONR ₄ R ₅ , a nitro group, a cyano group, or a halogen atom may be represented, and adjacent groups may form a ring. R _{1 to} R ₅ each independently represents a hydrogen atom or an alkyl group which may have a substituent. n represents an integer of 1 to 4. Z ⁺ represents a hydrogen ion or an inorganic or organic cation. ] The salt-forming compound according to claim 1, wherein the resin [B] having a cationic group in the side chain is a vinyl resin containing a structural unit represented by the following general formula (2).
General formula (2)

[In General Formula (2), R ₆ represents a hydrogen atom or an alkyl group which may have a substituent. R _{7 to} R ₉ each independently represent a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent; Two of _{7 to} R ₉ may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ₁₀ — or —COO—R ₁₁ —, and R ₁₀ and R ₁₁ represent an alkylene group. Y ⁻ represents an inorganic or organic anion. ]   An image forming material containing the salt-forming compound according to claim 1.   The image forming material according to claim 3, which is an electrophotographic toner, an ink for an ink jet printer, or an ink for letterpress, offset, flexo, gravure, or silk printing.