WO2008056626A1

WO2008056626A1 - Azo compound, ink composition, recording method, and colored body

Info

Publication number: WO2008056626A1
Application number: PCT/JP2007/071471
Authority: WO
Inventors: Takahiko Matsui; Yoshiyuki Dejima; Takashi Yoshimoto; Koji Hirota
Original assignee: Nippon Kayaku Kabushiki Kaisha
Priority date: 2006-11-08
Filing date: 2007-11-05
Publication date: 2008-05-15
Also published as: TW200833792A; JPWO2008056626A1

Abstract

Disclosed is an azo compound represented by the formula (1) below or a salt thereof. Also disclosed is an ink composition containing the azo compound or a salt thereof. (In the formula, group A represents a substituted phenyl group; R1 represents a (C1-C4) alkyl group or the like; R2 represents a cyano group or the like; R3 and R4 independently represent a sulfo group or the like; and R5-R10 independently represent a sulfo group or the like.) The azo compound exhibits high solubility in a medium mainly composed of water, and a high-concentration aqueous solution or ink thereof is stable even after long storage. When a recording is performed by using this azo compound, there is obtained a black recorded image which has a very high concentration, while being excellent in fastness, particularly in light resistance and ozone gas resistance. Consequently, this azo compound is useful as a dye for black ink.

Description

Specification

Azo compound, ink composition, recording method and colored body

Technical field

[0001] The present invention relates to a novel azo compound or a salt thereof, an ink composition containing these, and a colored product thereby.

Background art

[0002] A recording method using an ink jet printer, which is one of the representative methods among various color recording methods, generates ink droplets and attaches them to various recording materials (paper, film, fabric, etc.). It is for recording. This method has been spreading rapidly in recent years due to the fact that the recording head and the recording material are not in direct contact and is quiet with little sound generation, and is easy to downsize and speed up. Expected. Conventionally, water-based inks in which water-soluble dyes are dissolved in water-based media have been used as inks for fountain pens and felt-tip pens, and ink-jet recording inks. In general, water-soluble organic solvents are added to prevent clogging of ink at the ink discharge nozzles. These inks provide a recorded image with sufficient density, do not cause clogging of the pen tip and nozzles, have good drying properties on recording materials, have little bleeding, and have storage stability. It is required to be excellent. The water-soluble dye used is required to have a particularly high solubility in water and a high solubility in the water-soluble organic solvent added to the ink. Furthermore, the formed image is required to have image fastness such as water resistance, light resistance, ozone gas resistance and moisture resistance!

[0003] Of these, ozone gas resistance refers to resistance to a phenomenon in which ozone gas having an oxidizing action that exists in the air acts on a dye in recording paper and discolors the printed image. That is. In addition to ozone gas, NOx, SOx, etc. are examples of oxidizing gases that have this type of action. Among these oxidizing gases, ozone gas is the main causative substance that further promotes the discoloration phenomenon of ink jet recording images. It is! / The ink receiving layer provided on the surface of photographic quality ink jet paper uses materials such as porous white inorganic materials to speed up ink drying and reduce bleeding at high image quality. On many such recording papers, discoloration due to ozone gas is noticeable. Since this discoloration phenomenon caused by oxidizing gas is characteristic of ink jet images, improvement of ozone gas resistance is one of the most important issues in ink jet recording methods.

[0004] In the future, the ink composition used for inkjet recording and the colored bodies colored thereby should be expanded in the field of use of printing methods using ink. Light resistance, ozone gas resistance, moisture resistance There is a strong demand for further improvements in water resistance and water resistance!

[0005] A variety of hues of ink is being prepared from various dyes S, of which black ink is an important ink used for both mono-color and full-color images. Many of these dyes for black ink have been proposed to date. We have not yet provided products that fully satisfy market demands. Many of the proposed dyes are azo dyes. Among them, disazo dyes such as CI Food Black2 have low optical density of the image, poor water resistance and moisture resistance, light resistance and gas resistance. There are problems such as not enough. In general, polyazo dyes having a conjugated system have problems such as low water solubility, easily causing a bronzing phenomenon in which recorded images have a partial metallic luster, and insufficient light resistance and gas resistance. Similarly, many of the proposed azo-containing pigments have good light resistance. Since they contain metal ions, they are not preferable for biological safety and environmental problems. ! /, Etc.

[0006] As the most important issue in recent years, as an ozone gas resistance improved and / or improved as a compound for black ink for ink jet (pigment), for example, compounds described in Patent Documents 1 and 2 are listed. It is done. These compounds are not sufficient in terms of light resistance, which is not sufficient for ozone gas resistance to meet market requirements. In addition, examples of the azo compound having a benzimidazolopyridone skeleton are described in Patent Documents 3 to 6 and the like. Patent Document 3 specifically discloses a monoazo compound, and Patent Documents 4 and 5 also specifically disclose a trisazo compound having a benzimidazolopyridone skeleton symmetrically. Shiki, Tetrakisazo compounds are specifically disclosed.

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 2003-183545

Patent Document 2: JP 2003-201412 Patent Document 3: Internationally Published Patent 2004-050768

Patent Document 4: German Published Patent 2004488

Patent Document 5: German Published Patent No. 2023295

Patent Document 6: Japanese Patent Laid-Open No. 05-134435

Disclosure of the invention

Problems to be solved by the invention

The present invention is stable even when a highly concentrated aqueous solution and ink having high solubility in a medium containing water as a main component are stored for a long period of time, and the density of the printed image is very high. Black ink dyes (compounds) that give black recorded images with excellent image fastness, especially light resistance and ozone gas resistance, and are easy to synthesize and inexpensive, and ink compositions containing the same In particular, an object of the present invention is to provide a black ink composition for inkjet, an inkjet recording method using the ink, and a colored body using the pigment.

Means for solving the problem

[0009] As a result of intensive studies to solve the above-described problems, the present inventors have found that an azo compound represented by the following formula (1) can solve the above-mentioned problems. Invented. That is, the present invention

(1) an azo compound represented by the following formula (1) or a salt thereof,

[Wherein, the group A is a substituted phenyl group, and includes a carboxy group, a sulfo group, a hydroxy group, an acetylamino group, a chlorine atom, a cyano group, a nitro group, a sulfamoyl group, a (C1-C4) alkyl group, ( C1-C4) alkoxy group (which may be substituted with a group selected from the group consisting of hydroxy group, (C1-C4) alkoxy group, sulfo group and carboxy group) and (C1-C4) alkylsulfonyl group (hydroxy Having at least one substituent selected from the group consisting of a group, a sulfo group or a carboxy group! R ¹ represents a (C ¹ -C 4) alkyl group (substituted with a carboxy group! /, May be selected), a phenyl group (which may be substituted with a sulfo group), or a carboxy group,

R ² represents a cyano group, a strong rubermoyl group or a carboxy group,

R ³ and R ⁴ each independently represents a hydrogen atom, a methyl group, a chlorine atom or a sulfo group,

R ⁵ to R ^1Q are each independently a hydrogen atom, carboxy group, sulfo group, acetylamino group, (C1-C4) alkyl group or (C1-C4) alkoxy group (hydroxy group, (C1-C4) alkoxy group, Substituted with a sulfo group or a carboxy group! /, May represent! /))),

(2) At least one of the substituents of the group A is a sulfo group or a carboxy group, and among the combinations of three kinds of substituents R ⁵ and R ⁶ , R ⁷ and R ⁸ , and R ⁹ and R ^1Q , at least The azo compound according to the above (1), wherein one substituent of each combination is a sulfo group or a sulfopropoxy group,

(3) the azo compound according to the above (1) represented by the following formula (2):

[0012]

[In the formula, R ⁵ represents a sulfo group, a sulfoethoxy group, a sulfopropoxy group or a sulfobutoxy group, R ⁷ and R ⁹ represent a sulfoethoxy group, a sulfopropoxy group or a sulfobutoxy group, R ⁶ , R ⁸ And R ^1Q each independently represents a hydrogen atom, an acetylamino group, a methyl group, an ethyl group, a methoxy group or an ethoxy group, and R ^u , R ¹² and R ¹³ each independently represent a hydrogen atom, a carboxy group, Sulfo group, hydroxy group, acetylamino group, chlorine atom, cyano group, nitro group, sulfamoyl group, (C1-C4) alkyl group, (C1-C4) alkoxy group (hydroxy group, (C1-C4) alkoxy group, sulfo group Substituted with a group selected from the group consisting of a group and a carboxy group! /, May be! /, Or (C1-C4) an alkylsulfonyl group (a hydroxy group, a sulfo group or a carboxy group) In substituted represents may) be, at least one of R ^U, R ¹² and ³ represents a group other than a hydrogen atom}, (4) The azo compound according to the above (1) or (3), wherein R ¹ is a methyl group, R ² is a cyano group or a strong rubermoyl group, R ³ is a hydrogen atom, and R ⁴ is a sulfo group,

(5) R ^U, R ¹² and R ^13, R ^u, on the condition that one of at least one of a hydrogen atom other than groups R ¹² and R ^13, each independently, a hydrogen atom, a sulfo Group, carboxy group, sulfopropylsulfonyl group or acetylamino group, R ¹ is a methyl group, R ² is a cyano group or cananolamoyl group, R ³ is a hydrogen atom, R ⁴ is a sulfo group, R ⁵ is a sulfo group or a sulfooxy group R ⁷ and R ⁹ force S sulfopropoxy group, R ⁶ , R ⁸ and R ^1Q are each independently a hydrogen atom or a methyl group, the azo compound according to the above (3),

(6) When the substitution position on the benzene ring of R ^{U to} R ¹³ is the 1-position of the substitution position of the azo group, R ¹ ¹ is 2-position or 3-position, R ¹² is 4-position and R ¹³ is 5 R ^U is a hydrogen atom, a sulfo group or a carboxy group, R ¹² is a hydrogen atom, a sulfo group, an acetylamino group or a sulfopropylsulfonyl group, R ¹³ is a hydrogen atom or a sulfo group, R ^u At least one of R ¹² and R ¹³ is a group other than a hydrogen atom, R ¹ is a methyl group or an n-propyl group, R ² is a cyano group or a strong rubamoyl group, R ³ Is a hydrogen atom, R ⁴ is a sulfo group, R ⁵ is a sulfo group or a sulfopropoxy group, R ⁶ is a hydrogen atom or a methyl group, R ⁷ and R ^{9 are} sulfopropoxy groups, R ⁸ and R ^1Q are methyl groups, the azo compound according to the above (3),

(7) R ¹² is a sulfo group, the substitution position is para to the azo group, R ^U and R ¹³ are hydrogen atoms, R ¹ is a methyl group, R ² is a cyano group or cananolamoyl group, R ³ is The hydrogen atom, R ⁴ is a sulfo group, R ⁵ is a sulfo group, R ⁶ is a hydrogen atom, R ⁷ and R ⁹ force S sulfopropoxy group, and R ⁸ and R ^1Q are methyl groups (3) An azo compound according to

(8) An ink composition comprising at least one azo compound according to any one of (1) to (7) above,

(9) An ink jet recording method comprising attaching the ink composition according to (8) to a recording material by ink jet,

(10) The inkjet recording method according to (9), wherein the recording material in the inkjet recording method is an information transmission sheet,

(11) The information transmission sheet described in (10) above, which contains a porous white inorganic substance Jet recording method,

(12) An inkjet printer loaded with a container containing the ink composition according to (8) above,

(13) A colored product colored with the azo compound according to any one of (1) to (7) above,

About.

The invention's effect

[0014] The azo compound of the formula (1) and its tautomers or salts thereof (hereinafter collectively referred to simply as azo compounds) are excellent in water solubility. The filterability of the blank filter is good, and the storage stability and ejection stability of the recording liquid are also excellent. Further, the ink composition of the present invention containing this azo compound has good storage stability without crystal precipitation, physical property change, color change and the like after long-term storage. In addition, the ink composition containing the azo compound of the present invention is suitably used for inkjet recording and writing instruments, and has a very high print density of recorded images when recorded on plain paper and inkjet dedicated paper. Furthermore, it is excellent in various fastness properties, particularly light resistance and ozone gas resistance. When used together with an ink composition using magenta, cyan and yellow dyes, full-color ink jet recording with excellent fastness and storage stability is possible. Thus, the ink composition of the present invention is extremely useful as a black ink for inkjet recording.

BEST MODE FOR CARRYING OUT THE INVENTION

[0015] Hereinafter, the present invention will be described in detail.

As tautomers of the azo compound represented by the formula (1), in addition to the compound of the formula (1), the following formulas (3) and (4) are considered, and these compounds are also included in the present invention.

[Wherein the groups A and R ^ R ¹ "have the same meaning as in formula (1).]

[In the formula, the groups A and R ^ R ¹ "have the same meaning as in formula (1).]

[0020] In the present invention, examples of the (C1-C4) alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and t-butyl. Examples of the (C1-C4) alkoxy group include methoxy, ethoxy, n propoxy, isopropoxy, n butoxy, sec butoxy and t butoxy. For these alkyl groups or alkoxy groups, a straight chain alkyl group is preferable.

Examples of (C 1 -C 4) alkyl group optionally substituted with a carboxy group in R ¹ include, for example, methyl, ethyl, n propyl, isopropyl, n butyl, isobutyl, s ec butyl, t -Butyl, carboxymethyl, 2-carboxyethyl and the like are preferable, and straight chain unsubstituted (C1-C4) alkyl, t-butyl or carboxymethyl are preferable. More preferred is unsubstituted (C1 C3) alkyl, most preferred methinore.

[0022] Examples of the phenyl group which may be substituted with a sulfo group in R ¹ in the formula (1) and the like include, for example, phenyl, 3 sulfophenyl, 4 sulfophenyl, 2, 4 disulfophenyl, 3, 5— Examples include disulfophenyl, and phenyl or 4-sulfophenyl is preferred. The most preferred layer is 4-sulfophenyl.

In the present invention, examples of the (C1 to C4) alkoxy group optionally substituted with a hydroxy group, (C1 to C4) alkoxy group, sulfo group or carboxy group include, for example, methoxy, ethoxy, n propoxy , Isopropoxy, n butoxy, sec butoxy, t butoxy, 2 hydroxyethoxy, 2 hydroxypropoxy, 3 hydroxypropoxy, methoxyethoxy, ethoxyethoxy, n propoxyethoxy, isopropoxyethoxy, n butoxyethoxy, methoxypropoxy, ethoxypropoxy, n Propoxypropoxy, iso Examples include propoxybutoxy, n-propoxybutoxy, 2-hydroxyethoxyethoxy, canolepoxymethoxy, 2 carboxyethoxy, 3 carboxypropoxy, 3 sulfopropoxy, 4 sulfobutoxy and the like.

[0024] Examples of the alkylsulfonyl group which may be substituted with a hydroxy group, a sulfo group or a carboxy group in the substituent of the group A in the formula (1) include, for example, methinolesnorephoninore , Ethinores norehoninore, propinores norehoninole, p 'chinores norehoninole, hydroxy shechinores norehoninole, 2-hydroxypropinores norehoninole, 2-snorejochinole norehoni nore 3 snoreproppropenoles norehoninole, 2 force nerokische chinores norehoninole, 3 force nerboxoxypropylsulfonyl and the like. The (C ;! to C4) alkylsulfonyl group is more preferably sulfopropylsulfonyl, which is preferably a sulfo-substituted (C1 to C4) alkylsulfonyl group.

[0025] Preferred substituents of the group A in the formula (1) include carboxy-containing carboxy, sulfo, sulfamoinole, methinolesnorehoninore, 2 hydroxyethinolesnorehoninore, and 3snorehof. Mouth pinoles norehoninole, acetylamino, nitro, methyl, methoxy, ethyl, ethoxy, 2-hydroxy ethoxy, 2 sulfoethoxy, 3 sulfopropoxy, 4 sulfobutoxy, carboxy methoxy, 2-carboxyethoxy, etc. Carboxy, sulfo, snorefamoinole, methinolesnorehoninole, hydroxyethinoresnorehoninole, 3-sunorepropylpropylsulfonyl, acetylamino or nitro, more preferably carboxy or snorefo.

Preferred groups A in formula (1) can include phenyl groups having at least one sulfo substituent, more preferably mono- or disulfo-substituted phenyl, or force oxy, acetylamino and sulfo (C 1 C4). And a phenyl group having one substituent selected from alkylsulfonyl and mono- or disulfo substitution.

And more preferably mono- or disulfo-substituted phenyl. The monosulfo-substituted phenyl is preferably p-sulfophenyl, and the disulfo-substituted phenyl is preferably o- and p-disulfo-substituted phenyl, or o- and m-disulfo-substituted phenyl, and more preferably o- and p-disulfo-substituted phenyl.

[0026] In the present invention! /, Preferred! /, R ^{5 to} R ^1Q are each independently carboxy, sulfo, Acetylamino, methyl, methoxy, ethyl, ethoxy, 2-hydroxyethoxy, 2-sulphoethoxy, 3 sulfopropoxy, 4 sulfobutoxy, carboxymethoxy or 2-carboxyethoxy, more preferably sulfo, methyl, methoxy, 2- Hydroxyethoxy, 2 sulfoethoxy, 3 sulfopropoxy or carboxymethoxy, more preferably sulfo, methyl, methoxy or 3-sulfopropoxy. R ⁶ is also preferably a hydrogen atom.

Preferably, the combination of R ⁵ and R ⁶ is R ⁵ is sulfo, or sulfo (C1-C4) alkoxy, preferably sulfo (C2-C4) alkoxy, more preferably sulfopropoxy, and is a hydrogen atom, or Combinations that are (C1-C4) alkyl groups, preferably methyl. The substitution position is preferably such that R ⁵ is ortho to the azo group and R ⁶ is para to R ⁵ . In particular, the substitution position represented by the formula (2) is preferable. As a preferred combination of R ^{7 to} R ^1Q , R ⁷ and R ⁹ are sulfo (C1-C4) alkoxy, preferably sulfo (C2-C4) alkoxy, more preferably 3 sulfopropoxy, and R ⁸ and R 9 ^1Q is a (CI—C4) alkyl group, preferably methyl. A preferable combination of R ⁵ and R ⁶ and a preferable combination of R ^{7 to} R ^1Q are more preferable.

As a more preferable combination of R ^{5 to} R ^1Q , R ⁵ is sulfo or 3-sulfopropoxy, R ⁶ is hydrogen atom or methyl, R ⁷ and R ⁹ are 3-sulfopropoxy, R ⁸ and R ^1Q force S methyl is there.

[0027] Preferred R ¹ in the present invention is unsubstituted linear (CI-C4) alkyl, t-butyl, carboxymethyl, phenyl, 4-sulfophenyl, carboxy, and more preferably unsubstituted linear (CI-C3). ) Alkyl, carboxymethyl, 4 sulfophenyl. More preferred is unsubstituted straight chain (CI C3) alkyl, most preferably methyl. Preferred R ² is Ciano or force rubermoyl. Desirable R ³ and R ⁴ are each independently a hydrogen atom, methyl or sulfo.

In the present invention, a preferable combination of I ^ to R ⁴ is that R ¹ is an unsubstituted straight chain (CI—C 3) alkyl group, more preferably methyl, R ² is cyan or rubamoyl, and R ³ And R 4 are each independently a hydrogen atom, methyl or sulfo, and a preferred combination of R ³ and R ⁴ is when one is a hydrogen atom and the other is sulfo. [0029] One of the preferred compounds of the above formula (1) is a compound having 5 or 6 sulfo groups in the molecule of the formula (1). Further, the compound having the preferred group A is one of the preferred ones, and the compound having 5 or 6 sulfo groups in the molecule of the formula (1) is more preferred. In addition, a compound having a preferable combination of RR ⁴ in the above formula (1) is also one of the preferable compounds, and a compound having 5 or 6 sulfo groups in the molecule of the formula (1) is more preferable. preferable.

Further, as another preferred compound, a compound having a combination of the preferred group A and a preferred I ^ to R ⁴ can be mentioned. In this case, too, a sulfo group is present in the molecule of the formula (1). Compounds having 5 or 6 are more preferred.

[0030] Further, in each of the preferred compounds of the above, further, combining only preferred R ⁵ and R ^6, more preferably, in the above preferred R ⁵ to R ^{1 (compounds} having a combination ^of) can be further preferred compound is there.

Among them, one of the more preferable compounds is a compound represented by the following formula (2). Formula (2)

[0031]

[0032] In the above formula (2), 1 ^ to 1 ^ ° represents the same meaning as in the above formula (1), and the preferred group and preferred group are also the same as in the above formula (1). is there.

[0033] R ^{U to} R ¹³ in the above formula (2) each independently represent a hydrogen atom or the same substituent as the substituent in the group A in the above formula (1), and at least one of them is a hydrogen atom. Represents a group other than. The preferred group and the preferred combination of groups are the same as the substituent in the group A. When the group A has one substituent, it corresponds to the case where two of R ^{U to} R ¹³ are hydrogen atoms, When the substituent of group A is two, it corresponds to the case where one of R ^{U to} R ¹³ is a hydrogen atom, and when there are three substituents of group A, all of R ^{U to} R ¹³ are hydrogen atoms. Applicable when other groups are represented. In addition, R The substituted position of ^U to R ^13, when the 1-position substitution positions of § zone group, the R ^u is 2 or 3 position, the R ¹² is 4-position, and R ¹³ is 5-position Those substituted with are preferred. In this case, at least one is a group other than a hydrogen atom, preferably at least one is sulfo or carboxy, more preferably sulfo. More preferably, either R ¹¹ or R ¹² is sulfo, the other is a hydrogen atom, sulfo, carboxy, acetylamino or sulfo (C1-C4) alkoxy, more preferably a hydrogen atom or sulfo.

Further, R ^U is a hydrogen atom substituted at the 2- or 3-position, sulfo or carboxy, R ¹² is a hydrogen atom substituted at the 4-position, sulfo, acetylamino or sulfopropylsulfonyl, and R ¹³ is at the 5-position A combination that is a substituted hydrogen atom or sulfo is particularly preferred. In this case, at least one is a group other than a hydrogen atom, preferably at least one force S sulfo or carboxy, more preferably sulfo. More preferably, R ¹² is sulfo.

Particularly preferred in formula (2) are those in which the substitution positions of R ^{U to} R ¹³ are specified as described above, and preferred substituents in formula (2) are the same as those in formula (1) above. . The most preferred compounds, R ² is Shiano or Kanorebamoiru, R ⁴ and R ⁵ is ^{^{sulfo, R 3, R 6, R}} u and R ¹³ are hydrogen atoms, R ⁷ and R ⁹ force S sulfopropoxy,

R ⁸ and UR ^W are methyl, R ¹² is sulfo substituted at the 4-position, or R ² is cyan, R ⁴ is sulfo, R ³ and R ¹³ are hydrogen atoms, R ⁵ , R ⁷ and R ⁹ is sulfopropoxy,

R ⁶ , R ⁸ and R ^{1 ()} are methyl, sulfo substituted at the R ¹¹ position, and R ¹² is sulfo substituted at the 4 position.

The salt of the azo compound represented by the formula (1) is an inorganic or organic cation salt. Among these, specific examples of inorganic salts include alkali metal salts, alkaline earth metal salts and ammonium salts. Preferred inorganic salts are lithium, sodium, potassium salts and ammonium salts, and organic cations. Examples of the salt include, but are not limited to, a salt with an organic cation represented by the following formula (5). The free acids, their tautomers, and their various salts may also be a mixture, such as a mixture of sodium and ammonium salts, a mixture of free acid and sodium salts, lithium, sodium and ammonium salts. Any combination such as a mixture of salts may be used. salt The physical properties such as solubility may vary depending on the type of salt, and if necessary, select the type of salt as appropriate, or if multiple salts are included, change the ratio to make the physical property suitable for the purpose. It is also possible to obtain a mixture having.

Formula (5)

[0036] In the formula:

Z ⁴ each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group, a hydroxyalkyl group and a hydroxyalkoxyalkyl group.

Formula (5)

Specific examples of the alkyl group for Z ⁴ include methyl, ethyl, n-propyl, isopropyl, n butyl, isobutyl, sec butyl, tert butyl, and the like. Specific examples of the hydroxyalkyl group include hydroxymethyl, hydroxyethynole. Hydroxy- (C1-C4) alkyl groups such as 3-hydroxypropinole, 2-hydroxypropinole, 4-hydroxybutinole, 3-hydroxybutyl, 2-hydroxybutyl and the like. Examples of hydroxyalkoxyalkyl groups include hydroxy Hydroxy (C1-C4) alkoxy such as ethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutynole, 3-hydroxyethoxybutynole, 2-hydroxyethoxybutyryl (C1- C4) an alkyl group Of these, a hydroxyethoxy (C1-C4) alkyl group is preferred. Particularly preferred are a hydrogen atom; methyl; hydroxymethyl, hydroxyethyl, 3 hydroxypropyl, 2 hydroxypropynole, 4-hydroxybutyl, 3 hydroxybutyl, 2 hydroxybutynole, etc. hydroxy (C1-C4) Alkyl groups: hydroxyethoxy such as hydroxyethoxymethyl, 2-hydroxyethoxychetyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxychibutoxy butinore, 3-hydroxyethoxybutynole, 2-hydroxyethoxybutynole C1-C4) alkyl groups.

[0037] Formula (5)

Specific examples of Z ³ and Z ⁴ are shown in Table 1.

[0038] [Table 1] Compound No. Zl Z2 Z3 Z4

1-1 H CH3 CH3 CH3

1-2 CH3 CH3 CH3 CH3

1-3 H -C2H40H -C2H40H -C2H40H

1-4 CH3 -C2H40H -C2H40H -C2H40H

1-5 H -CH2CH (OH) CH3 -CH2CH (0H) CH3 -CH2CH (OH) CH3

1-6 CH3 -CH2CH (OH) CH3 -CH2CH (0H) CH3 -CH2CH (OH) CH3

1-7 H -C2H40H H -C2H40H

1-8 CH3 -C2H40H H -C2H40H

1-9 H -CH2CH (OH) CH3 H -CH2CH (0H) CH3

1-10 CH3 -CH2CH (OH) CH3 H -CH2CH (0H) CH3

1-11 CH3 -C2H40H CH3 -C2H40H

1-12 CH3 -CH2CH (0H) CH3 CH3 -CH2CH (OH) CH3

[0039] The tetrakisazo compound of the present invention represented by the formula (1) can be synthesized by, for example, the following method. The structural formula of the compound in each step is expressed in the form of a free acid. The groups A and ˜1 ^ ° used in the following formulas (6) to (; 13) have the same meaning as in the formula (1).

A compound represented by the following formula (6) is diazotized by a conventional method, and the resulting diazo compound and a compound represented by the following formula (7) are subjected to a coupling reaction by a conventional method to obtain a compound represented by the following formula (8): Get the compound.

Formula (6)

[0040]

A-NH _{2 (6)}

Formula (7)

[0041]

Formula (8)

After the obtained compound of the above formula (8) is used in a conventional manner, the obtained diazo compound and the compound represented by the following formula (9) are reacted in a conventional manner to obtain a compound represented by the following formula (10). obtain.

Formula (9)

R

N ΝΗ 2

R 8 formula (10)

The obtained compound of the above formula (10) is subjected to a conventional method, and the obtained diazo compound is reacted with a compound represented by the following formula (11) by a conventional method to obtain a compound represented by the following formula (12). obtain.

Formula (11)

Formula (12)

The obtained compound of the above formula (12) is diazotized by a conventional method, and then the obtained diazo compound and a compound represented by the following formula (13) are subjected to a coupling reaction by a conventional method, whereby The azo compound of the present invention represented by the formula (1) can be obtained. The compound represented by the following formula (13) can be synthesized according to the method described in Patent Document 4.

Formula (13)

[0051] The diazotization of the compound of the formula (6) is carried out by a method known per se, for example, in an inorganic acid medium, for example, 5-30 ° C, preferably 0-; nitrite at a temperature of 15 ° C, For example, using an alkali metal nitrite such as sodium nitrite. Coupling of the diazotized compound of formula (6) with the compound of formula (7) is also carried out under conditions known per se. It is advantageous to carry out in water or an aqueous organic medium, for example at a temperature of 5-30 ° C., preferably 0-25 ° C., and at an acidic to neutral pH value, eg pH; Since the diazotization reaction solution is acidic and the reaction system is further acidified by the progress of the coupling reaction, the pH value of the reaction solution is adjusted to a preferable pH condition by adding a base. Examples of the base include alkali metal hydroxides such as lithium hydroxide and sodium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate, acetates such as sodium acetate, ammonia, and organic amines. Can be used. The compound of formula (6) and the compound of formula (7) are used in approximately stoichiometric amounts.

[0052] The diazotization of the compound of the formula (8) is carried out by a method known per se, for example, a nitrite such as an inorganic acid medium at a temperature of, for example, 5 to 40 ° C, preferably 5 to 30 ° C. Nitrous acid This is done using an alkali metal nitrite such as sodium. The coupling of the diazotized compound of formula (8) with the compound of formula (9) is also carried out under conditions known per se. It is advantageous to carry out in water or an aqueous organic medium, for example at a temperature of −5 to 40 ° C., preferably 10 to 30 ° C., and at an acidic to neutral pH value, for example pH 2-7. Since the diazotization reaction liquid is acidic and the reaction system is further acidified by the progress of the coupling reaction, the pH value of the reaction liquid is adjusted to a preferable pH condition by adding a base. The same base as described above can be used. The compound of formula (8) and the compound of formula (9) are used in approximately stoichiometric amounts.

[0053] The diazotization of the compound of formula (10) is carried out in a manner known per se, for example nitrite, for example nitrous acid, in an inorganic acid medium, for example at a temperature of 5-50 ° C, preferably 5-40 ° C. It is carried out using an alkali metal nitrite such as sodium nitrate. Coupling of the diazotized compound of formula (10) with the compound of formula (11) is also carried out under conditions known per se. It is advantageous to carry out in water or an aqueous organic medium, for example at a temperature of -5 to 50 ° C, preferably 10 to 40 ° C, and at an acidic to neutral pH value, for example pH 2-7. Since the diazotization reaction solution is acidic and the reaction system is further acidified by the progress of the coupling reaction, the pH value of the reaction solution is adjusted to a preferable pH condition by adding a base. As the base, the same ones as described above can be used. The compound of formula (10) and the compound of formula (11) are used in approximately stoichiometric amounts.

[0054] The diazotization of the compound of formula (12) is also carried out in a manner known per se, for example nitrites such as eg -5 to 50 ° C, preferably 10 to 40 ° C in an inorganic acid medium. It is carried out using an alkali metal nitrite such as sodium nitrite. Coupling of the diazotized compound of formula (12) with the compound of formula (13) is also carried out under conditions known per se. It is advantageous to carry out in water or an aqueous organic medium, for example at a temperature of 5 to 50 ° C., preferably 10 to 40 ° C., and at a weakly acidic to alkaline pH value. Preferably, it is carried out at a weakly acidic to weakly annoying pH value, for example, pH 5 to 10; the pH value is adjusted by adding a base. Examples of the base include alkali metal hydroxides such as lithium hydroxide and sodium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate, acetates such as sodium acetate, ammonia and organic amines. Can be used. The compounds of formulas (12) and (13) are used in approximately stoichiometric amounts.

[0055] Preferable specific examples of the compound of the formula (1) include, but are not particularly limited to, compounds represented by the formulas shown in Tables 2 and 3 below. In each table, acidic functional groups such as sulfo and carboxy are described in the form of free acids.

[0056] [Table 2]

[0057] [Table 3]

In order to make the azo compound of the formula (1) into a desired salt, a salting-out force by adding a desired inorganic salt or organic cation salt to the reaction solution after the coupling reaction, or Then, the mineral compound is separated in the form of a free acid by adding a mineral acid to the reaction solution, and if necessary, the inorganic salt is washed with water, acidified water or / and an aqueous organic medium or the like. After removal, it is neutralized with the desired inorganic or organic base in an aqueous medium. In the latter case, the corresponding desired salt can be obtained in the form of a solution. In the former case, the desired salt precipitated by salting out is separated as a solid by means of filtration separation or the like, and if necessary, Then, the desired salt can be obtained in the form of a solid by purification by means of recrystallization from water or / and an aqueous organic medium, filtration separation or the like, and drying as necessary. In the above, acidic water refers to an acid obtained by dissolving an organic acid such as mineral acid such as sulfuric acid or hydrochloric acid in water. The aqueous organic medium means an organic substance miscible with water and / or a mixed solution of water and an organic solvent miscible with water. Specific examples of the organic solvent miscible with water include water-soluble organic solvents described later. Even if it is an organic substance not normally classified as a solvent, it can be dissolved in water and used as an aqueous organic medium as long as it is miscible with water.

Examples of inorganic salts include alkali metal salts such as lithium chloride, sodium chloride and potassium chloride, and ammonium salts such as ammonium chloride and ammonium bromide. Examples of organic cation salts include the above formula ( Examples thereof include halogen salts of organic amines represented by 5).

Examples of inorganic bases include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and lithium hydroxide, ammonium hydroxide, or alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate. Examples of organic bases include organic amines such as diethanolamine and triethanolamine, which are used to form organic ammonium ions represented by the above formula (5). However, it is not limited to these.

[0059] A typical use of the compound of the present invention includes use as a black dye for an ink composition. A solution obtained by dissolving the azo compound of the present invention in a liquid medium, for example, an aqueous composition containing the azo compound of the present invention can be used for coloring various materials. For example, it can be used for dyeing fibers, for producing an ink composition, or as an ink composition.

[0060] For example, a reaction liquid containing the azo compound of the present invention, such as a reaction liquid in Example 1 (4) described later, can be used directly in the production of the ink composition. However, usually, it is first dried, for example, spray-dried to separate the azo compound, or by adding inorganic salts such as sodium chloride, potassium chloride, calcium chloride, sodium sulfate to the reaction solution. Salting out, acid precipitation by adding mineral acids such as hydrochloric acid, sulfuric acid, nitric acid to the reaction solution Alternatively, the azo compound of the present invention is precipitated by acid salting out by combining salting out and acid precipitation as described above, taken out by filtration separation or the like, and then used to prepare an ink composition.

[0061] The ink composition of the present invention generally contains water containing the azo compound of the present invention in an amount of 0.;! To 20% by mass, preferably;! To 10% by mass, more preferably 2 to 8% by mass. It is a composition used as a main medium. The ink composition of the present invention may further contain, for example, 0 to 30% by mass of a water-soluble organic solvent and 0 to 15% by mass, preferably 0 to 10% by mass of an ink preparation agent. The pH of the ink composition is preferably pH 5 to 11 and more preferably pH 7 to 10 in order to improve storage stability. The surface tension of the ink composition is preferably 25 to 7 OmN / m, more preferably 25 to 60 mN / m. Furthermore, the viscosity of the ink composition is preferably 30 mPa's or less, more preferably 20 mPa's or less. The pH and surface tension of the ink composition of the present invention can be adjusted with a pH adjusting agent and a surfactant as will be described later.

[0062] As described above, the ink composition of the present invention dissolves the azo compound of the present invention in water or a water-soluble organic solvent (an organic solvent miscible with water), and an ink preparation agent is added as necessary. It is possible to manufacture by S. When this ink composition is used as an ink for an ink jet printer, it is preferable to use an azo compound having a low content of inorganic substances such as metal cation chlorides and sulfates as the azo compound of the present invention. The standard of the content is, for example, about 1% by mass or less (vs. the total mass of dye). In order to produce the azo compound of the present invention with a small amount of inorganic substances, for example, a conventional method using a reverse osmosis membrane or a dried product or wet cake of the azo compound of the present invention is mixed with alcohol such as methanol and water. It can be desalted by stirring, mixing, filtering and drying! /.

[0063] Specific examples of the water-soluble organic solvent used for the preparation of the ink composition include (C1-C4) such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, and the like. ) Al-Nol; Carboxylic amides such as N, N dimethylformamide or N, N dimethylacetamide; Ratatas such as 2-pyrrolidone, N-methylpyrrolidin 2one; 1,3 dimethylimidazolidine 2one or 1, 3 Cyclic ureas such as dimethylhexahydropyrimido-2-one; acetone, methyl ester Aliphatic ketones or aliphatic ketoalcohols such as tilketone, 2-methyl-2-hydroxypentane-4-one; cyclic ethers such as tetrahydrofuran, dioxane; ethylene glycol mononole, 1,2-propylene glycolenole, 1,3-propylene glycolenole 1, 2-butylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, methanol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol Mono-, oligo- or polyalkylene glycols or thioglycols having (C2 to C6) alkylene units such as thiodiglycol, dithiodiglycol, etc .; polyols such as glycerol, hexane 1, 2, 6 triol (Preferred Or triol); a monovalent mononole ether such as ethylene glycol monomethyl ether or monoethyl etherenole, diethyleneglycolenomonomethylenoateolene or monoethinoleethenore, triethyleneglycolenomonomonochinenoatenore or monoethinoreethenore Or di (C1 to C4) alkyl ether; _Ί -butyral rataton or dimethyl sulfoxide. These organic solvents may be used alone or in combination of two or more.

[0064] Examples of the ink preparation used in the preparation of the ink composition include antiseptic / antifungal agents, rhodium adjusting agents, chelating reagents, antifungal agents, water-soluble ultraviolet absorbers, and water-soluble polymer compounds. And dye solubilizers, antioxidants, and surfactants. These drugs are described below.

[0065] Specific examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ρ-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazoline-3one, and salts thereof. . These are preferably used in the ink composition in an amount of 0.02-1.00% by mass.

[0066] Examples of preservatives include organic sulfur-based, organic nitrogen-sulfur-based, organic halogen-based, halogenyl sulfone-based, odopropargyl-based, ハロ haloalkylthio-based, nitrile-based, pyridin-based, 8-year-old xylquinoline-based, Benzothiazole, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiazine, anilide, adamantane, dithiocarbamate, brominated indanone And compounds such as benzyl bromacetate and inorganic salts It is.

Specific examples of the organic halogen compounds include sodium pentachlorophenol.

Specific examples of pyridine oxide compounds include sodium 2-pyridinethiol 1-oxide.

Examples of isothiazoline-based compounds include 1,2-benzisothiazoline-3-one, 2 n otachinole 4 isothiazoline-3 on, 5 chloro-2 methylenole 4 isothiazoline 1-on, 5 black 1-methyl 4 isothiazoline 1-on 3 Examples thereof include magnesium chloride, 5 1-methyl 2-isothiazoline 3-on calcium chloride, 2-methyl 4-isothiazoline-3 on-calcium chloride, and the like. Specific examples of other antiseptic / antifungal agents include sodium sorbate, sodium benzoate, and anhydrous sodium acetate.

[0067] As the pH adjuster, any substance can be used as long as it can control the pH of the ink within a range of, for example, 5 to 11 without adversely affecting the prepared ink. Specific examples include alkanolamines such as diethanolamine, triethanolamine, and N-methylethanolamine; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; ammonium hydroxide ( Ammonia water), or alkali metal carbonates such as lithium carbonate, sodium carbonate, sodium bicarbonate, and potassium carbonate; inorganic bases such as sodium silicate and disodium phosphate; and alkali metals of organic acids such as potassium acetate Examples include salt.

[0068] Specific examples of the chelating reagent include, for example, sodium ethylenediamine tetraacetate, sodium nitrite triacetate, sodium hydroxyethylethylenediamine triacetate, sodium diethylenetriaminepentaacetate, sodium uracil diacetate and the like.

[0069] Specific examples of the antifungal agent include, for example, acidic sulfite, sodium thiosulfate, ammonium thiodalcholate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite. Light etc. are mentioned.

Examples of water-soluble ultraviolet absorbers include, for example, sulfonated benzophenone compounds, benzotriazole compounds, salicylic acid compounds, cinnamic acid compounds, and triazine compounds. Compounds.

Specific examples of the water-soluble polymer compound include polybulal alcohol, cellulose derivative, polyamine, polyimine and the like.

[0070] Specific examples of the dye dissolving agent include ε-force prolatatam, ethylene carbonate, urea and the like.

As examples of the antioxidant, for example, various organic and metal complex anti-fading agents can be used. Examples of the organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Is mentioned.

[0071] Examples of the surfactant include known surfactants such as anionic, cationic, and nonionic surfactants.

Examples of anionic surfactants include alkyl sulfonates, alkyl carboxylates, a-olefin sulfonates, polyoxyethylene alkyl ether acetates, N acyl amino acids and their salts, N acyl methyl taurate, Alkyl sulfate polyoxy alkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid sarcophagus, castor oil sulfate ester, lauryl alcohol sulfate ester, alkyl phenol type phosphate ester, alkyl type phosphate ester, alkyl Examples include aryl sulfonate, jetyl sulfonate, jetyl hexyl sulfonate, dioctenosulfonate sulfonate, and the like.

[0072] Examples of cationic surfactants include 2-bulupyridine derivatives and poly-4-bulupyridine derivatives.

[0073] Specific examples of amphoteric surfactants include lauryl dimethylamino acetate betaine, 2-alkynole N-carboxymethyl-N hydroxyethyl imidazolinium betaine, coconut oil fatty acid amidopropyl dimethylamino acetate betaine , Polyoctylpolyaminoethylglycine and other imidazoline derivatives.

[0074] Specific examples of the nonionic surfactant include polyoxyethylene nouryl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether. Tenoles, ethers such as polyoxyethylene alkyl ether, polyoxyethylene oleic acid, polyoxyethylene oleate, polyoxyethylene distearate estenole, sonorebitan laurate, sonorebitan monostearate, sonorebitan monoole Ester, Sorbitan Sesquioleate, Poly-xoxyethylene mono-rate, Poly-xoxyethylene stearate and other ester series, 2, 4, 7, 9 Tetramethyl-5 Decyne 4,7diol, 3, 6-Dimethyl 4 -Acetylene glycol (alcohol) series such as octyne 3, 6-diol, 3, 5-dimethyl-one hexin 3ol (for example, Nissin Chemical Industry Co., Ltd., quotient Lorofai Surfinore 104, 105, 82, 465 , Norefin STG, etc.). These ink preparation agents are used alone or in combination.

[0075] The ink composition of the present invention can be obtained by mixing and stirring the above components in an arbitrary order. The obtained ink composition may be filtered with a membrane filter or the like, if desired, in order to remove impurities. In addition to the azo compound of the present invention, other pigments having various hues may be mixed in order to adjust the black color as the ink composition. In that case, black having other hues, yellow, magenta, cyan, and other colors such as red and blue can be mixed and used.

[0076] The ink composition of the present invention is suitable for power writing inks, aqueous printing inks, information recording inks and the like that can be used in various fields. It is particularly suitable as an inkjet ink (composition), and is suitably used in the inkjet recording method of the present invention described later.

Next, the ink jet recording method of the present invention will be described. The ink jet recording method of the present invention is characterized by performing recording using the ink composition of the present invention. In the ink jet recording method of the present invention, recording is performed on the recording material by ejecting the ink composition of the present invention as small droplets by ink jetting and adhering to the recording material. There are no particular restrictions on the ink nozzles used in the ink jet, etc. The purpose can be appropriately selected according to the ink jet system. As an inkjet method, a known method, for example, a charge control method that ejects ink using electrostatic attraction, a drop-on-demand method (pressure pulse method) that uses vibration pressure of a piezoelectric element, an electric signal, and the like Is an acoustic beam that emits ink using radiation pressure by irradiating the ink with an acoustic beam An ink jet method, a thermal ink jet (Bubble Jet (registered trademark)) method, or the like that uses the pressure generated by forming bubbles by heating ink can be employed. The ink jet method includes a method called a photo ink which ejects a large number of inks with a low density / small ink volume. In addition, in order to improve the image quality, a method using a plurality of inks having substantially the same hue and different densities and a method using a colorless and transparent ink are also included.

[0078] The aqueous composition containing the azo compound of the present invention can also dye a material comprising cellulose. In addition, other materials having a carbonamide bond can be dyed, and can be widely used for dyeing leather, fabric, paper, and the like.

[0079] The colored product of the present invention includes any of those colored with the azo compound of the present invention.

Usually, it can be obtained by coloring various articles with the aqueous composition of the present invention containing the same, particularly the ink composition of the present invention. More preferably, the force obtained by coloring various articles such as a recording material with an ink jet printer using the ink composition of the present invention can be achieved. Examples of materials that can be colored include sheets for information transmission such as paper and film, fibers and cloths (cellulose, nylon, wool, etc.), leather, and base materials for color filters. Among them, the information transmission sheet is preferably a surface-treated sheet, specifically, a sheet, a synthetic paper, a film or the like provided with an ink receiving layer. The ink-receiving layer is formed by, for example, impregnating or coating the above-mentioned base material with a cationic polymer, or by using a porous white inorganic substance that can absorb the pigment in the ink such as porous silica, alumina sol, or special ceramics. It is provided by coating the surface of the base material together with a hydrophilic polymer such as polybulurpyrrolidone. Such an ink receiving layer is usually called ink jet paper (film), glossy paper (film), etc., for example, professional photo paper, sono photo photo, mat photo paper (g). Cannon Co., Ltd.), photo paper (glossy), PM matte paper, crispia (all made by CIE Epson Co., Ltd.), advanced photo paper, premium plus photo paper, premium gloss film, photo paper (all in Japan) Commercially available products such as Hewlett-Packard (manufactured by Packard Co., Ltd.) and Photolike QP (manufactured by Koni Riki Co., Ltd.) are available. Of course, regular paper can also be used.

[0080] Of these, information is recorded on an information transmission sheet coated with a porous white inorganic substance on the surface. The power of the ink composition of the present invention is known to increase the discoloration due to ozone gas. The ink composition of the present invention is excellent in ozone gas resistance! Demonstrate the effect.

In order to record on a recording material such as an information transmission sheet by the ink jet recording method of the present invention, droplets of the ink composition of the present invention may be attached to the recording material by ink jet V, . For example, a container containing the above ink composition may be set at a predetermined position of an ink jet printer, and ink may be ejected and recorded on a recording material by an ordinary method. In the ink jet recording method of the present invention, the black ink composition of the present invention is mixed with a known magenta ink composition, cyan ink composition, yellow ink composition, and if necessary, a green ink composition, blue (or violet). ) Ink compositions and red (or orange) ink compositions can be used in combination. The ink composition of each color is poured into each container, and the container is loaded into a predetermined position of the ink jet printer in the same manner as the container containing the aqueous black ink composition for ink jet recording of the present invention. Along with the ink composition, it is used for recording in full color.

[0082] The azo compound of the present invention is excellent in water solubility, and the ink composition of the present invention containing this azo compound has storage stability without crystal precipitation, physical property change, color change, etc. after long-term storage. Is good. Further, the black ink composition for recording containing the azo compound of the present invention is suitable for ink jet recording and writing instruments, and when the ink composition is recorded on plain paper and ink jet dedicated paper, The recorded image is black with high print density, and also has excellent ozone gas resistance and light resistance, and does not cause bronzing.

Example

[0083] Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to the following examples. In the text, “parts” and “%” are based on mass unless otherwise specified. In the following formulas, an acidic functional group such as sulfo is described in the form of a free acid. The solubility is the solubility in water at room temperature (usually 20-30 ° C).

[0084] Example 1

(1) Compound of formula (14) below (CI Acid Yellow 9) 5. Suspend 4 parts in 40 parts of water, By adding sodium hydroxide to the solution, the pH value was adjusted to 4.0 to 5.0 and dissolved. After adding 6.0 parts of 35% hydrochloric acid to this solution, 2.9 parts of 40% aqueous sodium nitrite solution was added at 15 to 25 ° C. to diazotize.

Formula (14)

[0086] This diazo suspension was prepared by adding the compound of the following formula (15) obtained by the method described in JP-A-2004-083492 with 3.6 kg of water and 30 mg of water and sodium hydroxide. The solution was added dropwise at 15 to 25 ° C. over about 30 minutes to a solution dissolved to pH 4.5 to 5.5 by caro. During the dropwise addition, the pH value of the solution was maintained at 4.0 to 5.0 by adding sodium carbonate. The mixture was then stirred for 2 hours, acidified by adding 35% hydrochloric acid, and the precipitate was separated by filtration to obtain a wet cake containing a disazo compound represented by the following formula (16).

[0089] (2) The wet cake containing the disazo compound of the formula (16) obtained in the above (1) was dissolved in 130 parts of water. Thereto was added 4.0 parts of 35% hydrochloric acid, and then 2.4 parts of 40% aqueous sodium nitrite solution was added at 20 to 35 ° C. to diazotize. This diazo suspension was added to a solution obtained by dissolving 2.9 parts of the compound of the formula (15) in 25 parts of water and adding ρΗ4 · 5 to 5 · 5 by adding sodium hydroxide. The solution was added dropwise at 5 to 25 ° C over about 30 minutes. During the dropwise addition, the pH value of the solution was kept at 3.5 to 4.5 by adding sodium carbonate. Thereafter, the solution was stirred for 2 hours, salted out by addition of sodium chloride, and the precipitate was separated by filtration to obtain a wet cake containing a trisazo compound of the following formula (17).

Formula (17)

[0090]

[0091] (3) 2- (Chanomethyl) benzimidazole and ethyl acetate are heated and reacted in ethanol in the presence of sodium methoxide, and acidified by addition of dilute hydrochloric acid to the reaction solution. 8. 8. 9 parts of compound were obtained. It was slowly added to 64 parts of 6% fuming sulfuric acid at 15-25 ° C. After the addition, the resulting liquid was stirred at the same temperature for 2 hours, and then dropped into 190 parts of ice water in about 10 minutes. The precipitated crystals were separated by filtration, washed with a solution of sodium chloride in dilute hydrochloric acid, and dried to obtain 10.7 parts of the compound of the following formula (19).

[0094] (4) The wet cake containing the trisazo compound of the formula (17) obtained in (2) above is dissolved in 150 parts of water to a pH value of 6.0 to 7.0 by adding sodium hydroxide, 40% nitrous acid here After the addition of 2.1 parts of an aqueous sodium solution, this solution was added dropwise to a mixture of 4.7 parts of 35% hydrochloric acid and 40 parts of water at 20 to 35 ° C. to diazotize. This diazo suspension was mixed with 3.0 mg of the compound of formula (19) obtained in (3) above, and the pH was adjusted to 8 by adding 50 kg of water and sodium hydroxide. It was added dropwise at 20 to 35 ° C. to the solution dissolved as 0 to 9.0. During the addition, the pH value was maintained at 7.0 to 8.0 by adding sodium carbonate. After the dropwise addition, the obtained liquid was stirred at the same temperature for 6 hours, salted out by adding sodium chloride, and the precipitate was separated by filtration. The obtained wet cake was dissolved in 150 parts of water, crystallized by adding 120 parts of methanol, and the precipitate was separated by filtration. The obtained wet cake is further dissolved in 150 parts of water, and then crystallized with an added force □ of 180 parts of methanol. The precipitate is separated by filtration, dried, and the azo compound of the following formula (20) of the present invention ( Compound No. 1 in Table 2) 9. 6 parts were obtained as the sodium salt. The maximum absorption wavelength (λ max) of this compound in an aqueous solution having a pH of 7 to 8 was 580 nm, and the solubility was 100 g / L or more. Formula (20)

Example 2

(1) 6.0 parts of the compound of the formula (19) were dissolved in 40 parts of 95% sulfuric acid, heated to 60 ° C. and stirred for 1.5 hours. After cooling to room temperature, the resulting reaction solution was added dropwise to 120 parts of ice water, followed by addition of sodium chloride, and the crystals were separated by filtration. The crystals were washed on a funnel with dilute hydrochloric acid in which sodium chloride was dissolved, and dried to obtain 5.1 parts of the compound of the following formula (21).

Formula (21)

(2) In the same manner as in Example 1 except that, in Example 1, (4), 3.0 parts of the compound of formula (19) are replaced with 3.2 parts of the compound of formula (21). The azo compound of the following formula (22) of the invention (the compound of No. 2 in Table 2) 9.7 parts was obtained as a sodium salt. The maximum absorption wavelength (λmax) of this compound in an aqueous solution having a pH of 7 to 8 was 573 nm, and the solubility was 100 g / L or more.

Formula (22)

[0099]

[0100] Example 3

(1) Dissolve 3.9 parts of 2-aminobenzene-1,5-disulfonic acid in 30 parts of water, add 2.2 parts of 35% hydrochloric acid to it, and adjust the liquid temperature to 0-5 ° C. 2.7 parts of 40% aqueous sodium nitrite solution was added dropwise to diazotize. To this diazo solution, a solution prepared by dissolving 4.3 parts of the compound of the formula (15) in 50 parts of water and adding sodium hydroxide to a pH value of 4.5 to 5.5 is added dropwise over about 20 minutes. did. After the dropwise addition, the obtained liquid was stirred at 10 to 20 ° C. for 4 hours to obtain a solution containing a compound of the following formula (23).

Formula (23)

[0102] (2) In Example 1, (1), instead of using 5/4 parts of the compound of formula (14), a solution containing the compound of formula (23) obtained in (1) above is used. Except for the above, in the same manner as in Example 1, 8.9 parts of the azo compound of the following formula (24) of the present invention (the compound of No. 6 in Table 2) was obtained as a sodium salt. The maximum absorption wavelength (λ max) of this compound in aqueous solution with pH 7-8 is 581 nm and the solubility was lOOg / L or more.

Formula (24)

[0103]

[0104] Examples 4 to 6

(A) Preparation of ink

The following components were mixed and filtered with a 0.45 m membrane filter to remove contaminants, thereby obtaining a black ink composition of the present invention.

Water used was ion exchange water. At the time of ink preparation, the pH of the ink was adjusted to pH 7-9 with sodium hydroxide, and then ion-exchanged water was added to make the total amount 100 parts.

[0105] Table 4

Compounds obtained in the above Examples;! To 3 4.0 parts

5. 0 copies

N-Methyl-2-pyrrolidone 4.0 parts

z call 3.0 copies

, Ichinore 2.0

Surfactant 0.1 part

(Product name Surfinol 104 manufactured by Nissin Chemical Industry Co., Ltd.)

Water + sodium hydroxide 76.9 parts

Total 100.0 copies

In Table 4, the compounds of the above formulas (20), (22) and (24) were used as the compounds obtained in Example 13 above. The obtained ink composition of the present invention and The tests used are Examples 4, 5 and 6, respectively.

These water-based ink compositions did not cause precipitation separation during storage and did not change their physical properties even after long-term storage!

[0107] Comparative Example 1

The ink of Comparative Example 1 having the same composition as in Table 4 (Examples 4 to 6) except that the dye of Table 11 in Table 11 of Patent Document 1 (the following formula (25)) is used as the water-soluble inkjet dye. A composition was prepared.

Formula (25)

[0108]

[0109] Comparative Example 2

As in Comparative Example 1, the above-mentioned Table 4 (Examples 4 to 6) was used except that the dye AN-250 (formula (26)) described in Example 1 of Patent Document 3 was used as the water-soluble inkjet dye. The ink composition of Comparative Example 2 was prepared with a composition similar to

Formula (26)

[0111] (B) Inkjet printing

Using the ink composition obtained above, using an inkjet printer (trade name: PIXUS ΪΡ4 100 manufactured by Canon), special glossy paper 1 (product name: Professional Photo Paper PR—101), special gloss Inkjet recording was performed on two types of paper 2 (manufactured by EPSON Corporation, trade name: photographic paper, glossy> KA420PSK).

At the time of printing, an image pattern was made so that the reflection density could be obtained in several gradations, and a black printed matter was obtained. [0112] The light resistance test and the ozone gas resistance test were evaluated using a colorimeter (SpectroEye GRETAG—manufactured by M ACBETH), using the gradation part where the reflection density D value of the printed material before the test was closest to 1.0. went.

[0113] (C) Evaluation of recorded image

The recorded image by the water-based ink composition of the present invention was evaluated for density change after the light resistance test and after the ozone gas resistance test. The test was conducted on special glossy papers 1 and 2. The results are shown in Table 5. The specific test method is shown below.

1) Light resistance test

Using a xenon weatherometer (manufactured by Ci4000 ATLAS), irradiation was carried out for 50 hours under the conditions of 0.36 W / square meter, illuminance, humidity 60% RH, and temperature 24 ° C. After completion of the test, the colorimetry was performed using the above colorimeter, and the dye residual ratio was determined by (reflected density after test / reflected density before test) X I 00 (%) and evaluated according to the following criteria.

〇 Survival rate: 90% or more

△ Residual rate: Less than 90%, 80% or more

X Residual rate: Less than 80%

The results are shown in Table 5.

2) Ozone gas resistance test

Using an ozone weatherometer (manufactured by Suga Test Instruments Co., Ltd.), the print sample was allowed to stand for 4 hours at an ozone concentration of 12 ppm, a humidity of 60% RH, and a temperature of 24 ° C. After completion of the test, the colorimetry was performed using the above colorimeter, and the dye residual ratio was determined by (reflected density after test / reflected density before test) X 100 (%) and evaluated according to the following criteria.

〇 Survival rate: 70% or more

△ Residual rate: 60% or more and less than 70%

X Residual rate: Less than 60%

The results are shown in Table 5.

[0114] Table 5

Light resistance Ozone gas resistance

Example 4 (Formula (20)) Exclusive glossy paper 1 〇〇

Exclusive glossy paper 2 ○ ○

Example 5 (Formula (22))

Exclusive glossy paper 1 〇〇

Exclusive glossy paper 2 ○ ○

Example 6 (Formula (24))

Exclusive glossy paper 1 〇〇

Exclusive glossy paper 2 ○ ○

Comparative Example 1 (Formula (25))

Exclusive glossy paper 1

Exclusive glossy paper 2 Δ 〇

Comparative Example 2 (Formula (26))

Exclusive glossy paper 1

Exclusive glossy paper 2 Δ 〇

As is apparent from the results in Table 5, the image recorded with the ink composition containing the azo compound of the present invention is equivalent in ozone gas resistance compared to the image of the conventional black dye (comparative example). It showed the above fastness, and good results were obtained with any special glossy paper. That is, Comparative Examples 1 and 2 have a dye residual ratio of less than 60% when dedicated glossy paper 1 is used, while Examples 4 to 6 of the present invention are 70 when any dedicated glossy paper is used. A pigment residual ratio of% or more was shown. Further, the difference in light resistance appears more clearly, and Examples 4 to 6, which are ink compositions containing the azo compound of the present invention, have a dye residual ratio of 90% in any of the dedicated light papers. Forces shown above Comparative Examples 1 and 2 are both less than 90% 80% when exclusive glossy paper 2 is used, and less than 80% when both special glossy paper 1 is used. Compared with these results, Examples 4 to 6 of the present invention obtained remarkably good results. This shows that the fastness of the image recorded by the azo compound of the present invention is extremely excellent.

In addition, the azo compound of the present invention is highly soluble and stable, so a high concentration ink can be designed. Industrial applicability

The ink composition containing the azo compound of the present invention is suitably used as a black ink liquid for ink jet recording and writing instruments.

Claims

The scope of the claims

An azo compound represented by the following formula (1) or a salt thereof

{In the formula, the group A is a substituted phenyl group, which is a carboxy group, a sulfo group, a hydroxy group, an acetylamino group, a chlorine atom, a cyano group, a nitro group, a sulfamoyl group, a (C1-C4) alkyl group, (C1-C4 ) Alkoxy group (which may be substituted with a group selected from the group consisting of hydroxy group, (C1-C4) alkoxy group, sulfo group and carboxy group), and (C1-C4) alkylsulfonyl group (hydroxy group) , Substituted with a sulfo group or a carboxy group, and having at least one substituent selected from the group consisting of V,

R ¹ represents a (C ¹ -C 4) alkyl group (substituted with a carboxy group! /, May be selected), a phenyl group (which may be substituted with a sulfo group), or a carboxy group,

R ² represents a cyano group, a strong rubermoyl group or a carboxy group,

R ⁵ to R ^1Q are each independently a hydrogen atom, carboxy group, sulfo group, acetylamino group, (C1-C4) alkyl group or (C1-C4) alkoxy group (hydroxy group, (C1-C4) alkoxy group, Substituted with a sulfo group or a carboxy group represents! /, Or may be! /,)}.

[2] At least one of the substituents of the group A is a sulfo group or a carboxy group, and among the combinations of three substituents of R ⁵ and R ⁶ , R ⁷ and R ⁸ , and R ⁹ and R ^1Q , at least The azo compound according to claim 1, wherein one substituent of each combination is a sulfo group or a sulfopropoxy group.

[3] The azo compound according to claim 1, which is represented by the following formula (2):

{Wherein R ⁵ represents a sulfo group, a sulfoethoxy group, a sulfopropoxy group or a sulfobutoxy group, R ⁷ and R ⁹ represent a sulfoethoxy group, a sulfopropoxy group or a sulfobutoxy group, R ⁶ , R ⁸ and R ^1Q Each independently represents a hydrogen atom, an acetylamino group, a methyl group, an ethyl group, a methoxy group or an ethoxy group, and R ^u , R ¹² and R ¹³ each independently represent a hydrogen atom, a carboxy group, a sulfo group, Hydroxy group, acetylamino group, chlorine atom, cyano group, nitro group, sulfamoyl group, (C1-C4) alkyl group, (C1-C4) alkoxy group (hydroxy group, (C1-C4) alkoxy group, sulfo group and carboxy group Substituted with a group selected from the group consisting of a group! /, Or may be! /, Or (C1-C4) an alkylsulfonyl group (a hydroxy group, a sulfo group or a carboxy group). It represents which may have been or may), respectively, at least one of R ¹ R ¹² and R ¹³ represents a group other than a hydrogen atom}.

[4] The azo compound according to claim 1 or 3, wherein R ¹ is a methyl group, R ² is a cyano group or a cananolamoyl group, R ³ is a hydrogen atom, and R ⁴ is a sulfo group.

[5] R ^U, R ¹² and R ^13, R ^U, on condition that one of at least one representative of the group other than a hydrogen atom of R ¹² and R ^13, each independently, a hydrogen atom, a sulfo group , Carboxy group, sulfopropylsulfonyl group or acetylamino group, R ¹ is methyl group, R ² is cyano group or rubamoyl group, R ³ is hydrogen atom, R ⁴ is sulfo group, R ⁵ is sulfo group or sulfopropoxy group The azo compound according to claim 3, wherein the group, R ⁷ and R ⁹ force S sulfopropoxy group, R ⁶ , R ⁸ and R ^1Q are each independently a hydrogen atom or a methyl group.

[6] When the substitution position on the benzene ring of R ^{U to} R ¹³ is the 1st position of the substitution of the azo group, R ¹¹ force ¾ position or 3 position, R ¹² is 4 position and R ¹³ is 5 position R ^U is a hydrogen atom, a sulfo group or a carboxy group, R ¹² is a hydrogen atom, a sulfo group, an acetylamino group or a sulfopropylsulfonyl group, R ¹³ is a hydrogen atom or a sulfo group, R ^u , At least one of R ¹² and R ¹³ is a group other than a hydrogen atom, and R ¹ is a methyl group or an n-propyl group. R ² is a cyano group or a strong rubamoyl group, R ³ is a hydrogen atom, R ⁴ is a sulfo group, R ⁵ is a sulfo group or a sulfopropoxy group, and R ⁶ is a hydrogen atom or a methyl group. The azo compound according to claim 3, wherein R ⁷ and R ^{9 are} sulfopropoxy groups, and R ⁸ and R ^1Q are methyl groups.

[7] R ¹² is a sulfo group, the substitution position is para to the azo group, and R ¹¹ and R ¹³ are hydrogen atoms

R ¹ is a methyl group, R ² is a cyano group or canolamoyl group, R ³ is a hydrogen atom, R ⁴ is a sulfo group, R ⁵ is a sulfo group, R ⁶ is a hydrogen atom, R ⁷ and R ⁹ force S sulfo The azo compound according to claim 3, wherein the propoxy group, R ⁸ and R ^1Q are methyl groups.

[8] An ink composition comprising at least one azo compound according to [1].

[9] An ink jet recording method comprising attaching the ink composition according to claim 8 to a recording material by ink jet.

10. The ink jet recording method according to claim 9, wherein the recording material in the ink jet recording method is an information transmission sheet.

11. The ink jet recording method according to claim 10, wherein the information transmission sheet contains a porous white inorganic substance.

12. An ink jet printer loaded with a container containing the ink composition according to claim 8.

[13] A colored product colored with the azo compound according to claim 1.