JP2007023072A - Yellow pigment composition for image recording and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a monoazo yellow pigment composition for image recording for forming a color image in an inkjet method or the like that exhibits excellent image reproducibility, image retention and light resistance with a good balance. <P>SOLUTION: The yellow pigment composition for image recording comprises a main monoazo yellow pigment represented by general formula (1) and one or two kinds of other monoazo yellow pigments. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a yellow pigment composition for image recording and a method for producing the same, and more specifically, to a yellow pigment composition for image recording used for color image formation such as electrophotography, electrostatic printing method, and ink jet method, and the production thereof. It is about the method.

  In order to obtain high-quality color image reproducibility in color image formation by electrophotography, electrostatic printing method, ink-jet method, etc., the following characteristics, that is, optical properties such as hue, transparency, coloring power, etc. Durability such as properties, light resistance, heat resistance, solvent resistance, etc. is required, and further, there is a requirement that there is no problem in the safety of mutagenesis and decomposition products caused by the colorant. Therefore, from the viewpoint of durability, the colorant used is generally preferably a pigment rather than a dye. Examples of yellow pigments include benzidine-based disazo compounds such as CI Pigment Yellow 12, 13, 17, and 83. Pigment, condensed pigment azo pigments such as CI Pigment Yellow 93, 95, 128, 151, 154, 155, and 180 are used.

  However, benzidine-based monoazo pigments are good for color image reproducibility mainly influenced by optical properties such as hue, transparency and coloring power, but are not preferable for image retention mainly affected by light resistance, In addition, safety has been questioned because of decomposition products derived from benzidines. On the other hand, condensed azo pigments have satisfactory image retention and safety compared to benzidine-based disazo pigments, but have disadvantages such as high price and insufficient color image reproducibility. Furthermore, there are also problems with dispersibility, and the current situation is that each has advantages and disadvantages.

For example, Patent Document 1 discloses a technique for imparting aptitude in color image formation by an inkjet method or the like. However, this azo dispersant has a tendency to have insufficient light resistance depending on the application.
JP 2004-204221 A

  The present invention provides a well-balanced yellow pigment for image recording with good image reproducibility and image retention, and excellent light fastness for color image forming methods such as electrophotography, electrostatic printing, and ink jet methods. It is an object of the present invention to provide a monoazo-based yellow pigment composition for image recording suitable as a colorant and a method for producing the same.

  The yellow pigment composition for image recording of the present invention comprises a monoazo yellow main pigment represented by the following general formula (1), a monoazo yellow pigment represented by the following general formula (2) and / or the following general formula (3). And the monoazo yellow pigment shown.

ここで、化１〜化３に於いて、Ｒ¹及びＲ²は互いに相違する水素原子、塩素原子、ニトロ基、メチル基又はメトキシ基を表し、Ｒ³，Ｒ⁴及びＲ⁵は同じか又は相違する水素原子、塩素原子、メチル基、メトキシ基又はエトキシ基を表し、Ｒ⁶はメチル基、カルボキシル基又はエトキシカルボニル基を表し、Ｒ⁷，Ｒ⁸及びＲ⁹は同じか又は相違する水素原子、塩素原子又はスルホン酸を表し、Ｑ¹〜Ｑ⁴はそれぞれ独立に水素原子、炭素数１〜２の低級アルキル基若しくは低級アルコキシ基又は水酸基を表し、Ｗは、化４に示される基から選択される置換基であり、ｍは０又は１の整数を表し、Ａ及びＢは、それぞれ独立に−ＮＨ−Ｙで示される基又は−ＯＨ基の何れかであり、ここでＹは、アミノアルキル基、アミノフェニル基、フタルイミド基、ナフタルイミド基及びベンズイミダゾロン基から選択される基であって置換基を含むものであってもよい。

Here, in Chemical Formulas 1 to 3, R ¹ and R ² represent different hydrogen atoms, chlorine atoms, nitro groups, methyl groups or methoxy groups, and R ³ , R ⁴ and R ⁵ are the same or Represents a different hydrogen atom, chlorine atom, methyl group, methoxy group or ethoxy group; R ⁶ represents a methyl group, a carboxyl group or an ethoxycarbonyl group; and R ⁷ , R ⁸ and R ⁹ are the same or different hydrogen atoms. Represents a chlorine atom or a sulfonic acid, Q ^{1 to} Q ⁴ each independently represent a hydrogen atom, a lower alkyl group having 1 to 2 carbon atoms, a lower alkoxy group or a hydroxyl group, and W is selected from the group represented by Chemical Formula 4 M represents an integer of 0 or 1, and A and B are each independently a group represented by —NH—Y or an —OH group, where Y is an aminoalkyl Group, aminophenyl group, phthalimi It may be a group selected from a group, a naphthalimide group, and a benzimidazolone group, and may contain a substituent.

一般式（１）で表される前記モノアゾ黄色主顔料の含有量が９９．８〜８０モル％であり、一般式（２）で示される前記モノアゾ黄色顔料及び／又は一般式（３）で示される前記モノアゾ黄色顔料の合計の含有量が０．２〜２０モル％であることが好ましい。

The content of the monoazo yellow main pigment represented by the general formula (1) is 99.8 to 80 mol%, and is represented by the monoazo yellow pigment represented by the general formula (2) and / or the general formula (3). It is preferable that the total content of the monoazo yellow pigment is 0.2 to 20 mol%.

  Further, the primary particle diameter of the monoazo yellow main pigment represented by the general formula (1), the primary particle diameter of the monoazo yellow pigment represented by the general formula (2), and the monoazo represented by the general formula (3) The primary particle diameter of the yellow pigment is preferably 0.2 μm or less.

  The method for producing the yellow pigment composition for image recording of the present invention comprises a diazonium constituted by the base (4) of the general formula (1) and the general formula (3) and / or the base (5) of the general formula (2). It is characterized by carrying out a coupling reaction between the salt and the coupler (6) of the general formula (1) and (2) and / or the coupler (7) of the general formula (3).

ここで、化５〜化８に於いて、Ｒ¹及びＲ²は互いに相違する水素原子、塩素原子、ニトロ基、メチル基又はメトキシ基を表し、Ｒ³，Ｒ⁴及びＲ⁵は同じか又は相違する水素原子、塩素原子、メチル基、メトキシ基又はエトキシ基を表し、Ｒ⁶はメチル基、カルボキシル基又はエトキシカルボニル基を表し、Ｒ⁷，Ｒ⁸及びＲ⁹は同じか又は相違する水素原子、塩素原子又はスルホン酸を表し、Ｑ¹〜Ｑ⁴はそれぞれ独立に水素原子、炭素数１〜２の低級アルキル基若しくは低級アルコキシ基又は水酸基を表し、Ｗは、化９に示される基から選択される置換基であり、ｍは０又は１の整数を表し、Ａ及びＢは、それぞれ独立に−ＮＨ−Ｙで示される基又は−ＯＨ基の何れかであり、ここでＹは、アミノアルキル基、アミノフェニル基、フタルイミド基、ナフタルイミド基及びベンズイミダゾロン基から選択される基であって置換基を含むものであってもよい。

Here, in Chemical Formulas 5 to 8, R ¹ and R ² represent different hydrogen atoms, chlorine atoms, nitro groups, methyl groups, or methoxy groups, and R ³ , R ^4, and R ⁵ are the same or Represents a different hydrogen atom, chlorine atom, methyl group, methoxy group or ethoxy group; R ⁶ represents a methyl group, a carboxyl group or an ethoxycarbonyl group; and R ⁷ , R ⁸ and R ⁹ are the same or different hydrogen atoms. Represents a chlorine atom or a sulfonic acid, Q ^{1 to} Q ⁴ each independently represent a hydrogen atom, a lower alkyl group having 1 to 2 carbon atoms, a lower alkoxy group or a hydroxyl group, and W is selected from the group represented by Chemical Formula 9 M represents an integer of 0 or 1, and A and B are each independently a group represented by —NH—Y or an —OH group, where Y is an aminoalkyl Group, aminophenyl group, phthalimi It may be a group selected from a group, a naphthalimide group, and a benzimidazolone group, and may contain a substituent.

ここで、上記において、一般式（１）で表される前記モノアゾ黄色主顔料９９．８〜８０モル％と、前記モノアゾ黄色主顔料とは別個に合成した一般式（２）で示される前記モノアゾ黄色顔料及び／又は一般式（３）で示される前記モノアゾ黄色顔料０．２〜２０モル％とを配合してもよい。

Here, in the above, the monoazo yellow main pigment 99.8 to 80 mol% represented by the general formula (1) and the monoazo yellow main pigment separately synthesized from the monoazo yellow main pigment are represented by the general formula (2). You may mix | blend 0.2-20 mol% of said monoazo yellow pigments shown by a yellow pigment and / or General formula (3).

  When the yellow pigment composition for image recording of the present invention is used, color reproducibility, image retention, and light resistance are improved with respect to a color image forming method based on electrophotography, electrostatic printing method, ink jet method and the like. An excellent yellow colorant for image recording is obtained. Moreover, according to the manufacturing method of the yellow pigment composition for image recording of this invention, the yellow pigment composition excellent in the said characteristic is provided.

  Hereinafter, the present invention will be described in more detail.

  In order to use the monoazo yellow main pigment as a colorant for image recording, in addition to improving the optical characteristics while maintaining the original characteristics of the monoazo main pigment, the crystal stability to solvents, heat, etc. is improved. Is required. In order to solve this problem, the monoazo yellow main pigment represented by the general formula (1) and the monoazo yellow pigment represented by the general formula (2) having a different structure from the monoazo yellow main pigment and / or the general formula ( By introducing and mixing the monoazo yellow pigment shown in 3), it is possible to prevent crystal growth during the preparation process of the color composition for image recording containing the monoazo yellow pigment.

  The blending ratio of the monoazo yellow main pigment represented by the general formula (1) is preferably 99.8 to 80 mol%, and is represented by the monoazo yellow pigment represented by the general formula (2) and / or the following general formula (3). The blending ratio of the monoazo yellow pigment is preferably 0.2 to 20 mol%. The primary particle diameter of these yellow main pigments and yellow pigments is set to a value of 0.2 μm or less to prevent crystal growth in the process of preparing a colored composition for image recording containing a monoazo yellow pigment. Can do.

  In order to introduce the yellow pigment represented by the general formula (2) and / or the general formula (3) into the monoazo yellow main pigment represented by the general formula (1), a base and / or coupling corresponding to the coupling reaction synthesis is performed. Agents are mixed, or pigments synthesized separately are mixed and blended in a paste or powder state. That is, in the case of introducing at the time of synthesis, a base represented by the general formula (4) (preferably 99.8 to 80 mol%) and a base represented by the general formula (5) as necessary (preferably 0.2 The diazonium salt may be prepared simultaneously or separately using ˜20 mol%), followed by a coupling reaction with the couplers represented by the general formula (6) and the general formula (7), or synthesized separately. When the pigment is mixed, blended and introduced, a coupling reaction is separately performed using the corresponding raw materials to synthesize the pigment of the general formula (1), the general formula (2) and / or the general formula (3). Thereafter, the monoazo yellow pigment represented by the general formula (2) and / or the general formula (3) may be mixed and blended so that the total content is preferably 0.2 to 20 mol%. In this case, after the coupling reaction synthesis of the pigment represented by the general formula (1), a predetermined amount of the pigment paste of the general formula (2) and / or the general formula (3) is added and mixed to finish the pigment of the present invention. Alternatively, a predetermined amount of each powder pigment may be blended and finished.

  Here, examples of the base represented by the general formula (4) include 2-methoxy-4-nitroaniline, 2-nitro-4-methoxyaniline, 2-nitro-4-chloroaniline, 4-nitroaniline, 2 -Nitroaniline etc. are mentioned.

  The base represented by the general formula (5) has A and B which are each independently a group represented by -NH-Y or -OH group, and Y represents an aminoalkyl group, an aminophenyl group, It may be a group selected from a phthalimide group, a naphthalimide group, and a benzimidazolone group, and may contain a substituent. Representative examples used as —NH—Y include dimethylaminopropylamine, aminophthalimide, aminobenzimidazolone, and the like.

As the preparation method of the base represented by the general formula (5), the following two methods represented by (1) and (2) are typical, and the outline thereof is shown below.
(1) First, 1.0 mol of the diamine represented by the general formula (8) is reacted with 1.0 mol of cyanuric chloride, and then the reaction product is represented by —NH—Y such as dimethylaminopropylamine. What is necessary is just to make 1.0-2.0 mol of compounds react.

（２）まず、塩化シアヌル１．０モルと、ジメチルアミノプロピルアミン等の−ＮＨ−Ｙで示される化合物１．０〜２．０モルとを反応させ、次に、一般式（８）で示されるジアミンの１．０モルとを反応させればよい。尚、（１）及び（２）で示した方法以外にも様々な調製法を使用することは可能である。

(2) First, 1.0 mol of cyanuric chloride is reacted with 1.0 to 2.0 mol of a compound represented by —NH—Y such as dimethylaminopropylamine, and then represented by the general formula (8). What is necessary is just to make it react with 1.0 mol of diamines. Various preparation methods other than the methods shown in (1) and (2) can be used.

  The couplers represented by the general formula (6) include acetoacetylanilide, 2-chloro-acetoacetanilide, 2-methoxy-acetoacetanilide, 4-methoxy-acetoacetanilide, 2-methyl-acetoacetanilide, 2,4-dimethyl- Examples include acetoacetanilide and 2,5-dimethoxy-4-chloro-acetoacetylanilide.

  In order to obtain the yellow pigment composition for image recording which is the object of the present invention, 99.8 to 80 mol% of the monoazo yellow main pigment represented by the general formula (1) and the general formula (2) containing a sulfonic acid group It is preferable to introduce and mix 0.2 to 20 mol% of the monoazo yellow pigment represented by the formula (1) and / or the monoazo yellow pigment represented by the general formula (3). Usually, when the primary particle size of the pigment is reduced to increase the transparency and coloring power, the light resistance generally decreases. However, the pigment composition of the present invention obtained in this way is not suitable for the prior art. Compared with the processed monoazo yellow pigment, the decrease in light resistance was very small, and there was no problem in the image retention property affected by light resistance.

  As described above, as a method for determining the basic suitability of the yellow pigment described above as a colorant for image recording, the following method that has been conventionally known as a general and simple method may be employed. it can. That is, if the yellow pigment composition for image recording is for water-based inkjet, first, a commonly used resin such as an acrylic resin having a dispersibility is used, and a high concentration and high dispersion of 20 to 30%. An aqueous dispersion of the pigment is prepared and the average particle size and viscosity of the pigment are measured. Next, the resin / pigment dispersion diluted with a solvent such as water / glycerin is prepared so that the application amount of the dispersion is 3 to 5% by weight. The sample is prepared by spreading the color.

The optical density of this sample [Optical Dencity = log ₁₀ (incident light quantity / exit light quantity), hereinafter referred to as OD value. ] With a Macbeth densitometer. Moreover, the light resistance of the same sample is also irradiated with a fed meter for a certain period of time, and the color is measured with the same spectrocolorimeter. The average particle diameter, OD value and light resistance result of these pigments, the shape of the monoazo yellow pigment obtained by an electron microscope, and the like are also observed, and these results are comprehensively determined.

  When an aqueous inkjet ink is produced from the yellow pigment composition for image recording produced by the above method, as a known constituent main component, a dispersant (surfactant or water-soluble resin), a surface tension adjuster (Surfactant), water-soluble organic solvent, preservative, pH adjuster, rust inhibitor and the like may be added as necessary.

  As the dispersant suitable for the aqueous inkjet ink in the above case, all known ones can be used, and all the anionic or nonionic surfactants used as pigment dispersants are used. Can be used. For example, anionic activators include fatty acid salts, alkyl sulfate esters, alkyl aryl sulfonates, alkyl naphthalene sulfonates, dialkyl sulfonates, dialkyl sulfosuccinates, alkyl diaryl ether disulfonates, alkyl phosphates. , Polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate ester salt, glycerol borate fatty acid ester, polyoxyethylene glycerol fatty acid ester it can.

  Nonionic activators include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, Examples include polyoxyethylene fatty acid ester polyoxyethylene alkylamine. These dispersants are used in the range of 0.3 to 40% by weight based on the total weight of the yellow ink.

  A water-soluble resin having dispersibility can also be used as a dispersant suitable for the aqueous inkjet ink of the present invention. As the water-soluble resin suitably used in the present invention, a resin that does not cause pigment precipitation or gelation at the use temperature or room temperature of an inkjet printer once it is dissolved in a solvent is selected. Examples of water-soluble resins that can be used include acrylic resins. Specifically, styrene-acrylic acid copolymers, acrylic acid-acrylic acid ester copolymers, and styrene-acrylic acid-acrylic acid ester copolymers. Polymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymer Polymer, polyacrylic acid, polymethacrylic acid, vinylnaphthalene-acrylic acid copolymer salt, styrene-maleic acid copolymer salt, styrene-maleic anhydride copolymer salt, vinylnaphthalene-maleic acid copolymer The salt of a thing etc. can be mentioned. In addition, monomers such as acrylonitrile, vinyl acetate, acrylamide, vinyl chloride, vinylidene chloride, ethylene, and hydroxyethyl acrylate may be copolymerized. Further, these may be added alone or in combination. These dispersants are used in the range of 0.1 to 30% by weight, preferably 1 to 30% by weight, based on the total weight of the yellow ink.

  As the surface tension adjusting agent preferably used in the present invention, any known one can be used as long as it does not adversely affect the ink to be prepared. As the surface tension adjusting agent, any of anionic, cationic, and nonionic surfactants can be used. Specifically, examples of the anionic surfactant include polyethylene glycol alkyl ether sulfate, higher alcohol sulfate, naphthalene sulfonic acid formalin condensate, and the like. Examples thereof include vinyl pyridine derivatives, poly 4-vinyl pyridine derivatives, etc. Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyalkyl phenyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan monoalkyl ether. And polyoxyethylene alkylamine.

  In order to adjust the physical properties of the ink to a desired value and to prevent the ink from drying, it is possible to use a mixture of water and the following water-soluble organic solvent. That is, alkyl alcohol having 1 to 4 carbon atoms such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, ketone or ketone alcohol such as acetone or acetone alcohol, tetrahydrofuran And ethers such as dioxane, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, glycerin, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether and other polyhydric alcohols and their ethers, acetates, N-methyl- Nitrogen-containing compounds such as 2-pyrrolidone, 1,3-dimethylimidazolinone, dimethylformamide, triethanolamine That. One or more kinds of these water-soluble organic solvents can be used. The amount of the water-soluble organic solvent used is not particularly limited, but is generally in the range of 3 to 50% by weight with respect to the total weight of the yellow ink.

  As the preservative that can be used in the present invention, any known preservative can be used as long as it does not adversely affect the ink to be prepared. Examples thereof include sodium dehydrosulfate, sodium sorbate, sodium 2-pyridinethiol-1-oxide, sodium benzoate, sodium pentachlorophenol, 1,2-benzisothiazolin-3-one and the like.

  As the pH adjusting agent suitably used in the present invention, almost any pH adjusting agent can be used as long as it can be controlled to a desired pH without adversely affecting the formulated ink. Specific examples include lower alkanolamine and ammonium hydroxide.

  As the rust preventive agent suitably used in the present invention, any known rust preventive agent can be used as long as it does not adversely affect the prepared ink. For example, acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and the like.

  Moreover, in order to give gloss etc. to printed matter, the low condensate of a vinyl pyrrolidone, an acrylic resin, a styrene-maleic acid resin etc. can be used as needed.

  As a medium in which the monoazo yellow pigment is dispersed, pure water and a general organic solvent can be used. For example, methanol, ethanol, isopropanol, ethylene glycol, glycerin and the like can be exemplified.

  If the yellow pigment composition for image recording is for color toners, first, a master batch in which the pigment is highly concentrated and dispersed in a resin such as polyester or acrylic that is usually used as a binder resin. Next, the above resin / pigment dispersion diluted with a solvent such as tetrahydrofuran or ethyl acetate is prepared so that the pigment content of this master batch is 3 to 5% by weight, and this is spread on a transparent film. To make a sample. This sample is set on an overhead projector (OHP), and the transmitted color is visually determined. At the same time, the spectral transmittance characteristics (Y value, transmittance) of the sample prepared in the same manner are measured. In addition, light resistance is also measured for a certain period of time with a fed meter and measured with the same spectrophotometer. Furthermore, the shape and the like of the monoazo yellow pigment obtained by an electron microscope can be observed, and these results can be comprehensively determined.

  In order to produce a color toner from the yellow pigment composition for image recording produced by the above method, the following procedure may be followed. That is, linear polyester resin (ethylene oxide adduct of bisphenol A-terephthalic acid condensation product, softening point 107 ° C., glass transition point 63 ° C.), or styrene acrylic resin (styrene / butyl methacrylate copolymer, softening Binder resin 55-75 parts by weight (preferably 115 ° C., glass transition point 63 ° C.), preferably 60-65 parts by weight is charged into a kneader and heated and melted at 105-135 ° C., preferably 110-120 ° C. A master batch is prepared by gradually adding 25 to 45 parts by weight, preferably 35 to 40 parts by weight of the yellow pigment of the present invention. Next, 7 to 20 parts by weight of this master batch, preferably 10 to 15 parts by weight, is bound to 80 to 93 parts by weight of a binder resin such as the linear polyester resin or styrene acrylic resin, preferably 85 to 90 parts by weight. It is added and diluted together with an appropriate amount of the charge control agent, and melted and kneaded at 105 to 135 ° C, preferably 110 to 120 ° C. After cooling this, the powder obtained by pulverization is classified to have an average particle size of 5 to 12 μm, and a fluidity improver, a cleaning aid and the like are further added to obtain a color toner.

  In the present invention, after the coupling reaction synthesis, it is preferable to add a fatty acid ester to perform surface treatment and to perform post-treatment such as heat treatment in order to improve dispersibility. Here, the fatty acid ester refers to a condensate obtained by dehydration condensation of an acid and an alcohol as shown below, and examples of the acid include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, Examples include behenic acid, bovine fatty acid, maleic acid, methacrylic acid, 2-ethylhexanoic acid, phthalic acid, adipic acid, trimellitic acid, and the like. On the other hand, examples of alcohol include methyl alcohol, isopropyl alcohol, and n-butyl alcohol. , Isobutyl alcohol, n-octyl alcohol, 2-ethylhexyl alcohol, n-decyl alcohol, isodecyl alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol Octyldodecyl alcohol and the like.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Unless otherwise specified, “%” and “part” in the following examples and comparative examples represent “% by weight” and “part by weight”, respectively.

[Synthesis of pigments]
Example 1
Add 100 parts of 2-methoxy-4-nitroaniline into a mixture of 800 parts of water and 158 parts of 35% hydrochloric acid, stir, add ice, cool to 0 ° C., add 43 parts of sodium nitrite and add diazo. Turned into. On the other hand, the coupler liquid was prepared by mixing 126 parts of 2-methoxy-acetoacetanilide and 3 parts of 3-methyl-1- (3-sulfophenyl) -5-pyrazolone in a mixed liquid of 400 parts of water and 94 parts of 30% sodium hydroxide. In addition, this solution is added to a solution obtained by dissolving 60 parts of sodium acetate in 2000 parts of water, and then precipitated by adding a mixed solution of 300 parts of water and 56 parts of 80% acetic acid. Was prepared. At 25 ° C., the above diazotization liquid was dropped into this coupler suspension in 120 minutes to complete the coupling reaction. Next, the temperature was raised to 90 ° C., heat treated for 30 minutes, filtered, washed with water, dried and pulverized to obtain 235 parts of a yellow pigment composition.

(Example 2)
100 parts of 2-methoxy-4-nitroaniline and 6.3 parts of base A shown in Chemical formula 11 are added to a mixed solution of 880 parts of water and 162 parts of 35% hydrochloric acid, and the mixture is stirred at 0 ° C. with ice. After cooling, 44 parts of sodium nitrite was added for diazotization.

一方、カップラー液は、２−メトキシ−アセトアセトアニリド１３２部を水４００部と３０％苛性ソーダ９４部の混合液中に加えて溶解させ、この溶解液を水２０００部に酢酸ソーダ６０部を溶解した溶解液に添加した後、水３００部と８０％酢酸５６部の混合液を添加することによって析出させて懸濁液を調製した。２５℃において、このカップラー懸濁液に上記のジアゾ化液を１２０分で滴下してカップリング反応を終了させた。次に、９０℃に昇温して３０分間熱処理し、濾過、水洗、乾燥及び粉砕を行って２３５部の黄色顔料組成物を得た。

On the other hand, the coupler solution was dissolved by adding 132 parts of 2-methoxy-acetoacetanilide to a mixed solution of 400 parts of water and 94 parts of 30% caustic soda, and dissolving this dissolved solution by dissolving 60 parts of sodium acetate in 2000 parts of water. After adding to the liquid, a suspension was prepared by precipitation by adding a mixed solution of 300 parts of water and 56 parts of 80% acetic acid. At 25 ° C., the above diazotization liquid was dropped into this coupler suspension in 120 minutes to complete the coupling reaction. Next, the temperature was raised to 90 ° C., heat treated for 30 minutes, filtered, washed with water, dried and pulverized to obtain 235 parts of a yellow pigment composition.

(Example 3)
100 parts of 2-methoxy-4-nitroaniline and 6.6 parts of base B are added to a mixture of 880 parts of water and 162 parts of 35% hydrochloric acid and stirred. After adding ice and cooling to 0 ° C., nitrous acid is added. Diazotization was carried out by adding 44 parts of soda.

一方、カップラー液は、２−メトキシ−アセトアセトアニリド１３２部を水４００部と３０％苛性ソーダ９４部の混合液中に加えて溶解させ、この溶解液を水２０００部に酢酸ソーダ６０部を溶解した溶解液に添加した後、水３００部と８０％酢酸５６部の混合液を添加することによって析出させて懸濁液を調製した。２５℃において、このカップラー懸濁液に上記のジアゾ化液を１２０分で滴下してカップリング反応を終了させた。次に、９０℃に昇温して３０分間熱処理し、濾過、水洗、乾燥及び粉砕を行って２３５部の黄色顔料組成物を得た。

On the other hand, the coupler solution was dissolved by adding 132 parts of 2-methoxy-acetoacetanilide to a mixed solution of 400 parts of water and 94 parts of 30% caustic soda, and dissolving this dissolved solution by dissolving 60 parts of sodium acetate in 2000 parts of water. After adding to the liquid, a suspension was prepared by precipitation by adding a mixed solution of 300 parts of water and 56 parts of 80% acetic acid. At 25 ° C., the above diazotization liquid was dropped into this coupler suspension in 120 minutes to complete the coupling reaction. Next, the temperature was raised to 90 ° C., heat treated for 30 minutes, filtered, washed with water, dried and pulverized to obtain 235 parts of a yellow pigment composition.

(Example 2)
100 parts of 2-methoxy-4-nitroaniline and 6.3 parts of base A shown in Chemical formula 11 are added to a mixture of 880 parts of water and 162 parts of 35% hydrochloric acid, and the mixture is stirred at 0 ° C. with ice. After cooling, 44 parts of sodium nitrite was added for diazotization.

  On the other hand, the coupler solution was a mixture of 132 parts of 2-methoxy-acetoacetanilide, 3 parts of 3-methyl-1- (3-sulfophenyl) -5-pyrazolone, 400 parts of water and 94 parts of 30% caustic soda. After adding this solution to a solution obtained by dissolving 60 parts of sodium acetate in 2000 parts of water, the mixture is precipitated and suspended by adding a mixed solution of 300 parts of water and 56 parts of 80% acetic acid. A suspension was prepared. At 25 ° C., the above diazotization liquid was dropped into this coupler suspension in 120 minutes to complete the coupling reaction. Next, the temperature was raised to 90 ° C., heat treated for 30 minutes, filtered, washed with water, dried and pulverized to obtain 240 parts of a yellow pigment composition.

(Comparative Example 1)
Add 100 parts of 2-methoxy-4-nitroaniline into a mixture of 800 parts of water and 158 parts of 35% hydrochloric acid, stir, add ice, cool to 0 ° C., add 43 parts of sodium nitrite and add diazo. Turned into. On the other hand, the coupler solution was prepared by adding 129 parts of 2-methoxy-acetoacetanilide to a mixed solution of 400 parts of water and 94 parts of 30% caustic soda, and dissolving this solution by dissolving 60 parts of sodium acetate in 2000 parts of water. After adding to the liquid, a suspension was prepared by precipitation by adding a mixed solution of 300 parts of water and 56 parts of 80% acetic acid. At 25 ° C., the above diazotization liquid was dropped into this coupler suspension in 120 minutes to complete the coupling reaction. Next, the temperature was raised to 90 ° C., heat-treated for 30 minutes, filtered, washed with water, dried and pulverized to obtain 231 parts of a yellow pigment composition.

(Comparative Example 2)
Add 100 parts of 2-methoxy-4-nitroaniline into a mixture of 800 parts of water and 158 parts of 35% hydrochloric acid, stir, add ice, cool to 0 ° C., add 43 parts of sodium nitrite and add diazo. Turned into. On the other hand, the coupler solution was prepared by adding 126 parts of 2-methoxy-acetoacetanilide and 3 parts of 2-carboxy-acetoacetanilide to a mixed solution of 400 parts of water and 94 parts of 30% caustic soda. A suspension was prepared by adding a mixed solution of 300 parts of water and 56 parts of 80% acetic acid to a solution prepared by dissolving 60 parts of sodium acetate in 2000 parts. At 25 ° C., the above diazotization liquid was dropped into this coupler suspension in 120 minutes to complete the coupling reaction. Next, the temperature was raised to 90 ° C., heat treated for 30 minutes, filtered, washed with water, dried and pulverized to obtain 235 parts of a yellow pigment composition.

(Comparative Example 3)
100 parts 2-methoxy-4-nitroaniline and 5.8 parts 2-sulfo-4-methylaniline are added to a mixture of 880 parts water and 162 parts 35% hydrochloric acid and stirred. After cooling to 0 ° C., 44 parts of sodium nitrite was added for diazotization. On the other hand, the coupler solution was prepared by adding 135 parts of 2-methoxy-acetoacetanilide to a mixed solution of 400 parts of water and 94 parts of 30% caustic soda, and dissolving this solution by dissolving 60 parts of sodium acetate in 2000 parts of water. After adding to the liquid, a suspension was prepared by precipitation by adding a mixed solution of 300 parts of water and 56 parts of 80% acetic acid. At 25 ° C., the above diazotization liquid was dropped into this coupler suspension in 120 minutes to complete the coupling reaction. Next, the temperature was raised to 90 ° C., heat treated for 30 minutes, filtered, washed with water, dried and pulverized to obtain 235 parts of a yellow pigment composition.

(Comparative Example 4)
100 parts of 2-methoxy-4-nitroaniline and 6.4 parts of base C are added to a mixture of 880 parts of water and 162 parts of 35% hydrochloric acid, stirred, cooled to 0 ° C. with ice, and then nitrous acid. Diazotization was carried out by adding 44 parts of soda.

一方、カップラー液は、２−メトキシ−アセトアセトアニリド１３２部を水４００部と３０％苛性ソーダ９４部の混合液中に加えて溶解させ、この溶解液を水２０００部に酢酸ソーダ６０部を溶解した溶解液に添加した後、水３００部と８０％酢酸５６部の混合液を添加することによって析出させて懸濁液を調製した。２５℃において、このカップラー懸濁液に上記のジアゾ化液を１２０分で滴下してカップリング反応を終了させた。次に、９０℃に昇温して３０分間熱処理し、濾過、水洗、乾燥及び粉砕を行って２３５部の黄色顔料組成物を得た。

On the other hand, the coupler solution was dissolved by adding 132 parts of 2-methoxy-acetoacetanilide to a mixed solution of 400 parts of water and 94 parts of 30% caustic soda, and dissolving this dissolved solution by dissolving 60 parts of sodium acetate in 2000 parts of water. After adding to the liquid, a suspension was prepared by precipitation by adding a mixed solution of 300 parts of water and 56 parts of 80% acetic acid. At 25 ° C., the above diazotization liquid was dropped into this coupler suspension in 120 minutes to complete the coupling reaction. Next, the temperature was raised to 90 ° C., heat treated for 30 minutes, filtered, washed with water, dried and pulverized to obtain 235 parts of a yellow pigment composition.

[Sample preparation and evaluation]
(Evaluation as a colorant for inkjet ink)
20 parts of each pigment obtained in Examples 1 to 4 and Comparative Examples 1 to 4, 12.5 parts of acrylic resin dispersant (John Crill 61J, manufactured by Johnson Polymer Co., Ltd.), 10 parts of ethylene glycol, 0.5 parts of diethanolamine And a composition consisting of 57 parts of pure water was placed in a sand mill and dispersed for 5 hours to prepare an inkjet ink having a pigment content of 20%.

<Pigment particle size>
An IJ ink having a pigment content of 20% was measured using a light scattering particle size distribution analyzer.

<OD value>
A dispersion was prepared by diluting an ink for IJ having a pigment content of 20% with a solvent (water / glycerin = 80/20) so that the pigment content would be 4%, and then it was spread on a color paper with a 0.15 mm bar coater. Colored. The OD value of this sample was measured with a RD-19 (I) model manufactured by Gretag Macbeth.

<Light resistance>
Using the same sample as the OD value measurement, irradiation was performed with a fedometer for 100 hours, and a color difference (ΔE value) with an unirradiated sample was obtained with a spectrocolorimeter (D65 light source 10 ° field of view).

  The evaluation results for the samples prepared above are summarized in Table 1.

その結果、実施例１〜４の顔料は、比較例１〜４の顔料に比べて、インクジェットインクに優れた適性を有していることがわかる。

As a result, it can be seen that the pigments of Examples 1 to 4 have better suitability for inkjet inks than the pigments of Comparative Examples 1 to 4.

(Evaluation as a color toner colorant)
Next, using the monoazo yellow pigments of Examples 1 to 4 and Comparative Examples 1 to 4, samples for testing the presence or absence of basic suitability as a color toner colorant were prepared by the following procedure. First, 60 parts of a linear polyester resin (ethylene oxide adduct of bisphenol A-terephthalic acid condensation product, softening point: 107 ° C., glass transition point: 63 ° C.) as a binder resin is charged into a kneader. 40 parts of monoazo yellow pigment was added little by little while heating and melting at 0 ° C., and a master batch having a pigment content of 40% was prepared by a conventional method. Next, 10 parts of this master batch was dissolved in 90 parts of tetrahydrofuran to prepare yellow pigment dispersions each having a pigment content of 4%. This pigment dispersion is developed on a transparent film and white art paper with a 0.15 mm bar coater, and the color-exposed product on the transparent film is used for measuring optical property values, and the color-exposed product on white art paper is A sample for light resistance measurement was used.

<Y value>
The brightness (brightness) of the sample was measured with a spectrocolorimeter (C light source 2 ° field of view).

<Transmissivity>
The difference T (%) between the transmittance at a wavelength of 550 nm and the transmittance at a wavelength of 410 nm was measured with a spectrocolorimeter.

<Light resistance>
Irradiation was performed for 100 hours with a fed meter, and a color difference (ΔE value) with an unirradiated sample was determined with a spectrocolorimeter (D65 light source 10 ° field of view).

  The evaluation results for the samples prepared above are summarized in Table 2.

その結果、実施例１〜４の顔料は、比較例１〜４の顔料に比べて、カラートナー用の顔料として優れた適性を有していることがわかる。

As a result, it can be seen that the pigments of Examples 1 to 4 have excellent suitability as pigments for color toners compared to the pigments of Comparative Examples 1 to 4.

Claims (5)

For image recording containing a monoazo yellow main pigment represented by the following general formula (1), a monoazo yellow pigment represented by the following general formula (2) and / or a monoazo yellow pigment represented by the following general formula (3) Yellow pigment composition.

[In the chemical formulas ¹ to 3, R ¹ and R ² represent different hydrogen atoms, chlorine atoms, nitro groups, methyl groups or methoxy groups, and R ³ , R ⁴ and R ⁵ are the same or different. Represents a hydrogen atom, a chlorine atom, a methyl group, a methoxy group or an ethoxy group, R ⁶ represents a methyl group, a carboxyl group or an ethoxycarbonyl group, and R ⁷ , R ⁸ and R ⁹ are the same or different, Q ^{1 to} Q ⁴ each independently represents a hydrogen atom, a lower alkyl group having 1 to 2 carbon atoms, a lower alkoxy group or a hydroxyl group, and W is selected from the group represented by Chemical Formula 4 A substituent, m represents an integer of 0 or 1,

A and B are each independently a group represented by —NH—Y or —OH group, where Y is an aminoalkyl group, an aminophenyl group, a phthalimide group, a naphthalimide group, or a benzimidazolone group. May be a group selected from the group consisting of a substituent. ]   The content of the monoazo yellow main pigment represented by the general formula (1) is 99.8 to 80 mol%, and is represented by the monoazo yellow pigment represented by the general formula (2) and / or the general formula (3). The yellow pigment composition for image recording according to claim 1, wherein the total content of the monoazo yellow pigment is 0.2 to 20 mol%.   The primary particle diameter of the monoazo yellow main pigment represented by the general formula (1), the primary particle diameter of the monoazo yellow pigment represented by the general formula (2), and the monoazo yellow pigment represented by the general formula (3) 3. The yellow pigment composition for image recording according to claim 1, wherein the primary particle diameter is 0.2 μm or less. A diazonium salt constituted by the base (4) of the general formula (1) and the general formula (3) and / or the base (5) of the general formula (2);
The yellow pigment composition for image recording according to claim 1 or 3, wherein the coupler (6) of the general formula (1) and the general formula (2) and / or the coupler (7) of the general formula (3) is subjected to a coupling reaction. Manufacturing method.

[In the chemical formulas 5 to 8, R ¹ and R ² represent different hydrogen atoms, chlorine atoms, nitro groups, methyl groups or methoxy groups, and R ³ , R ⁴ and R ⁵ are the same or different. Represents a hydrogen atom, a chlorine atom, a methyl group, a methoxy group or an ethoxy group, R ⁶ represents a methyl group, a carboxyl group or an ethoxycarbonyl group, and R ⁷ , R ⁸ and R ⁹ are the same or different, Q ^{1 to} Q ⁴ each independently represents a hydrogen atom, a lower alkyl group having 1 to 2 carbon atoms, a lower alkoxy group or a hydroxyl group, and W is selected from the group represented by Chemical Formula 9 A substituent, m represents an integer of 0 or 1,

A and B are each independently a group represented by -NH-Y or -OH group, where Y is an aminoalkyl group, aminophenyl group, phthalimide group, naphthalimide group, or benzimidazolone group. May be a group selected from the group consisting of a substituent. ] The monoazo yellow main pigment represented by the general formula (1) and the monoazo yellow pigment represented by the general formula (2) synthesized separately from the monoazo yellow main pigment 99.8 to 80 mol% and the monoazo yellow main pigment The method for producing a yellow pigment composition for image recording according to claim 2 or 3, wherein 0.2 to 20 mol% of the monoazo yellow pigment represented by the formula (3) is blended.