JP2016108450A - Naphthol red and method for producing the same, resin composition, water-based dispersion and solvent-based dispersion each using the same naphthol red - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide naphthol red that is excellent in dispersibility and color development by controlling the particle shape, to provide a resin composition, a water-based dispersion and a solvent-based dispersion each colored with the naphthol red and to provide a method for producing the naphthol red.SOLUTION: The naphthol red has an axial ratio (average major axis diameter/average minor axis diameter) of the primary particle in the range of 1.0 to 2.0 and a powder pH in the range of 4.0 to 9.0. The resin composition, the water-based dispersion and the solvent-based dispersion each contains the naphthol red. The method for producing the naphthol red is provided.SELECTED DRAWING: None

Description

  The present invention provides naphthol red having excellent dispersibility and color developability by highly controlling the axial ratio (average major axis diameter / average minor axis diameter) of primary particles.

  The present invention also provides a method for producing the naphthol red having excellent dispersibility and color developability.

  In addition, the present invention provides a resin composition, an aqueous dispersion, and a solvent dispersion that are colored with the naphthol red and have excellent dispersibility and color developability.

  Naphthol red is an artificial dye synthesized by an azo coupling reaction between a diazonium salt of an aromatic amine and various naphthols. The combination of aromatic amines and naphthol is extremely large, and it exhibits a yellowish to bluish red color (bordeaux, marron, violet, brown, etc.), covering most of them but more than other pigments of the same family. Has strong coloring power. In addition, dyes and pigments can be produced in various ways by selecting chemical species and synthesis methods, so that various color expressions are possible. Therefore, conventionally, it has been used for various applications such as paint, printing ink, paint, poster color, plastic coloring, cosmetics and the like. (Non-Patent Document 1)

  In particular, naphthol red represented by Chemical Formula 1, (official name: N- (5-chloro-2-methoxyphenyl) -3-hydroxy-4- [2-methoxy-5- (phenylcarbamoyl) phenylazo] -2-naphthamide : CI Pigment Red 269) is attracting attention as a pigment that well reproduces the Japanese color magenta.

Therefore, in addition to conventional applications, studies are being made for applications having strict quality standards, such as non-magnetic developers for electrophotography, inkjet inks, and color filters for liquid crystals. In these applications, magenta has mainly used quinacridone, which is a higher pigment. Quinacridone has excellent color developability and durability, but has disadvantages that it is expensive and lacks variation. In recent years, naphthol red, which is inexpensive, has abundant variations, and has high coloring power, has been attracting attention because of the demand for higher image quality and greater diversity in these applications.
As a substitute for quinacridone, naphthol red shown in Chemical Formula 1 is one of the promising candidates. (Patent Documents 1 to 5)

  However, naphthol red pigments are easy to obtain needle-like and columnar particle shapes, and in applications with the above strict quality standards, due to lack of transparency due to shape-induced dispersion and lack of color development, Has not been adopted. In order to solve this problem, various studies have been made, such as studies on particle size and shape control, mixing with other pigments, and studies on mixed crystals, and solutions have been devised for each purpose.

  For particle size and shape control, a monoazo pigment produced by mixing a diazonium salt and a coupler solution (naphthol derivative), and a fine monoazo pigment obtained by adding an anionic surfactant to the coupler solution was used. A magenta color toner (Patent Document 1) and an inkjet ink (Patent Document 2) using a fine monoazo pigment obtained by adding an anionic surfactant to a coupler solution are known.

  Further, as for the mixing of pigments and mixed crystals, water-insoluble azo pigments and quinacridone pigments are mixed (Patent Document 3), mixed crystals thereof (Patent Document 4), monoazo red pigments and monoazo red pigment derivatives. (Patent Document 5) is known.

W. Herbst, K.M. Published by Hunger, Industrial Organic Pigments, VCH A Wiley Company 1997 (p. 282-315)

JP-A-11-272014 JP 2000-186241 A Japanese Patent Laid-Open No. 04-226477 JP 200531275 A JP 2000-248191 A

  As mentioned above, naphthol red, which has high coloring power and a wide variety of colors, is used in conventional applications such as paints and printing inks, as well as non-magnetic developers for electrophotography, color filters for liquid crystals, and inkjet inks. It is expected to be used for strict quality standards. However, naphthol red tends to become needle-like and columnar particles, and its dispersion and color developability tend to be poor due to its shape, and it has not been fully adopted.

  That is, in the above-mentioned Patent Document 1, as shown in Comparative Example 1 below, the primary particles have a large axial ratio, so that the dispersibility is inferior and the color developability is hardly sufficient.

  As shown in Comparative Example 2 described later, the above-mentioned Patent Document 2 has a large axial ratio of primary particles, so that it is inferior in dispersibility and hardly has sufficient color developability.

  Since the thing of the above-mentioned patent document 4 has a large axial ratio of a primary particle as shown in the following comparative example 3, it is inferior to a dispersibility and it cannot be said that coloring property is enough.

  As shown in Comparative Example 4 described later, the above-mentioned Patent Document 5 has a large primary particle axial ratio, and thus is inferior in dispersibility and is not sufficiently satisfactory in color developability.

  Therefore, the present invention has a technical problem to provide naphthol red having excellent dispersibility and color developability by controlling the particle shape. Another object of the present invention is to provide a resin composition colored with the naphthol red, an aqueous dispersion, and a solvent dispersion.

  The technical problem can be achieved by the present invention as follows.

That is, the present invention is a naphthol red represented by Chemical Formula 2, wherein the primary particles have an axial ratio (average major axis diameter / average minor axis diameter) in the range of 1.0 to 2.0, and the powder pH Is in the range of 4.0 to 9.0. (Invention 1)

  Moreover, this invention is a naphthol red of this invention 1 whose average particle diameter of a primary particle is 0.02 micrometer-0.20 micrometer. (Invention 2)

  Moreover, this invention is a naphthol red of this invention 1 or 2 whose haze value in a film thickness of 3 micrometers is 10-20% in a polyester resin coating film with a pigment concentration of 5%. (Invention 3)

The present invention is also the naphthol red according to any one of the present inventions 1 to 3, wherein a saturation c ^* at a film thickness of 3 μm is 60 or more in a polyester resin coating film having a pigment concentration of 5%. (Invention 4)

Further, the present invention reacts by injecting and stirring an azonium salt cooled solution of an aromatic amine represented by Chemical Formula 3 into a naphthol cooled solution represented by Chemical Formula 4, and further, a hydrophilic naphthol derivative represented by Chemical Formula 5, Or it is a manufacturing method of the naphthol red manufactured by adding and reacting the hydrophilic phenol derivative shown by Chemical formula 6. (Invention 6)

  Further, the present invention reacts by injecting and stirring the naphthol cooling solution represented by the chemical formula 4 into the aromatic amine azonium salt cooling solution represented by the chemical formula 3, and further, a hydrophilic naphthol derivative represented by the chemical formula 5; Or it is a manufacturing method of the naphthol red manufactured by adding and reacting the hydrophilic phenol derivative shown by Chemical formula 6. (Invention 7)

  Moreover, this invention is a resin composition which comprises the naphthol red in any one of this invention 1-4. (Invention 8)

  Moreover, this invention is the aqueous dispersion which contains the naphthol red in any one of this invention 1-4. (Invention 9)

  Moreover, this invention is a solvent dispersion which contains the naphthol red in any one of this invention 1-4. (Invention 10)

  The naphthol red according to the present invention is suitable as a naphthol red having a small primary particle axial ratio and excellent dispersibility and color development.

  The method for producing naphthol red according to the present invention can be produced while suppressing particle growth by surface treatment with a hydrophilic naphthol derivative or a hydrophilic phenol derivative in the production process of naphthol red. Is suitable as a method for producing naphthol red having a small axial ratio and excellent dispersibility and color developability.

  The resin composition colored with naphthol red according to the present invention is suitable as a resin composition because of its excellent dispersibility and color developability. In addition, the aqueous dispersion colored with naphthol red and the solvent dispersion according to the present invention are suitable as various dispersions because they are excellent in dispersibility and color developability.

  The configuration of the present invention will be described in more detail as follows.

  First, naphthol red according to the present invention will be described.

  The axial ratio (average major axis diameter / average minor axis diameter) of primary particles of naphthol red according to the present invention is in the range of 1.0 to 2.0. When the axial ratio exceeds 2.0, dispersion becomes difficult and color developability is poor. Also, the axial ratio cannot be less than 1.0. A preferred axial ratio is in the range of 1.0 to 1.9, more preferably in the range of 1.1 to 1.8.

  The average major axis diameter of the primary particles of naphthol red according to the present invention is preferably 0.02 to 0.20 μm. When the average major axis diameter is less than 0.02 μm, dispersion tends to be difficult. When the average major axis diameter is larger than 0.2 μm, the color developability is poor. A more preferred average major axis diameter is 0.03 to 0.18 μm.

  The average minor axis diameter of the primary particles of naphthol red according to the present invention is preferably 0.02 to 0.20 μm. When the average minor axis diameter is less than 0.02 μm, dispersion tends to be difficult. When the average minor axis diameter is larger than 0.2 μm, the color developability is poor. A more preferred average minor axis diameter is 0.03 to 0.15 μm.

  The average particle diameter of the primary particles of naphthol red according to the present invention is preferably 0.02 to 0.20 μm. When the average particle size of the primary particles is less than 0.02, dispersion tends to be difficult. When the average particle size of the primary particles is larger than 0.20, the color developability is poor. A more preferable average particle size of the primary particles is 0.02 to 0.15 μm.

  The powder pH of the naphthol red according to the present invention is in the range of 4.0 to 9.0. When the powder pH is less than 4.0, dispersion into a resin or the like may be hindered. When the powder pH exceeds 9.0, dispersion in water or the like may be hindered. A more preferable powder pH is 4.1 to 8.5, and more preferably 4.2 to 8.0.

  In the polyester resin coating film of naphthol red having a pigment concentration of 5% according to the present invention, the haze value at a film thickness of 3 μm is preferably 10 to 20%. When the haze value is larger than 20%, it is difficult to say that the transparency of the coating film is excellent, and it can be said that the dispersion is poor. A more preferable haze value is 12 to 19%.

In the polyester resin coating film of naphthol red having a pigment concentration of 5% according to the present invention, the chroma c ^* at a film thickness of 3 μm is preferably 60 or more, and it can be said that the color developability is excellent. When the chroma c ^* is less than 60, it is difficult to say that color developability is excellent. A more preferred color index c ^* is 65 or more. Furthermore, a more preferred color index c ^* is 70 or more.

In the polyester resin coating film of naphthol red having a pigment concentration of 5% according to the present invention, a ^* and b ^* at a film thickness of 3 μm are not particularly limited. ^{* And} b ^* are both 0 or more. When magenta is expressed, a ^* is preferably 0 or more and b ^* is less than 0.

  The naphthol red according to the present invention may be subjected to a surface treatment in order to improve dispersibility, color developability and the like. The surface treatment material is not particularly limited, but surfactants such as alkyl alcohols, fatty acids and alkylamines, polymers such as acrylic resins, polyester resins and urethane resins, silane coupling agents, and organic silicon such as silanes. Examples include organic surface treatment agents such as compounds, inorganic surface treatment agents such as inorganic fine particles such as silica, alumina and titanium oxide, and organic and inorganic surface treatment agents such as rosin-calcium and rosin-magnesium, or two of them. What was processed with what was combined above is also good.

  Next, a method for producing naphthol red according to the present invention will be described.

  Naphthol red according to the present invention is obtained by using an azonium salt cooled solution of an aromatic amine (formal name: 3-amino-4-methoxybenzanilide) represented by chemical formula 7 as naphthol (formal name: N- ( 5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthalenecarboxamide) reaction by injecting and stirring into a cooled solution, and before the reaction is completed, a hydrophilic naphthol derivative represented by Chemical Formula 9 or By adding a hydrophilic phenol derivative represented by Chemical Formula 10 and reacting, fine particles with a small axial ratio are obtained. The mixture is stirred for a certain period of time while being cooled, and then heat-treated to form a pigment. Then, after adjusting pH, performing filtration, washing with water, and drying, it can grind | pulverize and the naphthol red based on this invention can be obtained.

  The naphthol red according to the present invention is reacted by injecting and stirring the naphthol cooling solution represented by the chemical formula 8 into the aromatic amine azonium salt cooling solution represented by the chemical formula 7, and before the reaction is completed, By adding and reacting the hydrophilic naphthol derivative shown or the hydrophilic phenol derivative shown by Chemical Formula 10, fine particles with a small axial ratio are obtained. The mixture is stirred for a certain period of time while being cooled, and then heat-treated to form a pigment. Then, after adjusting pH, performing filtration, washing with water, and drying, it can grind | pulverize and the naphthol red based on this invention can be obtained.

  A method of adding a diazonium salt cooling solution of an aromatic amine to a naphthol cooling solution is referred to as positive coupling, and is most commonly used for coupling using a diazonium salt. In the positive coupling, the diazonium salt coolant, which is an active species, is gradually added to the naphthol coolant and reacts sequentially, so that the reactivity is high and side reactions are unlikely to occur.

  A method that is produced by adding a naphthol cooling solution to a diazonium salt cooling solution of an aromatic amine is called reverse coupling, and is often used for coupling using a diazonium salt. In this case, the reactivity is not as high as that of the positive coupling. However, when the reactivity of the naphthol cooling liquid is low, the reaction can easily proceed because the reaction can be performed in a large excess of the diazonium salt cooling liquid.

  In the azo coupling method, either the forward coupling or the reverse coupling is not excellent, but it is selected depending on chemical species, required quality, and the like.

  A diazonium salt cooling solution of an aromatic amine is prepared by dissolving an aromatic amine represented by Chemical Formula 7 in an aqueous cooling solution of an acid and adding an aqueous sodium nitrite solution or the like thereto. Further, in order to remove excess nitrite, it is preferable to add a trace amount of sulfamic acid to remove nitrite. Then, it is used after adjusting to a predetermined pH with an acid, base, buffer solution or the like. The diazonium salt is prepared, stored, and reacted at 0 to 5 ° C. because the diazonium salt is extremely susceptible to heat. There is a possibility of freezing below 0 ° C, making it difficult to use. When the temperature is higher than 10 ° C., the diazonium salt is decomposed.

  Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, and organic acids such as formic acid, acetic acid, citric acid, adipic acid, and paratoluenesulfonic acid.

  The naphthol cooling solution is preferably obtained by suspending naphthol represented by Chemical Formula 8 in an aqueous base solution, dissolving it by heating at 80 ° C., and cooling to 0 to 5 ° C. Storage and reaction are performed at 0 to 5 ° C. There is a possibility of freezing below 0 ° C, making it difficult to use. When the temperature is higher than 5 ° C., the reacting diazonium salt is decomposed. Further, naphthol represented by Chemical Formula 8 can be used without being dissolved.

  Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia, and organic bases such as methylamine and triethylamine.

  The reaction temperature is not particularly limited, but the azo coupling reaction may be carried out at 0 to 10 ° C, preferably 0 to 5 ° C.

  The hydrophilic naphthol derivative is preferably 1-naphthol, 2-naphthol, or 1-naphthol, 2-naphthol derivative having one or more hydrophilic functional groups. For example, 1-naphthol, 2-naphthol, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1-naphthol-3-carboxylic acid, 2-naphthol-3-carboxylic acid, 1-naphthol-5 carboxylic acid, 2-naphthol-5-carboxylic acid, 1-naphthol-6-carboxylic acid, 2-naphthol-6-carboxylic acid, 1-naphthol-8-carboxylic acid, 2-naphthol-8-carboxylic acid, 2-naphthol-3 , 6-dicarboxylic acid, 2-naphthol-3,8-dicarboxylic acid, 2-naphthol-6,8- Carboxylic acid, 2-naphthol-3,6,8-tricarboxylic acid, 2-naphthol-3-carboxamide, 2-naphthol-3-carboxyamidophenyl-4-sulfonic acid, 1-naphthol-3-sulfonic acid, 1 -Naphthol-4-sulfonic acid, 1-naphthol-5-sulfonic acid, 1-naphthol-8-sulfonic acid, 1-naphthol-3,6-dicarboxylic acid, 1-naphthol-3,8-dicarboxylic acid, 2- Naphthol-3-sulfonic acid, 2-naphthol-4-sulfonic acid, 2-naphthol-5-sulfonic acid, 2-naphthol-6-sulfonic acid, 2-naphthol-7-sulfonic acid, 2-naphthol-8-sulfone Acid, 2-naphthol-3,6-disulfonic acid, 2-naphthol-3,8-disulfonic acid, 2-naphthol-6,8-disulfonic acid 2-naphthol-3,6,8-trisulfonic acid, 1,8-naphthalenediol-3-sulfonic acid, 1,8-naphthalenediol-3,6-sulfonic acid, 2,8-naphthalenediol-6-sulfone Acid, 2-naphthol-3-phosphate, 2-naphthol-5-phosphate, 2-naphthol-6-phosphate, 2-naphthol-8-phosphate, 2-naphthol-3,6-diphosphate, 2 -Naphthol-3,8-diphosphoric acid, 2-naphthol-6,8-diphosphoric acid, 2-naphthol-3,6,8-triphosphoric acid, or salts thereof such as sodium and potassium Is mentioned.

  The hydrophilic phenol derivative is preferably phenol or a derivative having one or more hydrophilic functional groups on phenol. For example, countless examples include phenol, catechol, hydroquinone, benzenetriol, phloroglucinol, salicylic acid, aminophenol, phenol-3-sulfonic acid, or a salt thereof such as sodium or potassium.

  The addition amount of the hydrophilic naphthol derivative or the hydrophilic phenol derivative is preferably 1 to 10% by weight with respect to the synthesized naphthol red. More preferably, it is 1 to 5% by weight.

  The hydrophilic naphthol derivative or the hydrophilic phenol derivative is dissolved in water or a hydrophilic solvent such as methanol, ethanol, isopropanol, dimethylformamide, N-methylpyrrolidone, and added after cooling to 0 to 5 ° C. It is preferable.

  Further, after completion of the azo coupling reaction, it is preferably heated to 90 ° C. with stirring in order to form a pigment.

  The pH is preferably adjusted to a range of 4.0 to 9.0 by adding an acid agent or an alkali agent. Furthermore, Preferably, it is the range of pH 4.0-8.0.

  As the acid agent, either an inorganic compound or an organic compound may be used. Examples of the inorganic compound include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, and examples of the organic compound include formic acid, acetic acid, citric acid, adipic acid, and paratoluenesulfonic acid.

  As the alkali agent, either an inorganic compound or an organic compound may be used. Examples of inorganic compounds include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and carbonates such as sodium carbonate, and examples of organic compounds include trialkanol amines such as triethanolamine and triisopropanolamine. It is done.

  After adjusting the pH, the target naphthol red according to the present invention can be obtained by filtering, washing with water, drying and pulverizing by a conventional method.

  Next, the resin composition according to the present invention will be described.

  The resin composition according to the present invention comprises naphthol red according to the present invention, a well-known thermoplastic resin, and additives such as lubricants, plasticizers, antioxidants, ultraviolet absorbers, and various stabilizers as necessary. The

  The blending ratio of naphthol red in the resin composition according to the present invention can be used within a range of 0.01 to 200 parts by weight with respect to 100 parts by weight of the constituent base, and if handling of the resin composition is taken into consideration. The amount is preferably 0.05 to 100 parts by weight, more preferably 0.1 to 50 parts by weight.

  The amount of the additive may be 50% by weight or less with respect to the total of naphthol red and the thermoplastic resin. When the content of the additive exceeds 50% by weight, the moldability is lowered.

The hue of the resin composition according to the present invention refers to the L ^* value, a ^* value, b ^* value, and c ^* value among the color index measured by an evaluation method described later.

  Next, the manufacturing method of the resin composition concerning this invention is described.

  In the resin composition according to the present invention, the resin raw material and naphthol red are mixed well in advance, and then a strong shearing action is applied under heating using a kneader or an extruder to break down the naphthol red aggregates. After naphthol red is uniformly dispersed in the resin, it is used after being molded into a shape suitable for the purpose.

  Next, the aqueous dispersion according to the present invention will be described.

  The aqueous dispersion according to the present invention is blended with naphthol red according to the present invention, water, if necessary, extender pigment, aqueous solvent, surfactant, pigment dispersant, resin, pH adjuster, antifoaming agent, etc. Composed.

  The blending ratio of naphthol red in the aqueous dispersion according to the present invention can be used in the range of 0.1 to 200 parts by weight with respect to 100 parts by weight of the dispersion-constituting substrate, and if the handling of the dispersion is taken into consideration. The amount is preferably 0.1 to 100 parts by weight, more preferably 0.1 to 50 parts by weight.

  Examples of extender pigments include inorganic pigments such as silica, titanium oxide, barium sulfate, zinc oxide, and magnesium oxide, and polymers such as acrylic fine particles and polyester fine particles.

  As the aqueous solvent, ethanol, isopropanol, butyl alcohol, glycerin, butyl cellosolve, or the like can be used.

  Surfactants include anionic surfactants such as dodecylbenzene sulfonic acid and alkyl polyoxyethylene sulfonic acid, nonionic surfactants such as alkyl polyoxyethylene, and cationic surfactants such as dodecylamine hydrochloride. Can be mentioned.

  Examples of the pigment dispersant include a polymer anion pigment dispersant, a polymer nonionic pigment dispersant, and a polymer cationic pigment dispersant.

  As the resin, commonly used water-soluble alkyd resins, water-soluble melamine resins, water-soluble acrylic resins, and various emulsion resins can be used.

  Antifoaming agents include Nopco 8034 (product name), SN deformer 477 (product name), SN deformer 5013 (product name), SN deformer 247 (product name), SN deformer 382 (product name) (all of these are San Nopco Manufactured products), Antihome 08 (trade name), Emulgen 903 (trade name) (all of which are manufactured by Kao) and the like can be used.

  The viscosity of the aqueous dispersion according to the present invention is preferably 20.0 mPa · s or less, more preferably 15.0 mPa · s or less. More preferably, it is 10.0 mPa · s or less. When the viscosity of the dispersion exceeds 20 mPa · s, the color developability is poor. The lower limit of the viscosity of the aqueous dispersion is about 1.0 mPa · s.

  The storage stability evaluation of the aqueous dispersion according to the present invention is preferably less than ± 10%, more preferably ± 6% or less, still more preferably ± 5% or less in the viscosity change rate measured by the evaluation method described later. .

The hue of the aqueous dispersion according to the present invention refers to the L ^* value, a ^* value, b ^* value, and c ^* value among the color index measured by the evaluation method described later.

  Next, the manufacturing method of the aqueous dispersion which concerns on this invention is described.

  The aqueous dispersion according to the present invention is mixed with naphthol red, water and additives, and dispersed using a media disperser such as a bead mill or a medialess disperser such as CLEARMIX, FILMIX, or an ultrasonic homogenizer. It is manufactured after post-treatment such as filtration. In order to improve the dispersion stability, it may be produced by a self-dispersion process or a microcapsule process.

  Next, the solvent dispersion according to the present invention will be described.

  The solvent-based dispersion according to the present invention comprises naphthol red according to the present invention, a resin, a solvent, and, if necessary, an extender pigment, a drying accelerator, a surfactant, a curing accelerator, an auxiliary agent, and the like. The

  The blending ratio of naphthol red in the solvent-based dispersion according to the present invention can be used in the range of 0.1 to 200 parts by weight with respect to 100 parts by weight of the dispersion-constituting substrate, and the handling of the dispersion is taken into consideration. For example, it is preferably 0.1 to 100 parts by weight, and more preferably 0.1 to 50 parts by weight.

  As the resin, commonly used acrylic resins, alkyd resins, polyester resins, polyurethane resins, epoxy resins, phenol resins, melamine resins, amino resins, and the like can be used.

  As the solvent, commonly used toluene, xylene, tetrahydrofuran, methyl acetate, ethyl acetate, butyl acetate, acetone, 2-butanone, methyl isobutyl ketone, ethyl solosolve, butyl cellosolve, propylene glycol monomethyl ether acetate, aliphatic hydrocarbon, etc. Can be used.

  The viscosity of the solvent-based dispersion according to the present invention is preferably 20.0 mPa · s or less, more preferably 10.0 mPa · s or less. If it exceeds 20 mPa · s, the dispersibility is poor and the color developability is poor. The lower limit of the viscosity of the solvent-based dispersion is about 2.0 mPa · s.

  The storage stability evaluation of the solvent-based dispersion according to the present invention is preferably less than ± 15%, more preferably ± 12% or less, still more preferably ± 10% or less, in the rate of change in viscosity measured by the evaluation method described later. is there.

The hue of the solvent-based dispersion according to the present invention refers to the L ^* value, a ^* value, b ^* value, and c ^* value among the color index measured by the evaluation method described later.

  Next, a method for producing a solvent-based dispersion according to the present invention will be described.

  The solvent-based dispersion according to the present invention is a mixture of naphthol red, a solvent, an additive and a resin, and a media disperser such as a bead mill or a medialess disperser such as a clear mix, a fill mix, and an ultrasonic homogenizer. Dispersed and manufactured by post-treatment such as filtration. In order to increase the dispersion stability, it may be produced by a self-dispersion process or a microcapsule process.

<Action>
The naphthol red according to the present invention is suitable as a naphthol red having a small primary particle axial ratio and excellent dispersibility and color development.

  The method for producing naphthol red according to the present invention is because the pigment surface has polarity and crystal growth is suppressed by surface treatment with a hydrophilic naphthol derivative or a hydrophilic phenol derivative at the end of the azo coupling reaction. Particles having a small primary particle axial ratio can be obtained. Since the axial ratio is small, it is excellent in dispersibility and color developability, and is suitable as a method for producing naphthol red having excellent color developability and transparency.

  The resin composition colored with naphthol red according to the present invention is suitable as a resin composition because of its excellent dispersibility and color developability. In addition, the aqueous dispersion colored with naphthol red and the solvent dispersion according to the present invention are suitable as various dispersions because they are excellent in dispersibility and color developability.

  A typical embodiment of the present invention is as follows.

  The average major axis diameter and the average minor axis diameter of the primary particles are both the major axis diameter and the minor axis diameter of 350 primary particles shown in the micrograph by transmission electron microscope JEM-1200EX II (manufactured by JASCO). Was measured and indicated by the average value.

  The axial ratio of primary particles is shown as the ratio of the average major axis diameter to the average minor axis diameter (average major axis diameter / average minor axis diameter).

  The average particle diameter of the primary particles is shown as an average value of the average major axis diameter and the average minor axis diameter.

  The pH value of the powder was measured by weighing 5 g of a sample into a 300 ml Erlenmeyer flask, adding 100 ml of boiled pure water, heating and holding the boiled state for about 5 minutes, then plugging it and letting it cool to room temperature. After adding water corresponding to the above, plugging again, shaking for 1 minute, allowing to stand for 5 minutes, the pH of the obtained supernatant was measured according to JIS Z8802-7, and the obtained value was determined as the powder pH value. did.

  The haze value is an application piece (coating film thickness: about 3 μm) prepared by applying the solvent-based dispersion prepared in the examples described later on a cast coated paper using a bar coater having a WET film thickness of 24 μm. It showed with the value which measured the haze value using the haze meter (Nippon Denshoku Industries Haze Meter NDH4000).

  Judgment of dispersibility of naphthol red according to the present invention is based on haze value of 10% to less than 15% ◎, 15% to less than 20% ○, 20% to less than 25% △, Those with 25% or more were rated as x.

For the hue, an application piece (coating film thickness: about 3 μm) was prepared by applying the solvent-based dispersion prepared in the examples described later on a cast coated paper using a bar coater having a WET film thickness of 24 μm. The color index L ^* value, a ^* value, and b ^* value were respectively measured by using a colorimeter X-Rite 939 (manufactured by X-Rite) according to JIS Z8729. The saturation c ^* was determined by the following formula 1 using a ^* value and b ^* value.

<Equation 1>
c ^* = ((a ^* ) ² + (b ^* ) ² ) ^1/2

The color development of the naphthol red according to the present invention is determined by chromaticity c ^* , 以上 65 or more, ◯ 60 to 65, ５５ 55 to less than 60 △, less than 55 ×. did.

Regarding the dispersibility of the resin composition according to the present invention, a resin composition having the composition described below was dispersed in an epoxy monomer with the following composition, and was allowed to cure at 60 ° C. for 24 hours to produce pellets.
(Epoxy resin embedding)
Resin composition 1mg
Epoxy resin embedding agent Quetol-812 for electron microscope 3.0g
(Manufactured by Nissin EM)
DDSA (curing agent) 1.0 g
(Manufactured by Nissin EM)
MNA (curing agent) 2.0g
(Manufactured by Nissin EM)
DMP-30 (polymerization accelerator) 0.01 g
(Manufactured by Nissin EM)
And this pellet was sliced to a film thickness of 2 μm with this RMC ultramicrotome MT2C (Keiwa Shoji), this was observed with a transmission electron microscope, and the dispersibility was evaluated in the following four stages.
(Double-circle): Undispersed material is not recognized.
A: 1 to 10 undispersed materials are observed per 100 μm ² .
Δ: 11 to 50 undispersed materials are observed per 100 μm ² .
X: 51 or more undispersed substances are recognized per 100 μm ² .

The color developability of the resin composition according to the present invention is as follows. After the resin composition is pulverized, 2.0 g is weighed, immersed in 8.0 g of tetrahydrofuran, and coated on cast coated paper using a bar coater having a WET film thickness of 24 μm. The coated strip (film thickness: about 3 μm) was prepared, and the coated strip was measured using a spectrocolorimeter X-Rite 939 (manufactured by X-Rite) according to JIS Z8729, and the color index L ^* value, The a ^* value and b ^* value are shown as measured values. The chroma c ^* was determined by the following formula 2 using a ^* value and b ^* value. A resin composition having a chroma c ^* of 60 or more can be used practically without any problem.

<Equation 2>
c ^* = ((a ^* ) ² + (b ^* ) ² ) ^1/2

  The viscosity of the aqueous dispersion according to the present invention was measured using an E-type viscometer TV-30 (manufactured by Toki Sangyo Co., Ltd.).

  For the storage stability evaluation of the aqueous dispersion according to the present invention, the initial viscosity and the time-lapse viscosity after 1 week at 25 ° C. were measured using an E-type viscometer TV-30 (manufactured by Toki Sangyo Co., Ltd.). The rate of change from the initial viscosity to the time-dependent viscosity was calculated by the following formula 3, and evaluated in the following three stages.

<Equation 3>
[Viscosity change rate] = ([Aging viscosity] − [Initial viscosity]) / [Initial viscosity] × 100

○: Viscosity change rate is less than ± 10% △: Viscosity change rate is ± 10% or more and less than ± 30% ×: Viscosity change rate is ± 30% or more

  Regarding the dispersibility of the aqueous dispersion according to the present invention, an application piece (coating thickness: about 3 μm) obtained by applying the aqueous dispersion prepared in Examples below onto a cast coated paper using a bar coater having a WET film thickness of 24 μm. The haze value was measured with a haze meter (Nippon Denshoku Industries Haze Meter NDH4000). For the determination of dispersibility, the haze value is 10% or more and less than 15% ◎, 15% or more and less than 20% ○, 20% or more and less than 25% Δ, 25% or more × It was.

About the hue of the aqueous dispersion which concerns on this invention, the hue of the coating film using the aqueous dispersion produced by the below-mentioned Example is defined in JISZ8729 using the spectrocolorimeter X-Rite939 (product made from X-Rite). Accordingly, the color index L ^* value, a ^* value, and b ^* value are shown as measured values. Saturation c ^* was calculated by the following formula 4 using a ^* value and b ^* value. An aqueous dispersion having a chroma c ^* of 60 or more can be used practically without any problem.

<Equation 4>
c ^* = ((a ^* ) ² + (b ^* ) ² ) ^1/2

  The viscosity of the solvent dispersion according to the present invention was measured using an E-type viscometer TV-30 (manufactured by Toki Sangyo Co., Ltd.).

  For the storage stability evaluation of the solvent-based dispersion according to the present invention, the initial viscosity and the viscosity with time after 1 week at 25 ° C. were measured using an E-type viscometer TV-30 (manufactured by Toki Sangyo Co., Ltd.). The change rate from the initial viscosity to the time-dependent viscosity was calculated by the following equation 5 and evaluated in the following three stages.

<Equation 5>
[Viscosity change rate] = ([Aging viscosity] − [Initial viscosity]) / [Initial viscosity] × 100

○: Viscosity change rate is less than ± 15% Δ: Viscosity change rate is ± 15% or more and less than ± 30% ×: Viscosity change rate is ± 30% or more

  Regarding the dispersibility of the solvent-based dispersion according to the present invention, an applied piece (coating thickness: about 3 μm) obtained by applying the solvent-based dispersion prepared in Examples below to a cast-coated paper using a bar coater having a WET film thickness of 24 μm. The haze value was measured using a haze meter (Haze Meter NDH4000 manufactured by Nippon Denshoku Industries Co., Ltd.). For the determination of dispersibility, the haze value is 10% or more and less than 15% ◎, 15% or more and less than 20% ○, 20% or more and less than 25% Δ, 25% or more × It was.

Regarding the hue of the solvent-based dispersion according to the present invention, the hue of the coating film using the solvent-based dispersion prepared in the examples described later is JIS Z8729 using a spectrocolorimeter X-Rite 939 (manufactured by X-Rite). The color index L ^* value, a ^* value, and b ^* value are shown as measured values in accordance with The saturation c ^* was determined by the following formula 6 using a ^* value and b ^* value. A solvent-based dispersion having a chroma c ^* of 60 or more can be used without any practical problem.

<Equation 6>
c ^* = ((a ^* ) ² + (b ^* ) ² ) ^1/2

<Manufacture of naphthol red>
Example 1
12.5 parts by weight of 35% HCl aqueous solution was added to 187.5 parts by weight of ice water and stirred, and the temperature was adjusted to 5 ° C. or lower. To this, 8 parts by weight of 3-amino-4-methoxybenzanilide was added and stirred to dissolve 3-amino-4-methoxybenzanilide and the hydrochloride of 3-amino-4-methoxybenzanilide. Precipitation was confirmed and it stirred at 5 degrees C or less for 30 minutes. Thereafter, 7.8 parts by weight of 30% aqueous sodium nitrite solution was added and stirred at 5 ° C. or less for 60 minutes, and 0.3 part by weight of sulfamic acid was added to eliminate nitrous acid. Further, 8 parts by weight of sodium acetate and 12 parts by weight of 90% acetic acid were added to obtain a diazonium salt cooling solution. Separately, 11 parts by weight of N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthalenecarboxamide was weighed, 150 g of pure water and 4 parts by weight of sodium hydroxide were added, and the mixture was stirred at 90 ° C. Until dissolved. Furthermore, it stirred and cooled to 5 degreeC and was set as the naphthol cooling solution. Then, the diazonium salt cooling solution is put into a syringe pump equipped with a 0.5 mm syringe and injected into the naphthol cooling solution stirring liquid at a rate of 15 parts by weight / min. The reaction solution was stirred at 300 rpm. Then, the solution which melt | dissolved 2-naphthol-3carboxylic acid and 0.4 weight part in ice water 20 weight part was prepared, and it was cooled to 5 degrees C or less. And the solution was added to the reaction liquid at 5 degrees C or less, and also stirred at 300 rpm for 1 hour. Then, it heated to 90 degreeC and stirred at 300 rpm as it was for 1 hour. Further, the pH is adjusted to 6.0 using 1N hydrochloric acid or 1N sodium hydroxide aqueous solution, filtered, washed with water, dried at 80 ° C. for 10 hours, pulverized, and naphthol red according to the present invention. Got. (Red pigment-1)

Examples 2-4
A naphthol red according to the present invention was obtained in the same manner as in Example 1 except that the hydrophilic naphthol derivative to be added or the kind and amount of the hydrophilic phenol derivative and the reaction conditions were variously changed. (Red pigment-2-4)

Example 5
In the same manner as in Example 1, a diazonium salt cooling solution and a naphthol cooling solution were obtained.
Then, the naphthol cooling solution is put into a syringe pump equipped with a 0.5 mm nozzle and injected into the diazonium salt cooling solution stirring liquid at a rate of 15 parts by weight / min. Stir at 300 rpm. Then, the solution which melt | dissolved 2-naphthol-3 carboxamide and 0.4 weight part in ice water 20 weight part was prepared, and it was cooled to 5 degrees C or less. And the solution was added to the reaction liquid at 5 degrees C or less, and also stirred at 300 rpm for 1 hour. And it heated to 90 degreeC and stirred at 1200 rpm as it was for 1 hour. Further, the pH is adjusted to 6.0 using 1N hydrochloric acid or 1N sodium hydroxide aqueous solution, filtered, washed with water, dried at 80 ° C. for 10 hours, pulverized, and naphthol red according to the present invention. Got. (Red pigment-5)

Examples 6-8
A naphthol red according to the present invention was obtained in the same manner as in Example 5 except that the kind and amount of the hydrophilic naphthol derivative or hydrophilic phenol derivative to be added and the reaction conditions were variously changed. (Red pigment-6-8)

The production conditions at this time are shown in Table 1, and the characteristics of the obtained naphthol red are shown in Table 2.

Comparative Example 1 (Follow-up experiment of Production Example 1 of JP-A-11-272014)
Disperse 50 parts by weight of 3-amino-4-methoxybenzanilide in 1000 parts by weight of water, add ice to set the temperature to 0 to 5 ° C., add 60 parts by weight of 35% HCl aqueous solution and stir for 20 minutes. did. Thereafter, 50 parts by weight of a 30% sodium nitrite aqueous solution was added and stirred for 60 minutes, and then 2 parts by weight of sulfamic acid was added to eliminate nitrous acid. Further, 50 parts by weight of sodium acetate and 75 parts by weight of 90% acetic acid were added to obtain a diazonium solution. Separately, 68 parts by weight of N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthalenecarboxamide was dissolved at 80 ° C. or less together with 1000 parts by weight of water and 25 parts by weight of sodium hydroxide, (A) 3 parts by weight of Minerite 100 was added as a component to prepare a coupler solution. This solution was added to the diazonium salt solution under a temperature condition of 10 ° C. or lower, a coupling reaction was performed, and a heat treatment at 90 ° C. was performed. Next, after filtering and washing with water, it was dried at 100 ° C. and pulverized to obtain a monoazo pigment. (Red pigment-9)

The production conditions at this time are shown in Table 1, and the properties of the obtained monoazo pigment are shown in Table 2.

Comparative Example 2 (Follow-up experiment of Production Example 1 of JP 2000-186241 A)
60 parts by weight of 3-amino-4-methoxybenzanilide was dispersed in 1000 parts by weight of water, ice was added to set the temperature to 0 to 5 ° C., 72 parts by weight of 35% aqueous HCl was added, and the mixture was stirred for 20 minutes. . Thereafter, 60 parts by weight of 30% sodium nitrite aqueous solution was added and stirred for 60 minutes, and 2.3 parts by weight of sulfamic acid was added to eliminate nitrous acid. Further, 60 parts by weight of sodium acetate and 89 parts by weight of 90% acetic acid were added to obtain a diazonium salt solution. Separately, 82 parts by weight of N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthalenecarboxamide is dissolved at a temperature of 80 ° C. or less together with 1000 parts by weight of water and 30 parts by weight of sodium hydroxide, As a component, 12 parts by weight of Neoperex F-25 (2.16% by weight based on the pigment) was added to prepare a coupler solution. This solution was added to the diazonium salt solution under a temperature condition of 10 ° C. or lower, a coupling reaction was performed, and a heat treatment at 90 ° C. was performed. Next, after filtering and washing with water, it was dried at 100 ° C. and pulverized to obtain a monoazo pigment. (Red pigment-10)

The production conditions at this time are shown in Table 1, and the properties of the obtained monoazo pigment are shown in Table 2.

Comparative example 3 (Follow-up experiment of Example 2 of JP-A-2005-3275)
C. I. Pigment Red122 50 parts by weight and C.I. I. 50 parts by weight of Pigment Red 269 was dissolved in sulfuric acid at room temperature, and a sulfuric acid solution of the pigment was added to 8 times the amount of cold water at 10 ° C. to effect hydrolysis, thereby obtaining a mixed crystal pigment. (Red Pigment-11)

The production conditions at this time are shown in Table 1, and the characteristics of the obtained mixed crystal pigment are shown in Table 2.

Comparative Example 4 (Follow-up test of Example 1 of JP 2000-248191 A)
Disperse 50 parts by weight of 3-amino-4-methoxybenzanilide in 1000 parts by weight of water, add ice to set the temperature at 0-5 ° C., add 55 parts by weight of 35% aqueous HCl, and stir for 30 minutes. did. Thereafter, 50 parts by weight of 30% sodium nitrite aqueous solution was added and stirred for 60 minutes, and then 2 parts by weight of sulfamic acid was added to eliminate excess nitrous acid. Furthermore, 40 parts by weight of sodium acetate and 58 parts by weight of 90% acetic acid were added to obtain a diazonium salt solution. Separately, 59 parts by weight of N- (5-chloro-2-methoxyphenyl-3-hydroxy-2-naphthalenecarboxamide and 5 parts by weight of 3-hydroxynaphthoic acid were mixed with 1000 parts by weight of water and 25 parts by weight of caustic soda. The solution was dissolved at 80 ° C. or less to prepare a coupler solution, which was added to the diazonium salt solution at a temperature condition of 10 ° C. or less to perform a coupling reaction, and heat-treated at 90 ° C. The reaction mixture was filtered, After washing with water, it was dried at 100 ° C. and pulverized to obtain a monoazo red pigment (red pigment-12).

The production conditions at this time are shown in Table 1, and the characteristics of the obtained monoazo red pigment are shown in Table 2.

  As described above, each of the naphthol reds in the examples has an axial ratio in the range of 1.0 to 2.0, and is clearly excellent in dispersibility and color developability.

<Manufacture of resin composition>
Example 9
3.0 parts by weight of red pigment-1 obtained in Example 1 and 57.0 parts by weight of polyester resin DIACRON ER561 (manufactured by Mitsubishi Rayon) were weighed and pulverized in a sample mill. This was kneaded in a Laboplast mill (manufactured by Toyo Seiki) at 120 ° C. and 25 rpm for 10 minutes, taken out, and then cooled to room temperature. Then, it grind | pulverized at 12000 rpm using the ultracentrifugal crusher (ZM200 made from Lecce), and obtained the resin composition.

Examples 10-16, Comparative Examples 5-8
A resin composition was obtained in the same manner as in Example 9 except that the type of naphthol red was variously changed.

  Various properties of the resin composition obtained at this time are shown in Table 3.

  As described above, it is clear that the resin compositions of the examples are excellent in dispersibility and excellent color developability.

<Production of aqueous dispersion>
Example 17
In a 140 ml glass bottle, 0.5 parts by weight of naphthol red obtained in Example 1 was used, and the aqueous dispersion composition was blended at the following ratio, and mixed and dispersed in a paint shaker for 60 minutes together with 50 parts by weight of 1.5 mmφ glass beads. An aqueous dispersion was obtained.

The aqueous dispersion was blended at the following ratio.
Naphthol red 0.50 parts by weight,
0.05 part by weight of anionic surfactant
(Neopelex GS: manufactured by Kao)
Acrylic emulsion (solid content 33%) 28.79 parts by weight,
(Nicazole RX-3002E: manufactured by Nippon Carbide)
Defoaming agent 0.05 parts by weight,
(Envelope Gem AD-01: Nissin Chemical Industry)
Pure water 20.61 parts by weight.

Examples 18-24, Comparative Examples 9-12
An aqueous dispersion was obtained in the same manner as in Example 17 except that the type of naphthol red was variously changed.

  Various characteristics of the aqueous dispersion obtained at this time are shown in Table 4.

  As described above, it is clear that the aqueous dispersions of the examples are excellent in storage stability, excellent in dispersibility, and excellent in color developability.

<Production of solvent-based dispersion>
Example 25
Using 0.50 parts by weight of naphthol red obtained in Example 1 in a 140 ml glass bottle, the solvent-based dispersion composition was blended in the following proportions and mixed and dispersed with a paint shaker for 60 minutes together with 50 parts by weight of 1.5 mmφ glass beads. A solvent-based dispersion was prepared.

The solvent-based dispersion was blended with the following composition.
Naphthol red 0.50 parts by weight,
9.50 parts by weight of polyester resin DIACRON ER561
(Made by Mitsubishi Rayon)
Tetrahydrofuran 40.00 parts by weight.

Examples 26-32, Comparative Examples 13-16
A solvent-based dispersion was obtained in the same manner as in Example 25 except that the type of naphthol red was variously changed.

Various properties of the solvent-based dispersion obtained at this time are shown in Table 5.

  As described above, it is apparent that the solvent-based dispersions of the examples have excellent storage stability, excellent dispersibility, and excellent color developability.

The naphthol red according to the present invention has a small primary particle axial ratio and is excellent in dispersibility and color developability, so that it can be used in fields such as non-magnetic developers for electrophotography, ink-jet inks, color filters for liquid crystals, etc. It is suitable for various uses such as printing inks, paints, poster colors, plastic colorants, and cosmetics. In addition, the resin composition comprising naphthol red according to the present invention is suitable as a resin composition because it is excellent in dispersibility and color developability. In addition, the aqueous dispersion colored with naphthol red and the solvent dispersion according to the present invention are suitable as various dispersions because they are excellent in dispersibility and color developability.

Claims (9)

A naphthol red represented by Chemical Formula 1, wherein the primary particle has an axial ratio (average major axis diameter / average minor axis diameter) in the range of 1.0 to 2.0, and a powder pH of 4.0 to 9. Naphthol red in the 0 range.

The naphthol red according to claim 1, wherein the average particle size of the primary particles is 0.02 µm to 0.20 µm. The naphthol red according to claim 1 or 2, wherein the haze value at a film thickness of 3 µm is 10 to 20% in a polyester resin coating film having a pigment concentration of 5%. The naphthol red according to any one of claims 1 to 3, wherein a saturation c ^* at a film thickness of 3 µm is 60 or more in a polyester resin coating film having a pigment concentration of 5%. Reaction with an azonium salt cooling solution of an aromatic amine represented by the chemical formula 2 by injecting and stirring into a naphthol cooling solution represented by the chemical formula 3, followed by a hydrophilic naphthol derivative represented by the chemical formula 4 or the formula 5 Of naphthol red produced by adding a hydrophilic phenol derivative to be reacted.

Reaction is performed by injecting and stirring the naphthol cooling solution represented by the chemical formula 3 into the azonium salt cooling solution of the aromatic amine represented by the chemical formula 2, and further, the hydrophilic naphthol derivative represented by the chemical formula 4 or the chemical formula 5 Of naphthol red produced by adding a hydrophilic phenol derivative to be reacted. The resin composition which comprises the naphthol red in any one of Claims 1-4. An aqueous dispersion comprising the naphthol red according to any one of claims 1 to 4. A solvent-based dispersion comprising the naphthol red according to claim 1.