WO2016088828A1 - Naphthol red, manufacturing method therefor, and resin composition, aqueous dispersion, and solvent dispersion using said naphthol red - Google Patents

Naphthol red, manufacturing method therefor, and resin composition, aqueous dispersion, and solvent dispersion using said naphthol red Download PDF

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Publication number
WO2016088828A1
WO2016088828A1 PCT/JP2015/083991 JP2015083991W WO2016088828A1 WO 2016088828 A1 WO2016088828 A1 WO 2016088828A1 JP 2015083991 W JP2015083991 W JP 2015083991W WO 2016088828 A1 WO2016088828 A1 WO 2016088828A1
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Prior art keywords
naphthol
chemical formula
naphthol red
red
represented
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PCT/JP2015/083991
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French (fr)
Japanese (ja)
Inventor
宗由 坂本
高平 上原
伸哉 志茂
功荘 青木
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戸田工業株式会社
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Priority claimed from JP2014247272A external-priority patent/JP6809774B2/en
Priority claimed from JP2014247273A external-priority patent/JP6551645B2/en
Priority claimed from JP2014247274A external-priority patent/JP2016108452A/en
Priority claimed from JP2014247271A external-priority patent/JP2016108449A/en
Application filed by 戸田工業株式会社 filed Critical 戸田工業株式会社
Publication of WO2016088828A1 publication Critical patent/WO2016088828A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C08K5/23—Azo-compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/10—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group
    • C09B29/18—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group ortho-Hydroxy carbonamides
    • C09B29/20—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group ortho-Hydroxy carbonamides of the naphthalene series
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B41/00—Special methods of performing the coupling reaction
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols

Definitions

  • 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 provides naphthol red, which is surface-treated with a hydrophilic derivative and has excellent dispersibility and color developability.
  • the present invention also provides a method for producing the naphthol red having excellent dispersibility and color development.
  • the present invention also 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 represented by the chemical formula (1) is an artificial dye synthesized by azo coupling reaction of diazonium salt of 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.
  • 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, they are used for various applications such as paints, printing inks, paints, poster colors, plastic colorants, cosmetics and the like.
  • naphthol red represented by the chemical formula (11) (formal name: N- (5-chloro-2-methoxyphenyl) -3-hydroxy-4- [2-methoxy-5- (phenylcarbamoyl) phenylazo] -2 -Naphthoamide: CI Pigment Red 269) is attracting attention as a pigment that well reproduces the Japanese color magenta.
  • magenta mainly uses quinacridone, which is a higher pigment.
  • Quinacridone has excellent color developability and durability, but has disadvantages that it is expensive and lacks variation.
  • naphthol red which is inexpensive, has abundant variations, and has high coloring power, has been attracting attention because of higher image quality and more versatility in these applications.
  • the chemical formula (1) The naphthol red shown is one of the promising candidates.
  • 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.
  • 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.
  • magenta is a monoazo pigment produced by mixing a diazonium salt and a coupler solution (naphthol), and a fine monoazo pigment obtained by adding an anionic surfactant to the coupler solution.
  • a 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.
  • Patent Document 3 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.
  • 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.
  • 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.
  • Patent Document 2 has a large primary particle axial ratio, and therefore is inferior in dispersibility and is not sufficiently satisfactory in color development.
  • the one in the above-mentioned Patent Document 4 has a large axial ratio of primary particles, so that the dispersibility is inferior and it is difficult to say that the color developability is sufficient.
  • Patent Document 5 has a large primary particle axial ratio, and therefore is inferior in dispersibility and hardly has sufficient color developability.
  • a technical problem of the present invention is to provide naphthol red having excellent dispersibility and color developability by controlling the particle shape. Another object of the present invention is to provide naphthol red having a controlled surface state, excellent dispersibility, and excellent color developability. 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 present invention is a naphthol red represented by the chemical formula (1), 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. (Invention 1).
  • the present invention is the naphthol red according to the present invention 1 wherein the average primary particle diameter is 0.02 ⁇ m to 0.20 ⁇ m (the present invention 2).
  • the present invention is the naphthol red according to the first or second aspect of the present invention having a pigment concentration of 5% and a polyester resin coating film having a haze value of 10 to 20% at a film thickness of 3 ⁇ m (Invention 3).
  • the present invention is the naphthol red according to any one of the present inventions 1 to 3, wherein the saturation c * at a film thickness of 3 ⁇ m is 60 or more in a polyester resin coating film having a pigment concentration of 5% (Invention 4) ).
  • the present invention is the naphthol red according to any one of the present inventions 1 to 4 having a powder pH in the range of 4.0 to 9.0 (Invention 5).
  • the present invention is the naphthol red according to any one of the present inventions 1 to 5, wherein the naphthol red represented by the chemical formula (1) is a compound represented by the chemical formula (11) (compound PR269) (the present invention 6). .
  • the present invention provides an operation including reacting in a minute region when adding a diazonium salt cooling solution of an aromatic amine represented by chemical formula (2) to a naphthol cooling solution represented by chemical formula (3), or chemical formula (3
  • the naphthol cooling solution represented by formula (2) is added to the benzanilide diazonium salt cooling solution represented by formula (2)
  • the naphthol red production method represented by chemical formula (1) is produced by an operation including reacting in a microregion.
  • the aromatic amine azonium salt cooling solution represented by the chemical formula (2) is reacted by injecting and stirring into the naphthol cooling solution represented by the chemical formula (3), or represented by the chemical formula (3).
  • the naphthol cooled solution is reacted by injecting and stirring the azonium salt cooled solution of the aromatic amine represented by the chemical formula (2), and the hydrophilic naphthol derivative represented by the chemical formula (4) or the chemical formula (5)
  • the aromatic amine is an aromatic amine represented by the chemical formula (12)
  • the naphthol is a naphthol represented by the chemical formula (13)
  • the naphthol red is a compound represented by the chemical formula (11) (compound PR269).
  • the method for producing naphthol red according to any one of the present inventions 7 to 8 (present invention 9).
  • the present invention also provides a naphthol red represented by the chemical formula (11), wherein the hydrophilic naphthol derivative represented by the chemical formula (4) or the hydrophilic phenol derivative represented by the chemical formula (5) is 0.01 to 0 3. 3% by weight surface-treated naphthol red (Invention 10).
  • the present invention is the naphthol red according to the present invention 10 in which the axial ratio (average major axis diameter / average minor axis diameter) of primary particles is in the range of 1.0 to 2.0 (Invention 11).
  • the present invention is the naphthol red according to the present invention 10 or 11, wherein the average primary particle size is 0.02 ⁇ m to 0.20 ⁇ m (the present invention 12).
  • the present invention is the naphthol red according to any one of the present inventions 10 to 12, wherein the polyester resin coating film has a pigment concentration of 5% and the haze value at a film thickness of 3 ⁇ m is 10 to 20% (Invention 13). ).
  • the present invention is the naphthol red according to any one of the present inventions 10 to 13, wherein the saturation c * at a film thickness of 3 ⁇ m is 60 or more in a polyester resin coating film having a pigment concentration of 5% (Invention 14). ).
  • the present invention is the naphthol red according to any one of the present inventions 10 to 14 having a powder pH in the range of 4.0 to 9.0 (Invention 15).
  • the present invention is a resin composition comprising the naphthol red according to any one of the present inventions 1 to 6 and 10 to 15 (invention 16).
  • the present invention is an aqueous dispersion comprising the naphthol red according to any one of the present inventions 1 to 6 and 10 to 15 (present invention 17).
  • the present invention also relates to a solvent-based dispersion comprising the naphthol red according to any one of the present inventions 1 to 6 and 10 to 15 (invention 18).
  • 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 naphthol red according to the present invention is surface-treated with a hydrophilic naphthol derivative or a hydrophilic phenol derivative, has polarity on the pigment surface, and has excellent dispersibility because particle growth is suppressed. Therefore, it is suitable as naphthol red excellent in color development and transparency.
  • the method for producing naphthol red according to the present invention can be produced by reacting naphthol red in a minute region, and is therefore suitable as a method for producing naphthol red having a small primary particle axial ratio and excellent dispersibility and color development. is there.
  • 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 it is excellent in dispersibility and color developability.
  • 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.
  • naphthol red according to the present inventions 1 to 6 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 naphthol red according to the present invention includes naphthol red represented by the chemical formula (1) (CI Pigment Red 5, CI Pigment Red 17, CI Pigment Red 22, CI Pigment Red 146, CI Pigment Red 146, CI Pigment Red 146, CI Pigment Red 146, CI Pigment Red 146, CI Pigment Red 146, and CI Pigment Red 146. Pigment Red 150, CI Pigment Red 170, CI Pigment Red 268, and CI Pigment Red 269). Among them, naphthol red (CI Pigment Red 269) represented by the chemical formula (11) of the present invention 6 is particularly preferable.
  • naphthol red CI Pigment Red 269 represented by the chemical formula (11) of the present invention 6 is particularly preferable.
  • the average major axis diameter of the primary particles of naphthol red according to the present invention is preferably 0.02 to 0.20 ⁇ m.
  • the average major axis diameter is less than 0.02 ⁇ m, dispersion tends to be difficult.
  • the average major axis diameter is larger than 0.2 ⁇ m, the color developability is poor.
  • a more preferable average major axis diameter is 0.03 to 0.18 ⁇ m.
  • the average minor axis diameter of the primary particles of naphthol red according to the present invention is preferably 0.02 to 0.20 ⁇ m.
  • the average minor axis diameter is less than 0.02 ⁇ m, dispersion tends to be difficult.
  • the average minor axis diameter is larger than 0.2 ⁇ m, the color developability is poor.
  • a more preferred average minor axis diameter is 0.03 to 0.15 ⁇ m.
  • the average particle size of the primary particles of naphthol red according to the present invention is preferably 0.02 to 0.20 ⁇ m.
  • the average particle size P50 of the primary particles is less than 0.02, dispersion tends to be difficult.
  • the average particle size P50 of the primary particles is larger than 0.20, the color developability is inferior.
  • a more preferable average particle size P50 of primary particles is 0.02 to 0.15 ⁇ m.
  • the haze value at a film thickness of 3 ⁇ m is preferably 10 to 20% in a polyester resin coating film of naphthol red pigment concentration of 5% according to the present invention.
  • the haze value is larger than 20%, it is difficult to say that the dispersibility of the coating film is excellent, and it can be said that the dispersion is poor.
  • a more preferred haze value is 12 to 19%.
  • the chroma c * at a film thickness of 3 ⁇ m is preferably 60 or more, and it can be said that the color development is excellent.
  • 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.
  • a more preferred color index c * is 70 or more.
  • a * and b * at a film thickness of 3 ⁇ m are not particularly limited.
  • * And b * are both 0 or more.
  • magenta is expressed, a * is preferably 0 or more and b * is less than 0.
  • the powder pH of the naphthol red according to the present invention is preferably in the range of 4.0 to 9.0.
  • the powder pH is less than 4.0, dispersion into a resin or the like may be hindered.
  • 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.
  • 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.
  • Organic surface treating agents such as compounds, inorganic surface treating agents such as inorganic fine particles such as silica, alumina and titanium oxide, and organic and inorganic surface treating agents such as rosin-calcium and rosin-magnesium, or two of them. What was processed with what was combined above is also good.
  • the naphthol red represented by the chemical formula (1) according to the present invention is manufactured by adding a diazonium salt cooling solution of an aromatic amine represented by the chemical formula (2) to the naphthol cooling solution represented by the chemical formula (3).
  • the diazonium salt of aromatic amine is injected and stirred using a syringe, injected and stirred using a spray, or continuously mixed while being dispersed with an ultrasonic homogenizer, or continuously mixed while being dispersed with a line mill.
  • an azo coupling reaction occurs in a minute region, and particles having a small axial ratio are obtained.
  • After stirring this at high speed it is heat-treated to form a pigment. Then, after adjusting pH, performing filtration, washing with water, and drying, it can grind
  • the aromatic amine represented by the chemical formula (12) (official name: 3-amino-4-methoxybenzanilide)
  • a diazonium salt cooling solution is added to a naphthol (formal name: N- (5-chloro-2-methoxyphenonyl) -3-hydroxy-2-naphthalenecarboxamide) cooling solution represented by the chemical formula (13).
  • the method for adding the diazonium salt of the aromatic amine is performed by injecting and stirring using a syringe, injecting and stirring using a spray, or continuously mixing while dispersing with an ultrasonic homogenizer, or continuously while dispersing with a line mill.
  • an azo coupling reaction occurs in a minute region, and fine particles having a small axial ratio are obtained.
  • it is heat-treated to form a pigment.
  • it after adjusting pH, performing filtration, washing with water, and drying, it can grind
  • the naphthol red represented by the chemical formula (1) according to the present invention is produced by adding the naphthol cooling solution represented by the chemical formula (3) to the diazonium salt cooling solution of the aromatic amine represented by the chemical formula (2). At that time, the naphthol cooling solution is injected and stirred using a syringe, injected and stirred using a spray, or continuously mixed while being dispersed by an ultrasonic homogenizer, or continuously mixed while being dispersed by a line mill. As a result, an azo coupling reaction occurs in a minute region, and particles having a small axial ratio are obtained. After stirring this at high speed, it is heat-treated to form a pigment. Then, after adjusting pH, performing filtration, washing with water, and drying, it can grind
  • the naphthol cooling solution represented by the chemical formula (13) is cooled with the diazonium salt of the aromatic amine represented by the chemical formula (12). Produced in addition to the solution.
  • the addition method of the naphthol cooling solution is injected and stirred using a syringe, injected and stirred using a spray, or continuously mixed while being dispersed by an ultrasonic homogenizer, and continuously mixed while being dispersed by a line mill.
  • an azo coupling reaction occurs in a minute region, resulting in fine particles having a small axial ratio. After stirring this at high speed, it is heat-treated to form a pigment. Then, after adjusting pH, performing filtration, washing with water, and drying, it can grind
  • a method produced by 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.
  • 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 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.
  • the reactivity is not as high as that of the positive coupling.
  • the reaction can easily proceed because the reaction can be performed in a large excess of the diazonium salt cooling liquid.
  • either forward coupling or reverse coupling is not excellent, but it is selected depending on chemical species, required quality, and the like.
  • Injecting and stirring using a syringe refers to stirring a naphthol cooling solution or a diazonium salt cooling solution of an aromatic amine, and quickly cooling the paired cooling solution using one or more syringes. This is an operation of injection, and by diffusing through a syringe, each substance is contact-reacted in a fine region to become fine naphthol red with a small axial ratio. It is preferable to use a syringe having a diameter of 1.0 mm or less. More preferably, a caliber having a diameter of 0.8 mm or less is used. More preferably, it is preferable to use one having a diameter of 0.5 mm or less.
  • Injecting and stirring by spraying is to stir a naphthol cooling solution or a diazonium salt cooling solution of an aromatic amine, and quickly cool the paired cooling solution using one or more nozzles.
  • This is an operation for spray injection, and by diffusing through the nozzle, each substance contacts and reacts in a fine region to become fine naphthol red with a small axial ratio.
  • a nozzle having a diameter of 1.0 mm or less More preferably, a caliber having a diameter of 0.8 mm or less is used. More preferably, it is preferable to use one having a diameter of 0.5 mm or less.
  • Continuous mixing while being dispersed with an ultrasonic homogenizer means that a naphthol cooling solution or a diazonium salt cooling solution of an aromatic amine is circulated, and a diazonium salt cooling solution of the paired aromatic amine or a part of the line, or Then, a naphthol cooling solution is injected, and an ultrasonic homogenizer is irradiated to the contact portion, and each substance comes into contact with each other in a fine region to form particles with a small axial ratio.
  • Continuous mixing while being dispersed by a line mill means that a naphthol cooling solution or a diazonium salt cooling solution of an aromatic amine is circulated, and a diazonium salt cooling solution of a paired aromatic amine or naphthol is part of the line.
  • the cooling solution is injected, and the contact portion is dispersed by a line mill, and each substance contacts and reacts in a fine region to form particles having a small axial ratio.
  • ⁇ Particles with a small axial ratio prepared by each method are crushed by high-speed stirring. Thereafter, it is pigmented by heat treatment with normal stirring.
  • High-speed stirring is preferably performed at a rotation speed of 1000 rpm or more. Usually, stirring is 100 to 300 rpm.
  • a diazonium salt cooling solution of an aromatic amine is obtained by converting an aromatic amine of chemical formula (2) (3-amino-4-methoxybenzanilide represented by chemical formula (12) in the case of production of naphthol red of chemical formula (11)) to an acid. It is prepared by dissolving in a cooling aqueous solution and adding a sodium nitrite aqueous solution and 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 vulnerable 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.
  • the acid examples 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.
  • inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid
  • organic acids such as formic acid, acetic acid, citric acid, adipic acid, and paratoluenesulfonic acid.
  • the naphthol cooling solution contains naphthol represented by the chemical formula (3) (in the case of producing naphthol red represented by the chemical formula (11), N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2- Naphthalenecarboxamide) is preferably suspended in an aqueous base solution, dissolved by heating at 80 ° C., and cooled to 0 to 5 ° C. Storage and reaction are carried out 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.
  • naphthol for example, N- (5-chloro-2-methoxyphenyl-3-hydroxy-2-naphthalenecarboxamide of the chemical formula (13)
  • naphthol for example, N- (5-chloro-2-methoxyphenyl-3-hydroxy-2-naphthalenecarboxamide of the chemical formula (13)
  • the base examples 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.
  • it is preferably heated to 90 ° C. as it is in order to form a pigment after stirring at high speed.
  • the pH is preferably adjusted to a range of 4.0 to 9.0 by adding an acid agent or an alkali agent. Furthermore, the pH is preferably in the range of 4.0 to 8.0.
  • an inorganic compound or an organic compound may be used as the acid agent.
  • the inorganic compound include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid
  • the organic compound include formic acid, acetic acid, citric acid, adipic acid, and paratoluenesulfonic acid.
  • an inorganic compound or an organic compound may be used as the alkali agent.
  • inorganic compounds include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and carbonates such as sodium carbonate
  • organic compounds include trialkanol amines such as triethanolamine and triisopropanolamine. It is done.
  • the target naphthol red according to the present invention can be obtained by filtering, washing with water, drying and pulverizing by a conventional method.
  • the naphthol red represented by the chemical formula (1) according to the present invention is prepared by continuously injecting and stirring the cooling solution of the aromatic amine azonium salt represented by the chemical formula (2) into the naphthol cooling solution represented by the chemical formula (3).
  • a hydrophilic naphthol derivative represented by the chemical formula (4) or a hydrophilic phenol derivative represented by the chemical formula (5) before the reaction is completed particles having a small axial ratio are obtained. .
  • This 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
  • the naphthol red according to the present invention will be described with reference to the method for producing naphthol red represented by the chemical formula (11).
  • -4-Methoxybenzanilide is cooled with a naphthol (formal name: N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthalenecarboxamide) represented by the chemical formula (13). It reacts by injecting and stirring into the solution, and before the reaction is completed, a hydrophilic naphthol derivative represented by the chemical formula (4) or a hydrophilic phenol derivative represented by the chemical formula (5) is added and reacted. Fine particles with a small ratio.
  • 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
  • the naphthol red represented by the formula 1 according to the present invention reacts by continuously injecting and stirring the naphthol cooling solution represented by the chemical formula (3) into the aromatic amine azonium salt cooling solution represented by the chemical formula (2). Then, before the reaction is completed, by adding a hydrophilic naphthol derivative represented by the chemical formula (4) or a hydrophilic phenol derivative represented by the chemical formula (5) and reacting, Become. This 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
  • the naphthol red concerning the present invention will convert the naphthol cooling solution shown by the chemical formula (13) by the chemical formula (12). It reacts by injecting and stirring the cooled aromatic amine azonium salt solution, and before the reaction is completed, the hydrophilic naphthol derivative represented by the chemical formula (4) or the hydrophilic phenol represented by the chemical formula (5) By adding a derivative 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
  • a method produced by 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.
  • 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 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.
  • the reactivity is not as high as that of the positive coupling.
  • the reaction can easily proceed because the reaction can be performed in a large excess of the diazonium salt cooling liquid.
  • either forward coupling or 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 obtained by dissolving these (3-amino-4-methoxybenzanilide represented by the chemical formula (12) in the case of the production of naphthol red of the chemical formula (11)) in a cooling aqueous solution of an acid, It is prepared by adding a sodium nitrite aqueous solution or the like to this. 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 vulnerable 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.
  • the acid examples 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.
  • inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid
  • organic acids such as formic acid, acetic acid, citric acid, adipic acid, and paratoluenesulfonic acid.
  • the naphthol cooling solution is preferably suspended in an aqueous base solution, dissolved by heating at 80 ° C., and cooled to 0 to 5 ° C. Storage and reaction are carried out 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.
  • naphthol for example, N- (5-chloro-2-methoxyphenyl-3-hydroxy-2-naphthalenecarboxamide of the chemical formula (13)
  • naphthol for example, N- (5-chloro-2-methoxyphenyl-3-hydroxy-2-naphthalenecarboxamide of the chemical formula (13)
  • the base examples 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 a derivative having one or more hydrophilic functional groups in 1-naphthol or 2-naphthol.
  • the hydrophilic phenol derivative is preferably phenol or a derivative having one or more hydrophilic functional groups on phenol.
  • phenol catechol, hydroquinone, benzenetriol, phloroglucinol, salicylic acid, aminophenol, phenol-3-sulfonic acid, or salts thereof such as sodium and potassium.
  • the addition amount of the hydrophilic naphthol derivative or the hydrophilic phenol derivative is 1 to 10% by weight with respect to the naphthol red to be synthesized. More preferably, it is 1 to 5% by weight.
  • 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 cooled to 0 to 5 ° C. and added. It is preferable.
  • the azo coupling reaction 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, the pH is preferably in the range of 4.0 to 8.0.
  • an inorganic compound or an organic compound may be used as the acid agent.
  • the inorganic compound include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid
  • the organic compound include formic acid, acetic acid, citric acid, adipic acid, and paratoluenesulfonic acid.
  • an inorganic compound or an organic compound may be used as the alkali agent.
  • inorganic compounds include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and carbonates such as sodium carbonate
  • organic compounds include trialkanol amines such as triethanolamine and triisopropanolamine. It is done.
  • the target naphthol red according to the present invention can be obtained by filtering, washing with water, drying and pulverizing by a conventional method.
  • the naphthol red according to the present invention 10 is a naphthol red represented by the chemical formula (11), and the hydrophilic naphthol derivative represented by the chemical formula (4) or the hydrophilic phenol derivative represented by the chemical formula (5) is 0.01. Naphthol red with a surface treatment of ⁇ 0.3% by weight.
  • hydrophilic naphthol derivative represented by the chemical formula (4) the same one as described for the hydrophilic naphthol derivative represented by the chemical formula (4) in the method for producing the second form of naphthol red can be used.
  • hydrophilic phenol derivative represented by the chemical formula (5) the same one as described for the hydrophilic naphthol derivative represented by the chemical formula (5) in the production method of the second form of naphthol red can be used.
  • the axial ratio (average major axis diameter / average minor axis diameter) of the primary particles of naphthol red according to the present invention 10 preferably has the axial ratio in the range described for the naphthol red according to the present invention 1 to 6, for the reason Are as described for naphthol red according to the first to sixth aspects of the present invention.
  • the average major axis diameter of the primary particles of naphthol red according to the present invention 10 preferably has an average major axis diameter in the range described for the naphthol red according to the present inventions 1 to 6, and the reason is also described in the present inventions 1 to 6. This is as described for the naphthol red.
  • the average minor axis diameter of the primary particles of naphthol red according to the present invention 10 preferably has an average minor axis diameter in the range described for the naphthol red according to the present inventions 1 to 6, and the reason is also described in the present inventions 1 to 6. This is as described for the naphthol red.
  • the average particle diameter of the primary particles of naphthol red according to the present invention 10 preferably has an average particle diameter in the range described for the naphthol red according to the present invention 1 to 6, and the reason thereof is also naphthol according to the present invention 1 to 6. As explained in red.
  • the haze value at a film thickness of 3 ⁇ m of the naphthol red pigment resin film having a pigment concentration of 5% according to the present invention 10 preferably has the haze value within the range described for the naphthol red according to the present invention 1 to 6. The reason for this is also as described in the naphthol red according to the present invention 1 to 6.
  • the chroma c * is in the thickness of 3 [mu] m, the range of the chroma c * described in Naphthol Red according to the present invention 1-6 The reason for this is also as described for the naphthol red according to the present invention 1-6.
  • the powder pH of the naphthol red according to the present invention 10 preferably has a powder pH in the range described with respect to the naphthol red according to the present invention 1 to 6, and the reason is also explained with the naphthol red according to the present invention 1 to 6. That's right.
  • the naphthol red according to the present invention may be subjected to further surface treatment in order to improve dispersibility, color developability and the like.
  • the surface treatment material those described for naphthol red according to the present invention 1 to 6 can be used.
  • the naphthol red is a solution of an aromatic amine (formal name: 3-amino-4-methoxybenzanilide) represented by the chemical formula (12) with an azonium salt cooling solution represented by the chemical formula (13).
  • an aromatic amine (formal name: 3-amino-4-methoxybenzanilide) represented by the chemical formula (12)
  • an azonium salt cooling solution represented by the chemical formula (13).
  • a hydrophilic naphthol derivative represented by the formula (2) or a hydrophilic phenol derivative represented by the chemical formula (5) is added and reacted, particles having 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
  • the naphthol red according to the present invention 10 reacts by continuously injecting and stirring the naphthol cooling solution represented by the chemical formula (13) into the aromatic amine azonium salt cooling solution represented by the chemical formula (12). Before completion, particles having a small axial ratio are obtained by adding a hydrophilic naphthol derivative represented by the chemical formula (4) or a hydrophilic phenol derivative represented by the chemical formula (5) for reaction. The mixture is stirred for a certain period of time while being cooled, and then heated to form a pigment. Then, after adjusting pH, performing filtration, washing with water, and drying, it can grind
  • a method produced by 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.
  • 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 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.
  • the reactivity is not as high as that of the positive coupling.
  • the reaction can easily proceed because the reaction can be performed in a large excess of the diazonium salt cooling liquid.
  • either forward coupling or reverse coupling is not excellent, but it is selected depending on chemical species, required quality, and the like.
  • the diazonium salt cooling solution of the aromatic amine is prepared by dissolving the aromatic amine represented by the chemical formula (12) in an acid cooling aqueous solution, and adding a sodium nitrite aqueous 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 vulnerable 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.
  • the acid examples 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.
  • inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid
  • 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 the chemical formula (13) in an aqueous base solution, dissolving the naphthol by heating at 80 ° C., and cooling to 0 to 5 ° C. Storage and reaction are carried out 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. Naphthol can also be used without being dissolved.
  • the base examples 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 addition amount of the hydrophilic naphthol derivative or the hydrophilic phenol derivative is 1 to 10% by weight with respect to the naphthol red to be synthesized. More preferably, it is 1 to 5% by weight.
  • 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 cooled to 0 to 5 ° C. and added. It is preferable.
  • the azo coupling reaction 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. More preferably, the pH is in the range of 4.0 to 8.0.
  • an inorganic compound or an organic compound may be used as the acid agent.
  • the inorganic compound include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid
  • the organic compound include formic acid, acetic acid, citric acid, adipic acid, and paratoluenesulfonic acid.
  • an inorganic compound or an organic compound may be used as the alkali agent.
  • inorganic compounds include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and carbonates such as sodium carbonate
  • organic compounds include trialkanol amines such as triethanolamine and triisopropanolamine. It is done.
  • the target naphthol red according to the present invention can be obtained by filtering, washing with water, drying and pulverizing by a conventional method.
  • 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.
  • additives such as lubricants, plasticizers, antioxidants, ultraviolet absorbers, and various stabilizers as necessary.
  • 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.
  • 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.
  • 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 base material, and considering the handling of the dispersion.
  • the amount is preferably 0.1 to 100 parts by weight, more preferably 0.1 to 50 parts by weight.
  • extender pigments include inorganic pigments such as silica, titanium oxide, barium sulfate, zinc oxide and magnesium oxide, polymers such as acrylic fine particles and polyester fine particles.
  • 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.
  • the pigment dispersant examples include a polymer anion pigment dispersant, a polymer nonionic pigment dispersant, and a polymer cationic pigment dispersant.
  • 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.
  • 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.
  • 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.
  • 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 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 base material, considering the handling of the dispersion.
  • it is preferably 0.1 to 100 parts by weight, and more preferably 0.1 to 50 parts by weight.
  • resin commonly used acrylic resin, alkyd resin, polyester resin, polyurethane resin, epoxy resin, phenol resin, melamine resin, amino resin and the like can be used.
  • Solvents include 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.
  • 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.
  • 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 developability.
  • the naphthol red according to the present invention has a surface treated with a hydrophilic naphthol derivative or a hydrophilic phenol derivative on the outermost surface thereof, has a polar pigment surface, and is excellent in dispersibility.
  • the primary particles are particles having a small axial ratio, and the axial ratio is small, so that the dispersibility is excellent. Because of these two excellent dispersibility effects, naphthol red has excellent color development and transparency.
  • the production method of the first form of naphthol red controls the addition and mixing method of a diazonium salt cooling solution of an aromatic amine and a naphthol cooling solution, and the azo coupling reaction proceeds in a minute region. Particles having a small 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 surface of the naphthol derivative or hydrophilic phenol derivative is surface-treated at the end of the azo coupling reaction, so that the pigment surface has polarity and crystal growth is reduced. Therefore, 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 it is excellent in dispersibility and color developability.
  • 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 minor minor axis diameter of the primary particles are both the major axis diameter and 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 primary particles is indicated by the 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 ⁇ m) 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 ⁇ m.
  • the haze value was measured using a haze meter (Haze Meter NDH4000 manufactured by Nippon Denshoku Industries Co., Ltd.).
  • 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.
  • an application piece (coating film thickness: about 3 ⁇ m) 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 ⁇ m.
  • 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.
  • the color development of the naphthol red according to the present invention is determined by chromaticity c * , ⁇ 65 or more, ⁇ 60 to 65, 55 55 to less than 60 ⁇ , less than 55 ⁇ . did.
  • 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.
  • 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) 0.01g (Manufactured by Nissin EM) And this pellet was sliced to a film thickness of 2 ⁇ m 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.
  • Undispersed material is not recognized. ⁇ : 1 to 10 undispersed materials are observed per 100 ⁇ m 2 . ⁇ : 11 to 50 undispersed materials are observed per 100 ⁇ m 2 . X: 51 or more undispersed substances are recognized per 100 ⁇ m 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 ⁇ m. The coated strip (film thickness: about 3 ⁇ m) was prepared, and the coated strip was measured using a spectrocolorimeter X-Rite 939 (manufactured by X-Rite) according to JIS Z8729, 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.
  • 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.).
  • the initial viscosity and the viscosity with time after one 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.
  • 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
  • an application piece 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 ⁇ m.
  • the haze value was measured using a haze meter (Haze Meter NDH4000 manufactured by Nippon Denshoku Industries Co., Ltd.).
  • 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% ⁇ , 25% or more ⁇ It was.
  • the hue of the coating film using the aqueous dispersion prepared in Examples described later is defined in JIS Z8729 using a spectrocolorimeter X-Rite 939 (manufactured by 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 saturation c * of 60 or more can be used practically without any problem.
  • 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.).
  • the initial viscosity and the viscosity with time after one 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.
  • Viscosity change rate is less than ⁇ 15% ⁇ : Viscosity change rate is ⁇ 15% or more and less than ⁇ 30% ⁇ : Viscosity change rate is ⁇ 30% or more
  • an applied piece 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 ⁇ m.
  • the haze value of the coated piece was measured using a haze meter (Haze Meter NDH4000 manufactured by Nippon Denshoku Industries Co., Ltd.).
  • 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% ⁇ , 25% or more ⁇ It was.
  • 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.
  • Identification and quantification of the hydrophilic naphthol derivative or hydrophilic phenol derivative present on the surface of the naphthol red according to the present invention were performed by the following procedure. First, 10 mg of naphthol red according to the present invention is soaked in 10 mL of methanol, and ultrasonic components are extracted with an ultrasonic cleaner (100 W, 30 minutes) to extract the surface-treated components, and the solid content is filtered. This was removed to obtain an extract from the surface. This extract is subjected to high performance liquid chromatography using a reversed phase column to identify and quantify hydrophilic naphthol derivatives or hydrophilic phenol derivatives from the peak position and peak intensity. It was defined as the identification and quantification of the substance. The measurement conditions are shown below.
  • High performance liquid chromatograph LaChrom Elite (manufactured by Hitachi High-Technologies) Detector: UV-vis (258 nm) Reversed phase column: TSKgel ODS-100Z (4.6 mm ID ⁇ 15 cm) (Tosoh Corporation) Eluent: 60% methanol aqueous solution Flow rate: 0.5 ml / min Oven temperature: 40.0 ° C Sample injection volume: 20 ⁇ L
  • Examples 1-1 to 1-32 are examples in which naphthol red represented by the chemical formula (11) was produced by the production method of the first embodiment (present invention 7).
  • Examples 2-1 to 2-32 This is an example in which the naphthol red represented by the chemical formula (11) is produced by the production method of the second form (present invention 8), and Examples 3-1 to 3-64 are naphthol red represented by the chemical formula (1).
  • This is an example of the case of production by the production method of the first form (Invention 7) and the production method of the second form (Invention 8).
  • Examples 4-1 to 4-32 are the chemical formulas (11) relating to the Invention 10. It is an example of naphthol red shown by.
  • Example 1-1 (syringe injection) 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.
  • 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 mixture was stirred at a high speed for 1200 hours.
  • it heated to 90 degreeC and stirred at 1200 rpm for 1 hour as it was at high speed.
  • 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.
  • Example 1-2 (mist injection) A diazonium salt cooling solution and a naphthol cooling solution were obtained in the same manner as in Example 1-1 except that the amount of the drug and the amount of water were changed. Then, the diazonium salt cooling solution is put into a sprayer equipped with a 0.5 mm nozzle and injected into the naphthol cooling solution stirring liquid at a rate of 15 parts by weight / min. Stir at 1200 rpm. Then, 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-1-2)
  • Example 1-3 (ultrasound) A diazonium salt cooling solution and a naphthol cooling solution were obtained in the same manner as in Example 1-1 except that the amount of the drug and the amount of water were changed. Then, an ultrasonic homogenizer equipped with a continuous crushing adapter (BRANSON-made SOFIFER II model 250D), a peristaltic pump, and a vessel with a cooling unit were connected, and the naphthol cooling solution was circulated at 150 parts by weight / min at 5 ° C. or less. In addition, a 0.5 mm syringe was attached to the lower 1 cm portion of the ultrasonic homogenizer crushing horn, and a syringe pump containing a diazonium salt cooling solution was attached to the tip.
  • a continuous crushing adapter BRANSON-made SOFIFER II model 250D
  • a peristaltic pump a vessel with a cooling unit
  • the diazonium salt cooling solution was injected at 15 parts by weight / minute at 5 ° C. or lower, and the naphthol cooling solution and the diazonium salt cooling were performed while irradiating ultrasonic waves at the nose of the crushing horn.
  • the solution reacted in diffusion contact.
  • the injection was stopped by irradiating with ultrasonic waves while continuously circulating the peristaltic pump for 5 minutes after the injection of the diazonium salt cooling solution. Then, this reaction liquid was returned to the vessel and stirred at 1200 rpm at 5 ° C. or lower for 1 hour.
  • Example 1-4 (line mill) A diazonium salt cooling solution and a naphthol cooling solution were obtained in the same manner as in Example 1-1 except that the amount of the drug and the amount of water were changed. Then, a line mill (Primix TK Pipeline Homomixer PL-2S) equipped with a raw material supply tank and a circulation stirring tank was prepared, and a naphthol cooling solution was added to the circulation stirring tank at 150 parts by weight / min at 5 ° C. or less. Circulated. Moreover, the diazonium salt cooling solution was put into the raw material supply tank.
  • a line mill Primary TK Pipeline Homomixer PL-2S
  • the diazonium salt cooling solution was added to the line mill at 15 parts by weight / min and 5 ° C. or less, and the naphthol cooling solution and the diazonium salt cooling solution were stirred at the nose of the line mill. Reacted by diffusion contact.
  • the mixture was continuously stirred for 5 minutes and then stopped. Thereafter, the reaction solution was transferred to another vessel and stirred at 1200 rpm at 5 ° C. or less for 1 hour. Then, it heated to 90 degreeC and stirred at 1200 rpm as it was for 1 hour.
  • Example 1-5 (syringe injection) A diazonium salt cooling solution and a naphthol cooling solution were obtained in the same manner as in Example 1-1 except that the amount of the drug and the amount of water were changed. Then, the naphthol cooling solution is put into a syringe pump equipped with a 0.5 mm nozzle, and injected into the liquid at a rate of 15 parts by weight / min into the diazonium salt cooling solution stirring liquid at 10 ° C. or lower, and 1 at 5 ° C. or lower. Stir for 1200 hours at time. Then, it heated to 90 degreeC and stirred at 1200 rpm as it was for 1 hour.
  • Example 1-6 (mist injection) A diazonium salt cooling solution and a naphthol cooling solution were obtained in the same manner as in Example 1-1 except that the amount of the drug and the amount of water were changed. Then, the naphthol cooling solution is put into a sprayer 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 1200 rpm. Then, 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-1-6)
  • Example 1-7 (ultrasound) A diazonium salt cooling solution and a naphthol cooling solution were obtained in the same manner as in Example 1-1 except that the amount of the drug and the amount of water were changed. Then, an ultrasonic homogenizer equipped with a continuous crushing adapter (BRANSON made SOFIFER II model 250D), a peristaltic pump, and a vessel with a cooling unit were connected, and the diazonium salt cooling solution was circulated at 150 ° C./min at 5 ° C. or less. Moreover, a 0.5 mm syringe was attached to a 1 cm lower part of the ultrasonic homogenizer crushing horn, and a syringe pump containing a naphthol cooling solution was attached to the tip.
  • BRANSON made SOFIFER II model 250D continuous crushing adapter
  • a peristaltic pump a vessel with a cooling unit
  • the naphthol cooling solution was injected at 15 parts by weight / minute at 5 ° C. or lower, and radiated with ultrasonic waves at the tip of the crushing horn, while the naphthol cooling solution and the diazonium salt cooling solution were applied. Reacted by diffusion contact.
  • the injection was stopped by irradiating ultrasonic waves while circulating the peristaltic pump continuously for 5 minutes after the injection of the naphthol cooling solution. Then, this reaction liquid was returned to the vessel and stirred at 1200 rpm at 5 ° C. or lower for 1 hour. Then, it heated to 90 degreeC and stirred at 1200 rpm as it was for 1 hour.
  • Example 1-8 (line mill) A diazonium salt cooling solution and a naphthol cooling solution were obtained in the same manner as in Example 1-1 except that the amount of the drug and the amount of water were changed. Then, a line mill (Primix TK Pipeline Homomixer PL-2S) equipped with a raw material supply tank and a circulation stirring tank is prepared, and a diazonium salt cooling solution is 150 parts by weight / minute, 5 ° C. or less in the circulation stirring tank. It circulated in. Moreover, the naphthol cooling solution was put into the raw material supply tank.
  • a line mill Primary TK Pipeline Homomixer PL-2S
  • the diazonium salt cooling solution was added to the line mill at 15 parts by weight / min and 5 ° C. or less, and the naphthol cooling solution and the diazonium salt cooling solution were stirred at the nose of the line mill. Reacted by diffusion contact. After the addition of the naphthol cooling solution, circulation stirring was continued for 5 minutes and stopped. Thereafter, the reaction solution was transferred to another vessel and stirred at 1200 rpm at 5 ° C. or less for 1 hour. Then, it heated to 90 degreeC and stirred at 1200 rpm as it was for 1 hour.
  • Comparative Example 1-1 (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 at 0-5 ° 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.
  • Comparative Example 1-2 (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 a temperature condition of 0 to 5 ° C., 72 parts by weight of 35% HCl aqueous solution was added and 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.
  • Comparative Example 1-4 (Follow-up experiment 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 to 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.
  • the naphthol reds of the examples all have an axial ratio in the range of 1.0 to 2.0, and are clearly excellent in dispersibility and color developability.
  • Example 1-9 3.0 parts by weight of the red pigment 1-1 obtained in Example 1-1 and 57.0 parts by weight of the polyester resin DIACRON ER561 (manufactured by Mitsubishi Rayon) were weighed and ground 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
  • Examples 1-10 to 1-16, Comparative Examples 1-5 to 1-8 A resin composition was obtained in the same manner as in Example 1-9 except that various types of naphthol red were used.
  • Example 1-17 Using 0.5 parts by weight of naphthol red obtained in Example 1-1 in a 140 ml glass bottle, the aqueous dispersion composition was blended in the following proportions and mixed and dispersed in a paint shaker for 60 minutes together with 50 parts by weight of 1.5 mm ⁇ 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 1-18 to 1-24, Comparative Examples 1-9 to 1-12 An aqueous dispersion was obtained in the same manner as in Example 1-17 except that the type of naphthol red was variously changed.
  • aqueous dispersions of the examples are excellent in storage stability, excellent in dispersibility, and excellent in color developability.
  • Example 1-25 Using 0.50 parts by weight of naphthol red obtained in Example 1-1 in a 140 ml glass bottle, the solvent-based dispersion composition was blended in the following proportions and mixed with a paint shaker for 60 minutes together with 50 parts by weight of 1.5 mm ⁇ glass beads. Dispersion was performed to obtain a solvent-based dispersion.
  • 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 1-26 to 1-32 and Comparative Examples 1-13 to 1-16 A solvent-based dispersion was obtained in the same manner as in Example 1-25 except that the type of naphthol red was variously changed.
  • the solvent-based dispersions of the examples have excellent storage stability, excellent dispersibility, and excellent color developability.
  • Example 2-1 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.
  • 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.
  • a solution in which 0.4 part by weight of 2-naphthol-3carboxylic acid was dissolved in 20 parts by weight of ice water was prepared and cooled to 5 ° C. or lower. 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.
  • Examples 2-2 to 2-4 A naphthol red according to the present invention was obtained in the same manner as in Example 2-1, 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 -2-2 to 4)
  • Example 2-5 In the same manner as in Example 2-1, 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. Thereafter, a solution in which 0.4 parts by weight of 2-naphthol-3carboxamide was dissolved in 20 parts by weight of ice water was prepared, and the solution was cooled to 5 ° C. or lower. And the solution was added to the reaction liquid at 5 degrees C or less, and also stirred at 300 rpm for 1 hour.
  • Examples 2-6 to 2-8 A naphthol red according to the present invention was obtained in the same manner as in Example 2-5 except that the hydrophilic naphthol derivative to be additionally added or the kind and amount of the hydrophilic phenol derivative and the reaction conditions were variously changed. (Red pigments 2-6 to 8)
  • Comparative Example 2-1 Additional Experiment of Production Example 1 of JP-A-11-272014
  • Comparative Example 1-1 Red Pigment-2-9
  • the production conditions at this time are shown in Table 2-1
  • the characteristics of the obtained monoazo pigment are shown in Table 2-2.
  • Comparative Example 2-2 (Follow-up experiment of Production Example 1 of JP 2000-186241 A) Same as Comparative Example 1-2 above (Red Pigment-2-10). The production conditions at this time are shown in Table 2-1, and the characteristics of the obtained monoazo pigment are shown in Table 2-2.
  • Comparative Example 2-3 (Follow-up experiment of Example 2 of JP-A-2005-3275) Same as Comparative Example 1-3 (Red Pigment-2-11). The production conditions at this time are shown in Table 2-1, and the characteristics of the obtained mixed crystal pigment are shown in Table 2-2.
  • Comparative Example 2-4 Fluorescence-up experiment of Example 1 of JP 2000-248191 A
  • Comparative Example 1-4 Red Pigment-2-12
  • the production conditions at this time are shown in Table 2-1, and the characteristics of the obtained monoazo red pigment are shown in Table 2-2.
  • the naphthol reds of the examples all have an axial ratio in the range of 1.0 to 2.0, and are clearly excellent in dispersibility and color developability.
  • Example 2-9 3.0 parts by weight of the red pigment 2-1 obtained in Example 2-1 and 57.0 parts by weight of the polyester resin DIACRON ER561 (manufactured by Mitsubishi Rayon) were weighed and ground 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
  • ZM200 ultracentrifugal crusher
  • Example 2-17 Using 0.5 parts by weight of naphthol red obtained in Example 2-1 in a 140 ml glass bottle, the aqueous dispersion composition was blended in the following proportions and mixed and dispersed in a paint shaker for 60 minutes together with 50 parts by weight of 1.5 mm ⁇ 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 2-18 to 2-24, Comparative Examples 2-9 to 2-12 An aqueous dispersion was obtained in the same manner as in Example 2-17 except that the type of naphthol red was variously changed.
  • aqueous dispersions of the examples are excellent in storage stability, excellent in dispersibility, and excellent in color developability.
  • Example 2-25 Using 0.50 parts by weight of naphthol red obtained in Example 2-1 in a 140 ml glass bottle, the solvent-based dispersion composition was blended at the following ratio and mixed with a paint shaker for 60 minutes together with 50 parts by weight of 1.5 mm ⁇ glass beads. A solvent dispersion was prepared by dispersion.
  • 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.
  • the solvent-based dispersions of the examples have excellent storage stability, excellent dispersibility, and excellent color developability.
  • Example 3-1 (syringe injection) Naphthol red (CI Pigment Red 269) according to the present invention was obtained in the same manner as in Example 1-1.
  • Example 3-2 (mist injection) A diazonium salt cooling solution and a naphthol cooling solution were obtained in the same manner as in Example 3-1, except that the amounts of aromatic amine, naphthol, drug, and water were changed. Then, the diazonium salt cooling solution is put into a sprayer equipped with a 0.5 mm nozzle and injected into the naphthol cooling solution stirring liquid at a rate of 15 parts by weight / min. Stir at 1200 rpm. Then, 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. (C.I. Pigment Red 5) was obtained. (Red pigment-3-2)
  • Example 3-3 (ultrasound) A diazonium salt cooling solution and a naphthol cooling solution were obtained in the same manner as in Example 3-1, except that the amounts of aromatic amine, naphthol, drug, and water were changed. Then, an ultrasonic homogenizer equipped with a continuous crushing adapter (BRANSON-made SOFIFER II model 250D), a peristaltic pump, and a vessel with a cooling unit were connected, and the naphthol cooling solution was circulated at 150 parts by weight / min at 5 ° C. or less.
  • a continuous crushing adapter BRANSON-made SOFIFER II model 250D
  • a peristaltic pump a vessel with a cooling unit
  • a 0.5 mm syringe was attached to the lower 1 cm portion of the ultrasonic homogenizer crushing horn, and a syringe pump containing a diazonium salt cooling solution was attached to the tip. Then, while irradiating with ultrasonic waves at an output of 100 W, the diazonium salt cooling solution was injected at 15 parts by weight / minute at 5 ° C. or lower, and the naphthol cooling solution and the diazonium salt cooling were performed while irradiating ultrasonic waves at the nose of the crushing horn. The solution reacted in diffusion contact.
  • Example 3-4 (line mill) A diazonium salt cooling solution and a naphthol cooling solution were obtained in the same manner as in Example 3-1, except that the amounts of aromatic amine, naphthol, drug, and water were changed. Then, a line mill (Primix TK Pipeline Homomixer PL-2S) equipped with a raw material supply tank and a circulation stirring tank was prepared, and a naphthol cooling solution was added to the circulation stirring tank at 150 parts by weight / min at 5 ° C. or less. Circulated. Moreover, the diazonium salt cooling solution was put into the raw material supply tank.
  • a line mill Primary TK Pipeline Homomixer PL-2S
  • the diazonium salt cooling solution was added to the line mill at 15 parts by weight / min and 5 ° C. or less, and the naphthol cooling solution and the diazonium salt cooling solution were stirred at the nose of the line mill. Reacted by diffusion contact.
  • the mixture was continuously stirred for 5 minutes and then stopped. Thereafter, the reaction solution was transferred to another vessel and stirred at 1200 rpm at 5 ° C. or less for 1 hour. Then, it heated to 90 degreeC and stirred at 1200 rpm as it was for 1 hour.
  • Example 3-5 (syringe injection) A diazonium salt cooling solution and a naphthol cooling solution were obtained in the same manner as in Example 3-1, except that the amounts of aromatic amine, naphthol, drug, and water were changed. Then, the naphthol cooling solution is put into a syringe pump equipped with a 0.5 mm nozzle, and injected into the liquid at a rate of 15 parts by weight / min into the diazonium salt cooling solution stirring liquid at 10 ° C. or lower, and 1 at 5 ° C. or lower. Stir for 1200 hours at time. Then, it heated to 90 degreeC and stirred at 1200 rpm as it was for 1 hour.
  • Example 3-6 (mist injection) A diazonium salt cooling solution and a naphthol cooling solution were obtained in the same manner as in Example 3-1, except that the amounts of aromatic amine, naphthol, drug, and water were changed. Then, the naphthol cooling solution is put into a sprayer 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 1200 rpm. Then, 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. (C.I. Pigment Red 150) was obtained. (Red pigment-3-6)
  • Example 3-7 (ultrasound) A diazonium salt cooling solution and a naphthol cooling solution were obtained in the same manner as in Example 3-1, except that the amounts of aromatic amine, naphthol, drug, and water were changed. Then, an ultrasonic homogenizer equipped with a continuous crushing adapter (BRANSON made SOFIFER II model 250D), a peristaltic pump, and a vessel with a cooling unit were connected, and the diazonium salt cooling solution was circulated at 150 ° C./min at 5 ° C. or less.
  • BRANSON made SOFIFER II model 250D
  • a 0.5 mm syringe was attached to a 1 cm lower part of the ultrasonic homogenizer crushing horn, and a syringe pump containing a naphthol cooling solution was attached to the tip. Then, while irradiating ultrasonic waves at an output of 100 W, the naphthol cooling solution was injected at 15 parts by weight / minute at 5 ° C. or lower, and radiated with ultrasonic waves at the tip of the crushing horn, while the naphthol cooling solution and the diazonium salt cooling solution were applied. Reacted by diffusion contact. The injection was stopped by irradiating ultrasonic waves while circulating the peristaltic pump continuously for 5 minutes after the injection of the naphthol cooling solution.
  • this reaction liquid was returned to the vessel and stirred at 1200 rpm at 5 ° C. or lower for 1 hour. Then, 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. (C.I. Pigment Red 170) was obtained. (Red pigment-3-7)
  • Example 3-8 (line mill) A diazonium salt cooling solution and a naphthol cooling solution were obtained in the same manner as in Example 3-1, except that the amounts of aromatic amine, naphthol, drug, and water were changed. Then, a line mill (Primix TK Pipeline Homomixer PL-2S) equipped with a raw material supply tank and a circulation stirring tank is prepared, and a diazonium salt cooling solution is 150 parts by weight / minute, 5 ° C. or less in the circulation stirring tank. It circulated in. Moreover, the naphthol cooling solution was put into the raw material supply tank.
  • a line mill Primary TK Pipeline Homomixer PL-2S
  • the diazonium salt cooling solution was added to the line mill at 15 parts by weight / min and 5 ° C. or less, and the naphthol cooling solution and the diazonium salt cooling solution were stirred at the nose of the line mill. Reacted by diffusion contact. After the addition of the naphthol cooling solution, circulation stirring was continued for 5 minutes and stopped. Thereafter, the reaction solution was transferred to another vessel and stirred at 1200 rpm at 5 ° C. or less for 1 hour. Then, it heated to 90 degreeC and stirred at 1200 rpm as it was for 1 hour.
  • Example 3-9 In the same manner as in Example 2-1, naphthol red (CI Pigment Red 269) according to the present invention was obtained. (Red pigment-3-9)
  • Example 3-10 to 3-12 The naphthol according to the present invention was the same as in Example 3-9, except that the kind and amount of the aromatic amine, naphthol, additionally added hydrophilic naphthol derivative, or hydrophilic phenol derivative, and the reaction conditions were variously changed. I got red. (Red pigment-3-10 to 12)
  • Example 3-13 A diazonium salt cooling solution and a naphthol cooling solution were obtained in the same manner as in Example 3-9 except that the aromatic amine and naphthol were changed. 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. Thereafter, a solution in which 0.4 part by weight of 2-naphthol-3 carxamide was dissolved in 20 parts by weight of ice water was prepared and cooled to 5 ° C. or lower. And the solution was added to the reaction liquid at 5 degrees C or less, and also stirred at 300 rpm for 1 hour.
  • Examples 3-14 to 3-16 According to the present invention, the same procedure as in Example 3-13 was conducted, except that the type and amount of the aromatic amine, naphthol, the additionally added hydrophilic naphthol derivative, or the hydrophilic phenol hot water conductor and the reaction conditions were variously changed. Naphthol red was obtained. (Red pigment-3-14 to 16)
  • Comparative Example 3-1 Additional Experiment of Production Example 1 of JP-A-11-272014 The same as Comparative Example 1-1 above.
  • a monoazo pigment (CI Pigment Red 269) was obtained (red pigment-3-17).
  • the production conditions at this time are shown in Table 3-5, and the properties of the obtained monoazo pigment are shown in Table 3-6.
  • Comparative Example 3-2 Fluorescence-activated fluorescent pigment (CI Pigment Red 269) was obtained (red pigment-3-18). The production conditions at this time are shown in Table 3-5, and the properties of the obtained monoazo pigment are shown in Table 3-6.
  • Comparative Example 3-3 (Follow-up experiment of Example 2 of JP-A-2005-3275) Same as Comparative Example 1-3 above. A mixed crystal pigment was obtained (red pigment-3-20). The production conditions at this time are shown in Table 3-5, and the characteristics of the obtained mixed crystal pigment are shown in Table 3-6.
  • Comparative Example 3-4 (Follow-up experiment of Example 1 of JP 2000-248191 A) The same as Comparative Example 1-4 above. A monoazo red pigment was obtained (red pigment-3-21). The production conditions at this time are shown in Table 3-5, and the characteristics of the obtained monoazo red pigment are shown in Table 3-6.
  • the naphthol reds of the examples all have an axial ratio in the range of 1.0 to 2.0, and are clearly excellent in dispersibility and color developability.
  • Example 3-17 3.0 parts by weight of the red pigment-3-1 obtained in Example 3-1 and 57.0 parts by weight of the polyester resin DIACRON ER561 (manufactured by Mitsubishi Rayon) were weighed and ground 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
  • Example 3-33 Using 0.5 parts by weight of naphthol red obtained in Example 3-1 in a 140 ml glass bottle, the aqueous dispersion composition is blended in the following proportions and mixed and dispersed in a paint shaker for 60 minutes together with 50 parts by weight of 1.5 mm ⁇ 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.
  • aqueous dispersions of the examples are excellent in storage stability, excellent in dispersibility, and excellent in color developability.
  • Example 3-49 Using 0.50 parts by weight of naphthol red obtained in Example 3-1 in a 140 ml glass bottle, the solvent-based dispersion composition was blended in the following proportions and mixed with a paint shaker for 60 minutes together with 50 parts by weight of 1.5 mm ⁇ glass beads. Dispersion was performed to obtain a solvent dispersion.
  • 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.
  • the solvent-based dispersions of the examples have excellent storage stability, excellent dispersibility, and excellent color developability.
  • Example 4-1 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.
  • 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.
  • a solution in which 0.4 part by weight of 2-naphthol-3carboxylic acid was dissolved in 20 parts by weight of ice water was prepared and cooled to 5 ° C. or lower. 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.
  • Examples 4-2 to 4-4 A naphthol red according to the present invention was obtained in the same manner as in Example 4-1, except that the type and amount of the hydrophilic naphthol derivative or hydrophilic phenol derivative to be added and the reaction conditions were variously changed. (Red pigment -4-2 to 4)
  • Example 4-5 In the same manner as in Example 4-1, 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. Thereafter, a solution in which 0.4 parts by weight of 2-naphthol-3carboxamide was dissolved in 20 parts by weight of ice water was prepared, and the solution was cooled to 5 ° C. or lower. And the solution was added to the reaction liquid at 5 degrees C or less, and also stirred at 300 rpm for 1 hour.
  • Examples 4-6 to 4-8 A naphthol red according to the present invention was obtained in the same manner as in Example 4-5 except that the hydrophilic naphthol derivative to be additionally added or the kind and amount of the hydrophilic phenol derivative and the reaction conditions were variously changed. (Red pigment-4-6-8)
  • Comparative Example 4-1 (Follow-up Experiment of Production Example 1 of JP-A-11-272014) Same as Comparative Example 1-1 (Red Pigment-4-9).
  • the production conditions at this time are shown in Table 4-1, and the characteristics of the obtained monoazo pigment are shown in Table 4-2.
  • Comparative Example 4-2 (Follow-up Experiment of Production Example 1 of JP 2000-186241 A) Same as Comparative Example 1-2 above (red pigment-4-10). The production conditions at this time are shown in Table 4-1, and the characteristics of the obtained monoazo pigment are shown in Table 4-2.
  • Comparative Example 4-3 (Follow-up experiment of Example 2 of JP-A-2005-3275) Same as Comparative Example 1-3 above (Red Pigment-4-11). The production conditions at this time are shown in Table 4-1, and the characteristics of the obtained mixed crystal pigment are shown in Table 4-2.
  • Comparative Example 4-4 (Follow-up experiment of Example 1 of JP 2000-248191 A) Same as Comparative Example 1-4 (Red Pigment-4-12). The production conditions at this time are shown in Table 4-1, and the characteristics of the obtained monoazo red pigment are shown in Table 4-2.
  • the naphthol red of the example is surface-treated with a hydrophilic naphthol derivative or a hydrophilic phenol derivative in an amount of 0.01 to 0.3% by weight, and is clearly excellent in dispersibility and color development. .
  • Example 4-9 3.0 parts by weight of the red pigment-4-1 obtained in Example 4-1 and 57.0 parts by weight of the polyester resin DIACRON ER561 (manufactured by Mitsubishi Rayon) were weighed and ground 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
  • Examples 4-10 to 4-16, Comparative Examples 4-5 to 4-8 A resin composition was obtained in the same manner as in Example 4-9 except that the type of naphthol red was variously changed.
  • Example 4-17 Using 0.5 parts by weight of naphthol red obtained in Example 4-1 in a 140 ml glass bottle, the aqueous dispersion composition was blended in the following proportions and mixed and dispersed in a paint shaker for 60 minutes together with 50 parts by weight of 1.5 mm ⁇ 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: manufactured by Nissin Chemical Industry) Pure water 20.61 parts by weight.
  • Examples 4-18 to 4-24, Comparative Examples 4-9 to 4-12 An aqueous dispersion was obtained in the same manner as in Example 4-17 except that the type of naphthol red was variously changed.
  • aqueous dispersions of the examples are excellent in storage stability, excellent in dispersibility, and excellent in color developability.
  • Example 4-25 Using 0.50 parts by weight of naphthol red obtained in Example 4-1 in a 140 ml glass bottle, the solvent-based dispersion composition was blended in the following proportions and mixed with a paint shaker for 60 minutes together with 50 parts by weight of 1.5 mm ⁇ glass beads. Dispersion was performed to obtain a solvent dispersion.
  • 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.
  • the solvent-based dispersions of the examples have excellent storage stability, excellent dispersibility, and excellent color developability.
  • the naphthol red surface-treated with naphthol red, a hydrophilic naphthol derivative, or a hydrophilic phenol derivative according to the present invention has a small primary particle axial ratio and is excellent in dispersibility and color development.
  • excellent, suitable for fields such as non-magnetic developers for electrophotography, inkjet inks, color filters for liquid crystals, and various applications such as paints, printing inks, paints, poster colors, plastic colorants, cosmetics, etc.
  • the method for producing naphthol red according to the present invention is suitable as a method for producing naphthol red having excellent dispersibility and color developability.
  • 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.
  • 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.

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Abstract

The purpose of the present invention is to provide a naphthol red having excellent dispersibility and color development by controlling particle shape, and to provide a resin composition, an aqueous dispersion, and a solvent dispersion that are colored with the naphthol red, and a manufacturing method. Said purpose is achieved by means of: a naphthol red in which the primary particles have an axial ratio (average major axis diameter/average minor axis diameter) of 1.0–2.0, or a naphthol red represented by chemical formula (11) in which 0.01–0.3 wt% of a hydrophilic naphthol derivative represented by chemical formula (4) or a hydrophilic phenol derivative represented by chemical formula (5) is surface treated; a resin composition, an aqueous dispersion, and a solvent dispersion that contain the naphthol red; and a manufacturing method.

Description

ナフトールレッド及びその製造方法、該ナフトールレッドを用いた樹脂組成物、水系分散体及び溶剤系分散体Naphthol red and method for producing the same, resin composition using the naphthol red, aqueous dispersion and solvent dispersion
　本発明は、一次粒子の軸比（平均長軸径／平均短軸径）を高度に制御した分散性、発色性に優れるナフトールレッドを提供するものである。 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.
　本発明は、親水性誘導体によって表面処理された分散性、発色性に優れるナフトールレッドを提供するものである。 The present invention provides naphthol red, which is surface-treated with a hydrophilic derivative and has excellent dispersibility and color developability.
　また、本発明は、前記ナフトールレッドの分散性、発色性に優れる製造方法を提供するものである。 The present invention also provides a method for producing the naphthol red having excellent dispersibility and color development.
　また、本発明は、前記ナフトールレッドによって着色した分散性、発色性に優れる樹脂組成物、水系分散体、および、溶剤系分散体を提供するものである。 The present invention also 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.
　化学式（１）で示されるナフトールレッドは、芳香族アミンのジアゾニウム塩と種々のナフトールのアゾカップリング反応により合成された人工色素である。この芳香族アミンとナフトールの組み合わせは極めて多く、また、黄味から青味の赤色（ボルドー、マロン、バイオレット、ブラウンなど）を呈し、そのほとんどを網羅しながら、その同一系統の他の色素よりも強い着色力をもっている。また、化学種や合成方法の選択により、染料、顔料など多様につくりわけることができるため、様々な色表現が可能である。そこで、従来から、塗料、印刷インキ、絵の具、ポスターカラー、プラスチック着色剤、化粧品等、各種用途に使用されている。（非特許文献１） Naphthol red represented by the chemical formula (1) is an artificial dye synthesized by azo coupling reaction of diazonium salt of 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, they are used for various applications such as paints, printing inks, paints, poster colors, plastic colorants, cosmetics and the like. (Non-Patent Document 1)
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　特に、化学式（１１）で示されるナフトールレッド、（正式名称：Ｎ－（５－クロロ－２－メトキシフェニル）－３－ヒドロキシ－４－　［２－メトキシ－５－（フェニルカルバモイル）フェニルアゾ］－２－ナフトアミド：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　２６９）はジャパンカラーのマゼンタをよく再現する顔料として注目されている。 In particular, naphthol red represented by the chemical formula (11) (formal name: N- (5-chloro-2-methoxyphenyl) -3-hydroxy-4- [2-methoxy-5- (phenylcarbamoyl) phenylazo] -2 -Naphthoamide: CI Pigment Red 269) is attracting attention as a pigment that well reproduces the Japanese color magenta.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　そこで、従来からの用途に加えて、電子写真用非磁性現像剤、インクジェットインク、液晶用カラーフィルターなど厳しい品質基準をもつ用途に検討されるようになってきている。これらの用途においてのマゼンタは、主に、高級顔料であるキナクリドンが使用されている。キナクリドンは優れた発色性、耐久性を持つが、高価でバリエーションに乏しい欠点がある。近年、これらの用途のさらなる高画質化や、さらなる多様性の要求から、安価でバリエーション豊富で高着色力のナフトールレッドが注目されるようになっており、キナクリドン代替として、前記化学式（１）に示されるナフトールレッドが有力候補のひとつとなっている。（特許文献１～５） Therefore, in addition to conventional applications, it has been studied 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 mainly uses 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 higher image quality and more versatility in these applications. As an alternative to quinacridone, the chemical formula (1) The naphthol red shown is one of the promising candidates. (Patent Documents 1 to 5)
　しかしながら、ナフトールレッド顔料は、針状、柱状の粒子形状を取りやすく、上記の厳しい品質基準をもつ用途においては、形状由来の分散不良からくる透明性の不足や発色性の不足のため、本格的な採用には至っていない。それを解消するため、粒径形状制御の検討、別の顔料との混合や混晶の検討など様々な検討がなされており、それぞれの目的に応じて、解決策が練られている。 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.
　粒径形状制御としては、ジアゾニウム塩とカップラー溶液（ナフトール）との混合によって生成されるモノアゾ系顔料で、カップラー溶液にアニオン性界面活性剤を添加して得られる微細なモノアゾ系顔料を用いたマゼンタカラートナー（特許文献１）、カップラー溶液にアニオン性界面活性剤を添加して得られる微細なモノアゾ系顔料を用いたインクジェット用インク（特許文献２）が知られている。 For the control of particle size and shape, magenta is a monoazo pigment produced by mixing a diazonium salt and a coupler solution (naphthol), and a fine monoazo pigment obtained by adding an anionic surfactant to the coupler solution. A 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.
　また、顔料の混合や混晶の検討としては、水不溶性アゾ顔料とキナクリドン系顔料の混合（特許文献３）や、それらの混晶（特許文献４）、モノアゾ系赤色顔料とモノアゾ系赤色顔料誘導体の混合（特許文献５）が知られている。 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.
特開平１１－２７２０１４号公報Japanese Patent Laid-Open No. 11-272014 特開２０００－１８６２４１号公報JP 2000-186241 A 特開平０４－２２６４７７号公報Japanese Patent Laid-Open No. 04-226477 特開２００５－３１２７５号公報JP 200531275 A 特開２０００－２４８１９１号公報JP 2000-248191 A
　これまで述べてきたように、着色力が高く、バリエーションの豊富なナフトールレッドは、従来からの塗料、印刷インキなどの用途に加え、電子写真用非磁性現像剤、液晶用カラーフィルターや、インクジェットインクといった厳しい品質基準の用途に期待されている。しかしながら、ナフトールレッドは針状、柱状粒子になりやすく、その形状に由来して分散、発色性が不良になりやすく、本格的な採用には至っていない。 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.
　即ち、前出特許文献１のものは、後出比較例１に示す通り、一次粒子の軸比が大きいため、分散性に劣り、発色性が十分とは言い難い。 That is, in the above-mentioned Patent Document 1, as shown in Comparative Example 1 described later, since the axial ratio of the primary particles is large, the dispersibility is inferior and it is difficult to say that the color developability is sufficient.
　前出特許文献２のものは、後出比較例２に示す通り、一次粒子の軸比が大きいため、分散性に劣り、発色性が十分とは言い難い。 As described in Comparative Example 2 described later, the above-mentioned Patent Document 2 has a large primary particle axial ratio, and therefore is inferior in dispersibility and is not sufficiently satisfactory in color development.
　前出特許文献４のものは、後出比較例３に示す通り、一次粒子の軸比が大きいため、分散性に劣り、発色性が十分とは言い難い。 As described in Comparative Example 3 below, the one in the above-mentioned Patent Document 4 has a large axial ratio of primary particles, so that the dispersibility is inferior and it is difficult to say that the color developability is sufficient.
　前出特許文献５のものは、後出比較例４に示す通り、一次粒子の軸比が大きいため、分散性に劣り、発色性が十分とは言い難い。 As described in Comparative Example 4 below, the above-mentioned Patent Document 5 has a large primary particle axial ratio, and therefore is inferior in dispersibility and hardly has sufficient color developability.
　そこで、本発明は、粒子形状を制御することにより、分散性に優れ、発色性に優れたナフトールレッドを提供することを技術的課題とする。また本発明は、表面状態が制御された、分散性に優れ、発色性に優れたナフトールレッドを提供することを技術的課題とする。ならびに該ナフトールレッドによって着色した樹脂組成物、水系分散体、および、溶剤系分散体を提供することを技術的課題とする。 Therefore, a technical problem of the present invention is to provide naphthol red having excellent dispersibility and color developability by controlling the particle shape. Another object of the present invention is to provide naphthol red having a controlled surface state, excellent dispersibility, and excellent color developability. Another object of the present invention is to provide a resin composition colored with the naphthol red, an aqueous dispersion, and a solvent dispersion.
　前記技術的課題は、次の通りの本発明によって達成できる。 The technical problem can be achieved by the present invention as follows.
　即ち、本発明は、化学式（１）で示されるナフトールレッドであって、一次粒子の軸比（平均長軸径／平均短軸径）が１．０～２．０の範囲であるナフトールレッドある（本発明１）。 That is, the present invention is a naphthol red represented by the chemical formula (1), 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. (Invention 1).
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　また、本発明は、一次粒子の平均粒径が０．０２μｍ～０．２０μｍである本発明１記載のナフトールレッドである（本発明２）。 Further, the present invention is the naphthol red according to the present invention 1 wherein the average primary particle diameter is 0.02 μm to 0.20 μm (the present invention 2).
　また、本発明は、顔料濃度５％ポリエステル樹脂塗膜にて、膜厚３μｍでのヘイズ値が１０～２０％である本発明１または２記載のナフトールレッドである（本発明３）。 Further, the present invention is the naphthol red according to the first or second aspect of the present invention having a pigment concentration of 5% and a polyester resin coating film having a haze value of 10 to 20% at a film thickness of 3 μm (Invention 3).
　また、本発明は、顔料濃度５％ポリエステル樹脂塗膜にて、膜厚３μｍでの彩度ｃ＊が６０以上である本発明１～３のいずれかに記載のナフトールレッドである（本発明４）。 Further, the present invention is the naphthol red according to any one of the present inventions 1 to 3, wherein the 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) ).
　また、本発明は、粉体ｐＨが４．０～９．０の範囲にある本発明１～４のいずれかに記載のナフトールレッドである（本発明５）。 Further, the present invention is the naphthol red according to any one of the present inventions 1 to 4 having a powder pH in the range of 4.0 to 9.0 (Invention 5).
　また、本発明は、化学式（１）で示されるナフトールレッドが化学式（１１）で示される化合物（化合物ＰＲ２６９）である本発明１～５のいずれかに記載のナフトールレッドである（本発明６）。 Further, the present invention is the naphthol red according to any one of the present inventions 1 to 5, wherein the naphthol red represented by the chemical formula (1) is a compound represented by the chemical formula (11) (compound PR269) (the present invention 6). .
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　また、本発明は、化学式（２）で示される芳香族アミンのジアゾニウム塩冷却溶液を化学式（３）で示されるナフトール冷却溶液に加える際、微小領域で反応させることを含む操作、または化学式（３）で示されるナフトール冷却溶液を化学式（２）で示されるベンズアニリドのジアゾニウム塩冷却溶液に加える際、微小領域で反応させることを含む操作で製造される化学式（１）に示すナフトールレッドの製造方法である（本発明７）。 Further, the present invention provides an operation including reacting in a minute region when adding a diazonium salt cooling solution of an aromatic amine represented by chemical formula (2) to a naphthol cooling solution represented by chemical formula (3), or chemical formula (3 When the naphthol cooling solution represented by formula (2) is added to the benzanilide diazonium salt cooling solution represented by formula (2), the naphthol red production method represented by chemical formula (1) is produced by an operation including reacting in a microregion. There is (Invention 7).
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　また、本発明は、化学式（２）で示される芳香族アミンのアゾニウム塩冷却溶液を、化学式（３）で示されるナフトール冷却溶液に注入攪拌させることによって反応させるか、又は化学式（３）で示されるナフトール冷却溶液を、化学式（２）で示される芳香族アミンのアゾニウム塩冷却溶液に注入攪拌させることによって反応させ、さらに化学式（４）で示される親水性ナフトール誘導体、あるいは、化学式（５）で示される親水性フェノール誘導体を加えて反応することで製造される化学式（１）に示すナフトールレッドの製造方法である（本発明８）。 In the present invention, the aromatic amine azonium salt cooling solution represented by the chemical formula (2) is reacted by injecting and stirring into the naphthol cooling solution represented by the chemical formula (3), or represented by the chemical formula (3). The naphthol cooled solution is reacted by injecting and stirring the azonium salt cooled solution of the aromatic amine represented by the chemical formula (2), and the hydrophilic naphthol derivative represented by the chemical formula (4) or the chemical formula (5) It is a manufacturing method of the naphthol red shown to Chemical formula (1) manufactured by adding and reacting the hydrophilic phenol derivative shown (invention 8).
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
ただし、Ｒｋは、－Ｈ、－ＯＨ、ＳＯ３Ｈ、－ＣＯＯＨ、－ＣＯＮＨ２、ＣＯＮＨ－Ｃ６Ｈ４－ＳＯ３Ｈから選択され、ｎ＝１～３である。 However, R k is selected from —H, —OH, SO 3 H, —COOH, —CONH 2 , CONH—C 6 H 4 —SO 3 H, and n = 1 to 3.
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
ただし、Ｒｋは、－Ｈ、－ＯＨ、ＳＯ３Ｈ、－ＣＯＯＨ、－ＣＯＮＨ２、ＣＯＮＨ－Ｃ６Ｈ４－ＳＯ３Ｈから選択され、ｎ＝１～３である。 However, R k is selected from —H, —OH, SO 3 H, —COOH, —CONH 2 , CONH—C 6 H 4 —SO 3 H, and n = 1 to 3.
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
　また、本発明は、芳香族アミンが化学式（１２）で示される芳香族アミンであり、ナフトールが化学式（１３）で示されるナフトールであり、ナフトールレッドが化学式（１１）で示される化合物（化合物ＰＲ２６９）である本発明７～８のいずれかに記載のナフトールレッドの製造方法である（本発明９）。 In the present invention, the aromatic amine is an aromatic amine represented by the chemical formula (12), the naphthol is a naphthol represented by the chemical formula (13), and the naphthol red is a compound represented by the chemical formula (11) (compound PR269). The method for producing naphthol red according to any one of the present inventions 7 to 8 (present invention 9).
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
　また、本発明は、化学式（１１）で示されるナフトールレッドであって、化学式（４）で示される親水性ナフトール誘導体、あるいは、化学式（５）で示される親水性フェノール誘導体が０．０１～０．３重量％表面処理されたナフトールレッドである（本発明１０）。 The present invention also provides a naphthol red represented by the chemical formula (11), wherein the hydrophilic naphthol derivative represented by the chemical formula (4) or the hydrophilic phenol derivative represented by the chemical formula (5) is 0.01 to 0 3. 3% by weight surface-treated naphthol red (Invention 10).
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
ただし、Ｒｋは、－Ｈ、－ＯＨ、ＳＯ３Ｈ、－ＣＯＯＨ、－ＣＯＮＨ２、ＣＯＮＨ－Ｃ６Ｈ４－ＳＯ３Ｈから選択され、ｎ＝１～３である。 However, R k is selected from —H, —OH, SO 3 H, —COOH, —CONH 2 , CONH—C 6 H 4 —SO 3 H, and n = 1 to 3.
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
ただし、Ｒｋは、－Ｈ、－ＯＨ、ＳＯ３Ｈ、－ＣＯＯＨ、－ＣＯＮＨ２、ＣＯＮＨ－Ｃ６Ｈ４－ＳＯ３Ｈから選択され、ｎ＝１～３である。 However, R k is selected from —H, —OH, SO 3 H, —COOH, —CONH 2 , CONH—C 6 H 4 —SO 3 H, and n = 1 to 3.
　また、本発明は、一次粒子の軸比（平均長軸径／平均短軸径）が１．０～２．０の範囲である本発明１０記載のナフトールレッドである（本発明１１）。 Further, the present invention is the naphthol red according to the present invention 10 in which the axial ratio (average major axis diameter / average minor axis diameter) of primary particles is in the range of 1.0 to 2.0 (Invention 11).
　また、本発明は、一次粒子の平均粒径が０．０２μｍ～０．２０μｍである本発明１０または１１記載のナフトールレッドである（本発明１２）。 Further, the present invention is the naphthol red according to the present invention 10 or 11, wherein the average primary particle size is 0.02 μm to 0.20 μm (the present invention 12).
　また、本発明は、顔料濃度５％ポリエステル樹脂塗膜にて、膜厚３μｍでのヘイズ値が１０～２０％である本発明１０～１２のいずれかに記載のナフトールレッドである（本発明１３）。 Further, the present invention is the naphthol red according to any one of the present inventions 10 to 12, wherein the polyester resin coating film has a pigment concentration of 5% and the haze value at a film thickness of 3 μm is 10 to 20% (Invention 13). ).
　また、本発明は、顔料濃度５％ポリエステル樹脂塗膜にて、膜厚３μｍでの彩度ｃ＊が６０以上である本発明１０～１３のいずれかに記載のナフトールレッドである（本発明１４）。 Further, the present invention is the naphthol red according to any one of the present inventions 10 to 13, wherein the 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 14). ).
　また、本発明は、粉体ｐＨが４．０～９．０の範囲にある本発明１０～１４のいずれかに記載のナフトールレッドである（本発明１５）。 Further, the present invention is the naphthol red according to any one of the present inventions 10 to 14 having a powder pH in the range of 4.0 to 9.0 (Invention 15).
　また、本発明は、本発明１～６及び１０～１５のいずれかに記載のナフトールレッドを含んでなる樹脂組成物である（本発明１６）。 Further, the present invention is a resin composition comprising the naphthol red according to any one of the present inventions 1 to 6 and 10 to 15 (invention 16).
　また、本発明は、本発明１～６及び１０～１５のいずれかに記載のナフトールレッドを含んでなる水系分散体である（本発明１７）。 Further, the present invention is an aqueous dispersion comprising the naphthol red according to any one of the present inventions 1 to 6 and 10 to 15 (present invention 17).
　また、本発明は、本発明１～６及び１０～１５のいずれかに記載のナフトールレッドを含んでなる溶剤系分散体である（本発明１８）。 The present invention also relates to a solvent-based dispersion comprising the naphthol red according to any one of the present inventions 1 to 6 and 10 to 15 (invention 18).
　本発明に係るナフトールレッドは、一次粒子の軸比が小さく、分散性、発色性に優れたナフトールレッドとして好適である。 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.
　本発明に係るナフトールレッドは、親水性ナフトール誘導体、あるいは、親水性フェノール誘導体によって表面処理されており、顔料表面に極性を持ち、粒子成長が抑えられているため、分散性に優れている。そのため、発色性、透明性に優れたナフトールレッドとして好適である。 The naphthol red according to the present invention is surface-treated with a hydrophilic naphthol derivative or a hydrophilic phenol derivative, has polarity on the pigment surface, and has excellent dispersibility because particle growth is suppressed. Therefore, it is suitable as naphthol red excellent in color development and transparency.
　本発明に係るナフトールレッドの製造方法は、ナフトールレッドを微小領域で反応し製造することができるので、一次粒子の軸比が小さく、分散性、発色性に優れたナフトールレッドの製造方法として好適である。 The method for producing naphthol red according to the present invention can be produced by reacting naphthol red in a minute region, and is therefore suitable as a method for producing naphthol red having a small primary particle axial ratio and excellent dispersibility and color development. is there.
　本発明に係るナフトールレッドの製造方法は、ナフトールレッドの製造過程において、親水性ナフトール誘導体、あるいは、親水性フェノール誘導体で表面処理することにより、粒子成長を抑えながら製造することができるので、一次粒子の軸比が小さく、分散性、発色性に優れたナフトールレッドの製造方法として好適である。 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.
　本発明に係るナフトールレッドによって着色した樹脂組成物は、分散性、発色性に優れるので樹脂組成物として好適である。また、本発明に係るナフトールレッドによって着色した水系分散体、および、溶剤系分散体は、分散性、発色性に優れるので、各種分散体として好適である。 The resin composition colored with 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.
　本発明の構成をより詳しく説明すれば次の通りである。 The configuration of the present invention will be described in more detail as follows.
　先ず、本発明１～６に係るナフトールレッドについて述べる。 First, naphthol red according to the present inventions 1 to 6 will be described.
　本発明に係るナフトールレッドの一次粒子の軸比（平均長軸径／平均短軸径）は１．０～２．０の範囲である。軸比が２．０を超える場合には、分散が困難になり、発色性に劣る。また、軸比が１．０より小さいことはありえない。好ましい軸比は１．０～１．９の範囲であり、より好ましくは１．１～１．８の範囲である。 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.
　本発明に係るナフトールレッドは、化学式（１）で示されるナフトールレッド（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ５、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ１７、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ２２、Ｃ．Ｉ．Ｐｉｇｅｍｎｔ　Ｒｅｄ１４６、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ１５０、Ｃ．Ｉ．Ｐｉｇｅｍｎｔ　Ｒｅｄ１７０、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ２６８、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ２６９）であることが好ましい。中でも本発明６の化学式（１１）で示されるナフトールレッド（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ２６９）であることが特に好ましい。 The naphthol red according to the present invention includes naphthol red represented by the chemical formula (1) (CI Pigment Red 5, CI Pigment Red 17, CI Pigment Red 22, CI Pigment Red 146, CI Pigment Red 146, CI Pigment Red 146, CI Pigment Red 146, CI Pigment Red 146, CI Pigment Red 146, CI Pigment Red 146, and CI Pigment Red 146. Pigment Red 150, CI Pigment Red 170, CI Pigment Red 268, and CI Pigment Red 269). Among them, naphthol red (CI Pigment Red 269) represented by the chemical formula (11) of the present invention 6 is particularly preferable.
　本発明に係るナフトールレッドの一次粒子の平均長軸径は、０．０２～０．２０μｍが好ましい。平均長軸径が０．０２μｍ未満の場合は分散が困難になりやすい。平均長軸径が０．２μｍより大きい場合は発色性に劣る。より好ましい平均長軸径は０．０３～０．１８μｍである。 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 preferable average major axis diameter is 0.03 to 0.18 μm.
　本発明に係るナフトールレッドの一次粒子の平均短軸径は、０．０２～０．２０μｍが好ましい。平均短軸径が０．０２μｍ未満の場合は分散が困難になりやすい。平均短軸径が０．２μｍより大きい場合は発色性に劣る。より好ましい平均短軸径は０．０３～０．１５μｍである。 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.
　本発明に係るナフトールレッドの一次粒子の平均粒径は、０．０２～０．２０μｍが好ましい。一次粒子の平均粒径Ｐ５０が０．０２未満の場合は分散が困難になりやすい。一次粒子の平均粒径Ｐ５０が０．２０より大きい場合は発色性に劣る。より好ましい一次粒子の平均粒径Ｐ５０は、０．０２～０．１５μｍである。 The average particle size 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 P50 of the primary particles is less than 0.02, dispersion tends to be difficult. When the average particle size P50 of the primary particles is larger than 0.20, the color developability is inferior. A more preferable average particle size P50 of primary particles is 0.02 to 0.15 μm.
　本発明に係るナフトールレッドの顔料濃度５％のポリエステル樹脂塗膜にて、膜厚３μｍでのヘイズ値は１０～２０％が好ましい。ヘイズ値が２０％よりも大きい場合、塗膜の分散性が優れているとは言い難く、分散不良と云える。より好ましいヘイズ値は１２～１９％である。 The haze value at a film thickness of 3 μm is preferably 10 to 20% in a polyester resin coating film of naphthol red pigment concentration of 5% according to the present invention. When the haze value is larger than 20%, it is difficult to say that the dispersibility of the coating film is excellent, and it can be said that the dispersion is poor. A more preferred haze value is 12 to 19%.
　本発明に係るナフトールレッドの顔料濃度５％のポリエステル樹脂塗膜にて、膜厚３μｍでの彩度ｃ＊は６０以上が好ましく、発色性に優れているといえる。彩度ｃ＊が６０未満の場合は発色性が優れているとは言い難い。より好ましい表色指数ｃ＊は６５以上である。さらに、より好ましい表色指数ｃ＊は７０以上である。 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 development 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.
　本発明に係るナフトールレッドの顔料濃度５％のポリエステル樹脂塗膜にて、膜厚３μｍでの　ａ＊、ｂ＊は、特に限定されるものではないが、通常、レッドを表現する場合は、ａ＊、ｂ＊はともに０以上、マゼンタを表現する場合は、ａ＊は０以上、ｂ＊は０未満であることが好ましい。 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.
　本発明に係るナフトールレッドの粉体ｐＨは、４．０～９．０の範囲が好ましい。粉体ｐＨが４．０未満の場合には、樹脂などへの分散が阻害される恐れがある。粉体ｐＨが９．０を超える場合には、水などへの分散が阻害される恐れがある。より好ましい粉体ｐＨは４．１～８．５、より好ましくは４．２～８．０である。 The powder pH of the naphthol red according to the present invention is preferably 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.
　本発明に係るナフトールレッドは、分散性、発色性などを向上させるために、表面処理を行われていてもよい。表面処理材料としては、特に限定されるものではないが、アルキルアルコール、脂肪酸、アルキルアミンなどの界面活性剤、アクリル樹脂、ポリエステル樹脂、ウレタン樹脂などのポリマー、シランカップリング剤、シランなどの有機ケイ素化合物などの有機表面処理剤、シリカ、アルミナ、酸化チタンなどの無機微粒子などの無機表面処理剤、ロジン－カルシウム、ロジン－マグネシウムなどの有機無機表面処理剤などが挙げられ、あるいは、それらが２つ以上組み合わさったもので処理されたものも良い。 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. Organic surface treating agents such as compounds, inorganic surface treating agents such as inorganic fine particles such as silica, alumina and titanium oxide, and organic and inorganic surface treating agents such as rosin-calcium and rosin-magnesium, or two of them. What was processed with what was combined above is also good.
　次に、本発明に係るナフトールレッドの第一形態の製造方法（本発明７）について述べる。 Next, a method for producing the first form of naphthol red according to the present invention (present invention 7) will be described.
　本発明に係る化学式（１）で示されるナフトールレッドは、化学式（２）で示される芳香族アミンのジアゾニウム塩冷却溶液を化学式（３）で示されるナフトール冷却溶液に加えて製造される。その折、芳香族アミンのジアゾニウム塩をシリンジを用いて注入攪拌する、噴霧を用いて注入攪拌する、または、超音波ホモジナイザーで分散しながら連続混合する、ラインミルにて分散しながら連続混合する、いずれかの方法により、微小な領域でアゾカップリング反応が発生し、軸比の小さい粒子となる。これを高速攪拌した後、加熱処理を行い、顔料化させる。その後、ｐＨを調整して、濾過、水洗、乾燥を行った後、粉砕して本発明に係るナフトールレッドを得ることができる。 The naphthol red represented by the chemical formula (1) according to the present invention is manufactured by adding a diazonium salt cooling solution of an aromatic amine represented by the chemical formula (2) to the naphthol cooling solution represented by the chemical formula (3). At that time, the diazonium salt of aromatic amine is injected and stirred using a syringe, injected and stirred using a spray, or continuously mixed while being dispersed with an ultrasonic homogenizer, or continuously mixed while being dispersed with a line mill. By such a method, an azo coupling reaction occurs in a minute region, and particles having a small axial ratio are obtained. After stirring this at high speed, it is 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.
　具体的に、本発明に係る化学式（１１）で示されるナフトールレッドの製造方法で説明すれば、化学式（１２）で示される芳香族アミン（正式名称：３－アミノ－４－メトキシベンズアニリド）のジアゾニウム塩冷却溶液を化学式（１３）で示されるナフトール（正式名称：Ｎ－（５－クロロ－２－メトキシフェノニル）－３－ヒドロキシ－２－ナフタレンカルボキシアミド）冷却溶液に加えて製造される。その際、芳香族アミンのジアゾニウム塩の添加方法を、シリンジを用いて注入攪拌する、噴霧を用いて注入攪拌する、または、超音波ホモジナイザーで分散しながら連続混合する、ラインミルにて分散しながら連続混合する、いずれかの方法で行うことにより、微小な領域でアゾカップリング反応が発生し、軸比の小さな微細な粒子となる。これを高速攪拌した後、加熱処理をして顔料化させる。その後、ｐＨを調整して、濾過、水洗、乾燥を行った後、粉砕して、本発明に係るナフトールレッドを得ることができる。 Specifically, the method for producing naphthol red represented by the chemical formula (11) according to the present invention will be described. The aromatic amine represented by the chemical formula (12) (official name: 3-amino-4-methoxybenzanilide) A diazonium salt cooling solution is added to a naphthol (formal name: N- (5-chloro-2-methoxyphenonyl) -3-hydroxy-2-naphthalenecarboxamide) cooling solution represented by the chemical formula (13). At that time, the method for adding the diazonium salt of the aromatic amine is performed by injecting and stirring using a syringe, injecting and stirring using a spray, or continuously mixing while dispersing with an ultrasonic homogenizer, or continuously while dispersing with a line mill. By performing any of the mixing methods, an azo coupling reaction occurs in a minute region, and fine particles having a small axial ratio are obtained. After stirring this at high speed, it is 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.
　本発明に係る化学式（１）で示されるナフトールレッドは、化学式（３）で示されるナフトール冷却溶液を化学式（２）で示される芳香族アミンのジアゾニウム塩冷却溶液に加えて製造される。その折、ナフトール冷却溶液をシリンジを用いて注入攪拌する、噴霧を用いて注入攪拌する、または、超音波ホモジナイザーで分散しながら連続混合する、ラインミルにて分散しながら連続混合する、いずれかの方法により、微小な領域でアゾカップリング反応が発生し、軸比の小さい粒子となる。これを高速攪拌した後、加熱処理を行い、顔料化させる。その後、ｐＨを調整して、濾過、水洗、乾燥を行った後、粉砕して本発明に係るナフトールレッドを得ることができる。 The naphthol red represented by the chemical formula (1) according to the present invention is produced by adding the naphthol cooling solution represented by the chemical formula (3) to the diazonium salt cooling solution of the aromatic amine represented by the chemical formula (2). At that time, the naphthol cooling solution is injected and stirred using a syringe, injected and stirred using a spray, or continuously mixed while being dispersed by an ultrasonic homogenizer, or continuously mixed while being dispersed by a line mill. As a result, an azo coupling reaction occurs in a minute region, and particles having a small axial ratio are obtained. After stirring this at high speed, it is 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.
　具体的に、本発明に係る化学式（１１）で示されるナフトールレッドの製造方法で説明すれば、化学式（１３）で示されるナフトール冷却溶液を化学式（１２）で示される芳香族アミンのジアゾニウム塩冷却溶液に加えて製造される。その際、ナフトール冷却溶液の添加方法を、シリンジを用いて注入攪拌する、噴霧を用いて注入攪拌する、または、超音波ホモジナイザーで分散しながら連続混合する、ラインミルにて分散しながら連続混合する、いずれかの方法で行うことにより、微小な領域でアゾカップリング反応が発生し、軸比の小さな微細な粒子となる。これを高速攪拌した後、加熱処理して顔料化させる。その後、ｐＨを調整して、濾過、水洗、乾燥を行った後、粉砕して、本発明に係るナフトールレッドを得ることができる。 Specifically, in the method for producing naphthol red represented by the chemical formula (11) according to the present invention, the naphthol cooling solution represented by the chemical formula (13) is cooled with the diazonium salt of the aromatic amine represented by the chemical formula (12). Produced in addition to the solution. At that time, the addition method of the naphthol cooling solution is injected and stirred using a syringe, injected and stirred using a spray, or continuously mixed while being dispersed by an ultrasonic homogenizer, and continuously mixed while being dispersed by a line mill. By performing any of the methods, an azo coupling reaction occurs in a minute region, resulting in fine particles having a small axial ratio. After stirring this at high speed, it is 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.
　芳香族アミンのジアゾニウム塩冷却溶液をナフトール冷却溶液に加えて製造される方法を正カップリングといい、ジアゾニウム塩を用いたカップリングでは、最も一般的である。正カップリングにおいては、活性種であるジアゾニウム塩冷却液が、徐々にナフトール冷却液に加えられ、逐次に反応するため、反応性が高く、副反応が起こりにくい。 A method produced by 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.
　ナフトール冷却溶液を芳香族アミンのジアゾニウム塩冷却溶液に加えて製造される方法を逆カップリングといい、ジアゾニウム塩を用いたカップリングでは、よく採用されている。この場合、正カップリングほど反応性は高くはないが、ナフトール冷却液の反応性が低い場合、ジアゾニウム塩冷却液大過剰の状態で反応できるため、反応が進行しやすい。 A method 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.
　カップリングの方法においては、正カップリング、逆カップリングのどちらかが優れているというわけではなく、化学種、求められる品質などによって、選ばれる。 In the coupling method, either forward coupling or reverse coupling is not excellent, but it is selected depending on chemical species, required quality, and the like.
　シリンジを用いて注入攪拌する（シリンジインジェクション）とは、ナフトール冷却溶液、もしくは、芳香族アミンのジアゾニウム塩冷却溶液を攪拌し、そこに対となる冷却溶液を、１本以上のシリンジを用いて素早く注入する操作をいい、シリンジを通して拡散することにより、それぞれの物質が微細な領域で接触反応して軸比の小さい微細なナフトールレッドとなる。シリンジは、１．０ｍｍ以下の口径のものを使用するのが好ましい。さらに好ましくは、０．８ｍｍ以下の口径のものを使用することが好ましい。よりさらに好ましくは、０．５ｍｍ以下の口径のものを使用することが好ましい。 Injecting and stirring using a syringe (syringe injection) refers to stirring a naphthol cooling solution or a diazonium salt cooling solution of an aromatic amine, and quickly cooling the paired cooling solution using one or more syringes. This is an operation of injection, and by diffusing through a syringe, each substance is contact-reacted in a fine region to become fine naphthol red with a small axial ratio. It is preferable to use a syringe having a diameter of 1.0 mm or less. More preferably, a caliber having a diameter of 0.8 mm or less is used. More preferably, it is preferable to use one having a diameter of 0.5 mm or less.
　噴霧を用いて注入攪拌する（ミストインジェクション）とは、ナフトール冷却溶液、もしくは、芳香族アミンのジアゾニウム塩冷却溶液を攪拌し、そこに対となる冷却溶液を、１本以上のノズルを用いて素早く噴霧注入する操作をいい、ノズルを通して拡散することにより、それぞれの物質が微細な領域で接触反応して軸比の小さい微細なナフトールレッドとなる。ノズルは、１．０ｍｍ以下の口径のものを使用するのが好ましい。さらに好ましくは、０．８ｍｍ以下の口径のものを使用することが好ましい。よりさらに好ましくは、０．５ｍｍ以下の口径のものを使用することが好ましい。 Injecting and stirring by spraying (mist injection) is to stir a naphthol cooling solution or a diazonium salt cooling solution of an aromatic amine, and quickly cool the paired cooling solution using one or more nozzles. This is an operation for spray injection, and by diffusing through the nozzle, each substance contacts and reacts in a fine region to become fine naphthol red with a small axial ratio. It is preferable to use a nozzle having a diameter of 1.0 mm or less. More preferably, a caliber having a diameter of 0.8 mm or less is used. More preferably, it is preferable to use one having a diameter of 0.5 mm or less.
　超音波ホモジナイザーで分散しながら連続混合するとは、ナフトール冷却溶液、もしくは、芳香族アミンのジアゾニウム塩冷却溶液を循環させ、そのラインの一部にその対となる芳香族アミンのジアゾニウム塩冷却溶液、もしくは、ナフトール冷却溶液を注入し、その接触部分に超音波ホモジナイザーを照射して、それぞれの物質がそれぞれの物質が微細な領域で接触反応して軸比の小さい粒子となる。 Continuous mixing while being dispersed with an ultrasonic homogenizer means that a naphthol cooling solution or a diazonium salt cooling solution of an aromatic amine is circulated, and a diazonium salt cooling solution of the paired aromatic amine or a part of the line, or Then, a naphthol cooling solution is injected, and an ultrasonic homogenizer is irradiated to the contact portion, and each substance comes into contact with each other in a fine region to form particles with a small axial ratio.
　ラインミルで分散しながら連続混合するとは、ナフトール冷却溶液、もしくは、芳香族アミンのジアゾニウム塩冷却溶液を循環させ、そのラインの一部にその対となる芳香族アミンのジアゾニウム塩冷却溶液、もしくは、ナフトール冷却溶液を注入し、その接触部分をラインミルにて分散し、それぞれの物質が微細な領域で接触反応して軸比の小さい粒子となる。 Continuous mixing while being dispersed by a line mill means that a naphthol cooling solution or a diazonium salt cooling solution of an aromatic amine is circulated, and a diazonium salt cooling solution of a paired aromatic amine or naphthol is part of the line. The cooling solution is injected, and the contact portion is dispersed by a line mill, and each substance contacts and reacts in a fine region to form particles having a small axial ratio.
　それぞれの方法で調製された、軸比の小さい粒子は高速攪拌することで、解砕される。その後、通常攪拌にて加熱処理をされることで顔料化される。高速攪拌は１０００ｒｐｍ以上の回転数で行うことが好ましい。通常攪拌は１００～３００ｒｐｍである。 粒子 Particles with a small axial ratio prepared by each method are crushed by high-speed stirring. Thereafter, it is pigmented by heat treatment with normal stirring. High-speed stirring is preferably performed at a rotation speed of 1000 rpm or more. Usually, stirring is 100 to 300 rpm.
　芳香族アミンのジアゾニウム塩冷却溶液は、化学式（２）の芳香族アミン（化学式（１１）のナフトールレッドの製造の場合は化学式（１２）で示される３－アミノ－４－メトキシベンズアニリド）を酸の冷却水溶液に溶解し、これに、亜硝酸ナトリウム水溶液などを加えることにより調製される。また、過剰な亜硝酸塩を除くため、微量のスルファミン酸を加えて亜硝酸塩を除くことが好ましい。その後、酸、塩基、緩衝液などで所定のｐＨに調整して用いられる。ジアゾニウム塩調製および、保存、反応においては、ジアゾニウム塩が熱に極めて弱いため、０～５℃にて行われる。０℃以下では凍ってしまう可能性があり、使いづらい。１０℃よりも温度が高くなるとジアゾニウム塩が分解してしまう。 A diazonium salt cooling solution of an aromatic amine is obtained by converting an aromatic amine of chemical formula (2) (3-amino-4-methoxybenzanilide represented by chemical formula (12) in the case of production of naphthol red of chemical formula (11)) to an acid. It is prepared by dissolving in a cooling aqueous solution and adding a sodium nitrite aqueous solution and 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 vulnerable 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.
　酸としては、塩酸、硫酸、硝酸、リン酸などの無機酸、蟻酸、酢酸、クエン酸、アジピン酸、パラトルエンスルホン酸などの有機酸が挙げられる。 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.
　ナフトール冷却溶液は、化学式（３）のナフトール（化学式（１１）のナフトールレッドの製造の場合は化学式（１３）で示されるＮ－（５－クロロ－２－メトキシフェニル）－３－ヒドロキシ－２－ナフタレンカルボキシアミド）を塩基水溶液に懸濁し、これを８０℃加熱することで溶解し、０～５℃に冷却することが好ましい。保存、反応は０～５℃にて行われる。０℃以下では凍ってしまう可能性があり、使いづらい。５℃よりも温度が高くなると反応するジアゾニウム塩が分解してしまう。また、ナフトール（例えば、化学式（１３）のＮ－（５－クロロ－２－メトキシフェニル－３－ヒドロキシ－２－ナフタレンカルボキシアミド）は、溶解させず用いることもできる。 The naphthol cooling solution contains naphthol represented by the chemical formula (3) (in the case of producing naphthol red represented by the chemical formula (11), N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2- Naphthalenecarboxamide) is preferably suspended in an aqueous base solution, dissolved by heating at 80 ° C., and cooled to 0 to 5 ° C. Storage and reaction are carried out 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. In addition, naphthol (for example, N- (5-chloro-2-methoxyphenyl-3-hydroxy-2-naphthalenecarboxamide of the chemical formula (13)) can be used without being dissolved.
　塩基としては、水酸化ナトリウム、水酸化カリウム、アンモニアなどの無機塩基、メチルアミン、トリエチルアミンなどの有機塩基が挙げられる。 Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia, and organic bases such as methylamine and triethylamine.
　反応温度は、特に限定されるものではないが、アゾカップリング反応は０～１０℃、好ましくは、０～５℃で反応させればよい。また、アゾカップリング反応終了後、高速攪拌した後、顔料化させるため、そのまま、９０℃まで加熱することが好ましい。 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. In addition, after completion of the azo coupling reaction, it is preferably heated to 90 ° C. as it is in order to form a pigment after stirring at high speed.
　ｐＨは酸剤、あるいは、アルカリ剤を加えることにより、４．０～９．０の範囲に調整されることが好ましい。さらに、好ましくは、ｐＨ４．０～８．０の範囲である。 The pH is preferably adjusted to a range of 4.0 to 9.0 by adding an acid agent or an alkali agent. Furthermore, the pH is preferably in the range of 4.0 to 8.0.
　酸剤としては、無機化合物、有機化合物のいずれかでもよい。無機化合物としては、塩酸、硫酸、硝酸、リン酸などの無機酸が挙げられ、有機化合物としては、蟻酸、酢酸、クエン酸、アジピン酸、パラトルエンスルホン酸などが挙げられる。 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.
　アルカリ剤としては、無機化合物、有機化合物のいずれでもよい。無機化合物としては、水酸化ナトリウムや水酸化カリウムなどの水酸化アルカリ金属や炭酸ナトリウムなどの炭酸塩などが挙げられ、有機化合物としては、トリエタノールアミンやトリイソプロパノールアミンなどのトリアルカノールアミンなどが挙げられる。 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.
　ｐＨを調整した後、常法によって濾過、水洗し、乾燥、粉砕すれば、目的の本発明に係るナフトールレッドを得ることができる。 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.
　次に、本発明に係るナフトールレッドの第二形態の製造方法（本発明８）について述べる。 Next, a method for producing a second form of naphthol red according to the present invention (Invention 8) will be described.
　本発明に係る化学式（１）で示されるナフトールレッドは、化学式（２）で示される芳香族アミンのアゾニウム塩冷却溶液を、化学式（３）で示されるナフトール冷却溶液に連続的に注入攪拌させることによって反応し、反応が完結する前に、化学式（４）で示される親水性ナフトール誘導体、あるいは、化学式（５）で示される親水性フェノール誘導体を加えて反応することで軸比の小さい粒子となる。これを冷却しながら一定時間攪拌した後、加熱処理を行い、顔料化させる。その後、ｐＨを調整して、濾過、水洗、乾燥を行った後、粉砕して本発明に係るナフトールレッドを得ることができる。 The naphthol red represented by the chemical formula (1) according to the present invention is prepared by continuously injecting and stirring the cooling solution of the aromatic amine azonium salt represented by the chemical formula (2) into the naphthol cooling solution represented by the chemical formula (3). By reacting with a hydrophilic naphthol derivative represented by the chemical formula (4) or a hydrophilic phenol derivative represented by the chemical formula (5) before the reaction is completed, particles having a small axial ratio are obtained. . This 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.
　具体的に、本発明に係る化学式（１１）で示されるナフトールレッドの製造方法で説明すれば、本発明に係るナフトールレッドは、化学式（１２）で示される芳香族アミン（正式名称：３－アミノ－４－メトキシベンズアニリド）のアゾニウム塩冷却溶液を、化学式（１３）で示されるナフトール（正式名称：Ｎ－（５－クロロ－２－メトキシフェニル）－３－ヒドロキシ－２－ナフタレンカルボキシアミド）冷却溶液に注入攪拌させることによって反応し、反応が完結する前に、化学式（４）で示される親水性ナフトール誘導体、あるいは、化学式（５）で示される親水性フェノール誘導体を加えて反応することで軸比の小さな微細な粒子となる。これを冷却しながら一定時間攪拌した後、加熱処理をして顔料化させる。その後、ｐＨを調整して、濾過、水洗、乾燥を行った後、粉砕して本発明に係るナフトールレッドを得ることができる。 Specifically, the naphthol red according to the present invention will be described with reference to the method for producing naphthol red represented by the chemical formula (11). -4-Methoxybenzanilide) is cooled with a naphthol (formal name: N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthalenecarboxamide) represented by the chemical formula (13). It reacts by injecting and stirring into the solution, and before the reaction is completed, a hydrophilic naphthol derivative represented by the chemical formula (4) or a hydrophilic phenol derivative represented by the chemical formula (5) is added and reacted. Fine particles with a small ratio. 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.
　本発明に係る式１で示されるナフトールレッドは、化学式（３）で示されるナフトール冷却溶液を、化学式（２）で示される芳香族アミンのアゾニウム塩冷却溶液に連続的に注入攪拌させることによって反応し、反応が完結する前に、化学式（４）で示される親水性ナフトール誘導体、あるいは、化学式（５）で示される親水性フェノール誘導体を加えて反応することで、軸比の小さい微細な粒子となる。これを冷却しながら一定時間攪拌した後、加熱処理を行い、顔料化させる。その後、ｐＨを調整して、濾過、水洗、乾燥を行った後、粉砕して本発明に係るナフトールレッドを得ることができる。 The naphthol red represented by the formula 1 according to the present invention reacts by continuously injecting and stirring the naphthol cooling solution represented by the chemical formula (3) into the aromatic amine azonium salt cooling solution represented by the chemical formula (2). Then, before the reaction is completed, by adding a hydrophilic naphthol derivative represented by the chemical formula (4) or a hydrophilic phenol derivative represented by the chemical formula (5) and reacting, Become. This 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.
　具体的に、本発明に係る化学式（１１）で示されるナフトールレッドの製造方法で説明すれば、本発明に係るナフトールレッドは、化学式（１３）で示されるナフトール冷却溶液を、化学式（１２）で示される芳香族アミンのアゾニウム塩冷却溶液に注入攪拌させることによって反応し、反応が完結する前に、化学式（４）で示される親水性ナフトール誘導体、あるいは、化学式（５）で示される親水性フェノール誘導体を加えて反応することで、軸比の小さい微細な粒子となる。これを冷却しながら一定時間攪拌した後、加熱処理をして顔料化させる。その後、ｐＨを調整して、濾過、水洗、乾燥を行った後、粉砕して本発明に係るナフトールレッドを得ることができる。 Specifically, if it explains with the manufacturing method of naphthol red shown by the chemical formula (11) concerning the present invention, the naphthol red concerning the present invention will convert the naphthol cooling solution shown by the chemical formula (13) by the chemical formula (12). It reacts by injecting and stirring the cooled aromatic amine azonium salt solution, and before the reaction is completed, the hydrophilic naphthol derivative represented by the chemical formula (4) or the hydrophilic phenol represented by the chemical formula (5) By adding a derivative 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.
　芳香族アミンのジアゾニウム塩冷却溶液をナフトール冷却溶液に加えて製造される方法を正カップリングといい、ジアゾニウム塩を用いたカップリングでは、最も一般的である。正カップリングにおいては、活性種であるジアゾニウム塩冷却液が、徐々にナフトール冷却液に加えられ、逐次に反応するため、反応性が高く、副反応が起こりにくい。 A method produced by 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.
　ナフトール冷却溶液を芳香族アミンのジアゾニウム塩冷却溶液に加えて製造される方法を逆カップリングといい、ジアゾニウム塩を用いたカップリングでは、よく採用されている。この場合、正カップリングほど反応性は高くはないが、ナフトール冷却液の反応性が低い場合、ジアゾニウム塩冷却液大過剰の状態で反応できるため、反応が進行しやすい。 A method 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.
　カップリングの方法においては、正カップリング、逆カップリングのどちらかが優れているというわけではなく、化学種、求められる品質などによって、選ばれる。 In the coupling method, either forward coupling or reverse coupling is not excellent, but it is selected depending on chemical species, required quality, and the like.
　芳香族アミンのジアゾニウム塩冷却溶液は、これら（化学式（１１）のナフトールレッドの製造の場合は化学式（１２）で示される３－アミノ－４－メトキシベンズアニリド）を酸の冷却水溶液に溶解し、これに、亜硝酸ナトリウム水溶液などを加えることにより調製される。また、過剰な亜硝酸塩を除くため、微量のスルファミン酸を加えて亜硝酸塩を除くことが好ましい。その後、酸、塩基、緩衝液などで所定のｐＨに調整して用いられる。ジアゾニウム塩調製および、保存、反応においては、ジアゾニウム塩が熱に極めて弱いため、０～５℃にて行われる。０℃以下では凍ってしまう可能性があり、使いづらい。１０℃よりも温度が高くなるとジアゾニウム塩が分解してしまう。 A diazonium salt cooling solution of an aromatic amine is obtained by dissolving these (3-amino-4-methoxybenzanilide represented by the chemical formula (12) in the case of the production of naphthol red of the chemical formula (11)) in a cooling aqueous solution of an acid, It is prepared by adding a sodium nitrite aqueous solution or the like to this. 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 vulnerable 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.
　酸としては、塩酸、硫酸、硝酸、リン酸などの無機酸、蟻酸、酢酸、クエン酸、アジピン酸、パラトルエンスルホン酸などの有機酸が挙げられる。 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.
　ナフトール冷却溶液は、これらを塩基水溶液に懸濁し、これを８０℃加熱することで溶解し、０～５℃に冷却することが好ましい。保存、反応は０～５℃にて行われる。０℃以下では凍ってしまう可能性があり、使いづらい。５℃よりも温度が高くなると反応するジアゾニウム塩が分解してしまう。また、ナフトール（例えば、化学式（１３）のＮ－（５－クロロ－２－メトキシフェニル－３－ヒドロキシ－２－ナフタレンカルボキシアミド）は、溶解させず用いることもできる。 The naphthol cooling solution is preferably suspended in an aqueous base solution, dissolved by heating at 80 ° C., and cooled to 0 to 5 ° C. Storage and reaction are carried out 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. In addition, naphthol (for example, N- (5-chloro-2-methoxyphenyl-3-hydroxy-2-naphthalenecarboxamide of the chemical formula (13)) can be used without being dissolved.
　塩基としては、水酸化ナトリウム、水酸化カリウム、アンモニアなどの無機塩基、メチルアミン、トリエチルアミンなどの有機塩基が挙げられる。 Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia, and organic bases such as methylamine and triethylamine.
　反応温度は、特に限定されるものではないが、アゾカップリング反応は０～１０℃、好ましくは、０～５℃で反応させればよい。 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.
　親水性ナフトール誘導体は、１－ナフトール、２－ナフトール、あるいは、１－ナフトール、２－ナフトールに１つ以上の親水性官能基のついた誘導体が好ましい。例えば、１－ナフトール、２－ナフトール、１，２－ジハイドロキシナフタレン、１，３－ジハイドロキシナフタレン、１，５－ジハイドロキシナフタレン、１，６－ジハイドロキシナフタレン、１，７－ジハイドロキシナフタレン、２，３－ジハイドロキシナフタレン、２，６－ジハイドロキシナフタレン、２，７－ジハイドロキシナフタレン、１－ナフトール－３－カルボン酸、２－ナフトール－３－カルボン酸、１－ナフトール－５カルボン酸、２－ナフトール－５－カルボン酸、１－ナフトール－６－カルボン酸、２－ナフトール－６－カルボン酸、１－ナフトール－８－カルボン酸、２－ナフトール－８－カルボン酸、２－ナフトール－３，６－ジカルボン酸、２－ナフトール－３，８－ジカルボン酸、２－ナフトール－６，８－ジカルボン酸、２－ナフトール－３，６，８－トリカルボン酸、２－ナフトール－３－カルボキシアミド、２－ナフトール－３－カルボキシアミドフェニル－４－スルホン酸、１－ナフトール－３－スルホン酸、１－ナフトール－４－スルホン酸、１－ナフトール－５－スルホン酸、１－ナフトール－８－スルホン酸、１－ナフトール－３，６－ジカルボン酸、１－ナフトール－３，８－ジカルボン酸、２－ナフトール－３－スルホン酸、２－ナフトール－４－スルホン酸、２－ナフトール－５－スルホン酸、２－ナフトール－６－スルホン酸、２－ナフトール－７－スルホン酸、２－ナフトール－８－スルホン酸、２－ナフトール－３，６－ジスルホン酸、２－ナフトール－３，８－ジスルホン酸、２－ナフトール－６，８－ジスルホン酸、２－ナフトール－３，６，８－トリスルホン酸、１，８－ナフタレンジオール－３－スルホン酸、１，８－ナフタレンジオール－３，６－スルホン酸、２，８－ナフタレンジオール－６－スルホン酸、２－ナフトール－３－リン酸、２－ナフトール－５－リン酸、２－ナフトール－６－リン酸、２－ナフトール－８－リン酸、２－ナフトール－３，６－ジリン酸、２－ナフトール－３，８－ジリン酸、２－ナフトール－６，８－ジリン酸、２－ナフトール－３，６，８－トリリン酸、あるいは、それらのナトリウムやカリウムなどの塩、など、無数に例が挙げられる。 The hydrophilic naphthol derivative is preferably 1-naphthol, 2-naphthol or a derivative having one or more hydrophilic functional groups in 1-naphthol or 2-naphthol. 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-carboxamidophenyl-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 their salts such as sodium and potassium Is mentioned.
　親水性フェノール誘導体は、フェノール、あるいは、フェノールに１つ以上の親水性官能基のついた誘導体が好ましい。例えば、フェノール、カテコール、ハイドロキノン、ベンゼントリオール、フロログルシノール、サリチル酸、アミノフェノール、フェノール－３－スルホン酸、あるいは、それらのナトリウムやカリウムなどの塩、など、無数に例が挙げられる。 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 salts thereof such as sodium and potassium.
　親水性ナフトール誘導体、あるいは、親水性フェノール誘導体の添加量は、合成されるナフトールレッドに対して、１～１０重量％である。より好ましくは、１～５重量％である。 The addition amount of the hydrophilic naphthol derivative or the hydrophilic phenol derivative is 1 to 10% by weight with respect to the naphthol red to be synthesized. More preferably, it is 1 to 5% by weight.
　親水性ナフトール誘導体、あるいは、親水性フェノール誘導体は、水、あるいは、メタノール、エタノール、イソプロパノール、ジメチルホルムアミド、Ｎ－メチルピロリドン、などの親水性溶媒に溶解し、０～５℃に冷却して添加することが好ましい。 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 cooled to 0 to 5 ° C. and added. It is preferable.
また、アゾカップリング反応終了後、顔料化させるため、攪拌しながら、９０℃まで加熱することが好ましい。 Further, after completion of the azo coupling reaction, it is preferably heated to 90 ° C. with stirring in order to form a pigment.
　ｐＨは酸剤、あるいは、アルカリ剤を加えることにより、４．０～９．０の範囲に調整されることが好ましい。さらに、好ましくは、ｐＨ４．０～８．０の範囲である。 The pH is preferably adjusted to a range of 4.0 to 9.0 by adding an acid agent or an alkali agent. Furthermore, the pH is preferably in the range of 4.0 to 8.0.
　酸剤としては、無機化合物、有機化合物のいずれかでもよい。無機化合物としては、塩酸、硫酸、硝酸、リン酸などの無機酸が挙げられ、有機化合物としては、蟻酸、酢酸、クエン酸、アジピン酸、パラトルエンスルホン酸などが挙げられる。 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.
　アルカリ剤としては、無機化合物、有機化合物のいずれでもよい。無機化合物としては、水酸化ナトリウムや水酸化カリウムなどの水酸化アルカリ金属や炭酸ナトリウムなどの炭酸塩などが挙げられ、有機化合物としては、トリエタノールアミンやトリイソプロパノールアミンなどのトリアルカノールアミンなどが挙げられる。 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.
　ｐＨを調整した後、常法によって濾過、水洗し、乾燥、粉砕すれば、目的の本発明に係るナフトールレッドを得ることができる。 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.
　次に本発明１０のナフトールレッドについて説明する。 Next, naphthol red of the present invention 10 will be described.
　本発明１０に係るナフトールレッドは、化学式（１１）で示されるナフトールレッドであり、化学式（４）で示される親水性ナフトール誘導体、あるいは、化学式（５）で示される親水性フェノール誘導体が０．０１～０．３重量％表面処理されたナフトールレッドである。 The naphthol red according to the present invention 10 is a naphthol red represented by the chemical formula (11), and the hydrophilic naphthol derivative represented by the chemical formula (4) or the hydrophilic phenol derivative represented by the chemical formula (5) is 0.01. Naphthol red with a surface treatment of ˜0.3% by weight.
　化学式（４）で示される親水性ナフトール誘導体は、上記のナフトールレッドの第二形態の製造方法における化学式（４）で示される親水性ナフトール誘導体で説明したものと同一のものが使用できる。 As the hydrophilic naphthol derivative represented by the chemical formula (4), the same one as described for the hydrophilic naphthol derivative represented by the chemical formula (4) in the method for producing the second form of naphthol red can be used.
　化学式（５）で示される親水性フェノール誘導体は、上記のナフトールレッドの第二形態の製造方法における化学式（５）で示される親水性ナフトール誘導体で説明したものと同一のものが使用できる。 As the hydrophilic phenol derivative represented by the chemical formula (5), the same one as described for the hydrophilic naphthol derivative represented by the chemical formula (5) in the production method of the second form of naphthol red can be used.
　本発明１０に係るナフトールレッドの一次粒子の軸比（平均長軸径／平均短軸径）は、本発明１～６に係るナフトールレッドで説明した範囲の軸比を有することが好ましく、その理由も本発明１～６に係るナフトールレッドで説明した通りである。 The axial ratio (average major axis diameter / average minor axis diameter) of the primary particles of naphthol red according to the present invention 10 preferably has the axial ratio in the range described for the naphthol red according to the present invention 1 to 6, for the reason Are as described for naphthol red according to the first to sixth aspects of the present invention.
　本発明１０に係るナフトールレッドの一次粒子の平均長軸径は、本発明１～６に係るナフトールレッドで説明した範囲の平均長軸径を有することが好ましく、その理由も本発明１～６に係るナフトールレッドで説明した通りである。 The average major axis diameter of the primary particles of naphthol red according to the present invention 10 preferably has an average major axis diameter in the range described for the naphthol red according to the present inventions 1 to 6, and the reason is also described in the present inventions 1 to 6. This is as described for the naphthol red.
　本発明１０に係るナフトールレッドの一次粒子の平均短軸径は、本発明１～６に係るナフトールレッドで説明した範囲の平均短軸径を有することが好ましく、その理由も本発明１～６に係るナフトールレッドで説明した通りである。 The average minor axis diameter of the primary particles of naphthol red according to the present invention 10 preferably has an average minor axis diameter in the range described for the naphthol red according to the present inventions 1 to 6, and the reason is also described in the present inventions 1 to 6. This is as described for the naphthol red.
　本発明１０に係るナフトールレッドの一次粒子の平均粒径は、本発明１～６に係るナフトールレッドで説明した範囲の平均粒径を有することが好ましく、その理由も本発明１～６に係るナフトールレッドで説明した通りである。 The average particle diameter of the primary particles of naphthol red according to the present invention 10 preferably has an average particle diameter in the range described for the naphthol red according to the present invention 1 to 6, and the reason thereof is also naphthol according to the present invention 1 to 6. As explained in red.
　本発明１０に係るナフトールレッドの顔料濃度５％のポリエステル樹脂塗膜にて、膜厚３μｍでのヘイズ値は、本発明１～６に係るナフトールレッドで説明した範囲のヘイズ値を有することが好ましく、その理由も本発明１～６に係るナフトールレッドで説明した通りである。 The haze value at a film thickness of 3 μm of the naphthol red pigment resin film having a pigment concentration of 5% according to the present invention 10 preferably has the haze value within the range described for the naphthol red according to the present invention 1 to 6. The reason for this is also as described in the naphthol red according to the present invention 1 to 6.
　本発明１０に係るナフトールレッドの顔料濃度５％のポリエステル樹脂塗膜にて、膜厚３μｍでの彩度ｃ＊は、本発明１～６に係るナフトールレッドで説明した範囲の彩度ｃ＊を有することが好ましく、その理由も本発明１～６に係るナフトールレッドで説明した通りである。 At naphthol red pigment concentration of 5% of the polyester resin film according to the present invention 10, the chroma c * is in the thickness of 3 [mu] m, the range of the chroma c * described in Naphthol Red according to the present invention 1-6 The reason for this is also as described for the naphthol red according to the present invention 1-6.
　本発明１０に係るナフトールレッドの顔料濃度５％のポリエステル樹脂塗膜にて、膜厚３μｍでのａ＊、ｂ＊は、本発明１～６に係るナフトールレッドで説明した範囲のａ＊、ｂ＊を有することが好ましく、その理由も本発明１～６に係るナフトールレッドで説明した通りである。 At naphthol red pigment concentration of 5% polyester resin film according to the present invention 10, in a thickness of 3 [mu] m a *, b * is in the range described in Naphthol Red according to the present invention 1 ~ 6 a *, b It is preferable to have * for the same reason as described for naphthol red according to the present inventions 1 to 6.
　本発明１０に係るナフトールレッドの粉体ｐＨは、本発明１～６に係るナフトールレッドで説明した範囲の粉体ｐＨを有することが好ましく、その理由も本発明１～６に係るナフトールレッドで説明した通りである。 The powder pH of the naphthol red according to the present invention 10 preferably has a powder pH in the range described with respect to the naphthol red according to the present invention 1 to 6, and the reason is also explained with the naphthol red according to the present invention 1 to 6. That's right.
　本発明に係るナフトールレッドは、分散性、発色性などを向上させるために、さらなる表面処理を行われていてもよい。表面処理材料としては、本発明１～６に係るナフトールレッドで説明したものが使用できる。 The naphthol red according to the present invention may be subjected to further surface treatment in order to improve dispersibility, color developability and the like. As the surface treatment material, those described for naphthol red according to the present invention 1 to 6 can be used.
　次に、本発明１０に係るナフトールレッドの製造方法について述べる。 Next, a method for producing naphthol red according to the present invention 10 will be described.
　本発明１０に係るナフトールレッドは、化学式（１２）で示される芳香族アミン（正式名称：３－アミノ－４－メトキシベンズアニリド）のアゾニウム塩冷却溶液を、化学式（１３）で示されるナフトール（正式名称：Ｎ－（５－クロロ－２－メトキシフェニル）－３－ヒドロキシ－２－ナフタレンカルボキシアミド）冷却溶液に連続的に注入攪拌させることによって反応し、反応が完結する前に、化学式（４）で示される親水性ナフトール誘導体、あるいは、化学式（５）で示される親水性フェノール誘導体を加えて反応することで軸比の小さい粒子となる。これを冷却しながら一定時間攪拌した後、加熱処理をして顔料化させる。その後、ｐＨを調整して、濾過、水洗、乾燥を行った後、粉砕して本発明に係るナフトールレッドを得ることができる。 The naphthol red according to the tenth aspect of the present invention is a solution of an aromatic amine (formal name: 3-amino-4-methoxybenzanilide) represented by the chemical formula (12) with an azonium salt cooling solution represented by the chemical formula (13). Name: N- (5-Chloro-2-methoxyphenyl) -3-hydroxy-2-naphthalenecarboxamide) Reaction by continuously injecting and stirring into a cooled solution, and before the reaction is completed, the chemical formula (4) When a hydrophilic naphthol derivative represented by the formula (2) or a hydrophilic phenol derivative represented by the chemical formula (5) is added and reacted, particles having 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.
　本発明１０に係るナフトールレッドは、化学式（１３）で示されるナフトール冷却溶液を、化学式（１２）で示される芳香族アミンのアゾニウム塩冷却溶液に連続的に注入攪拌させることによって反応し、反応が完結する前に、化学式（４）で示される親水性ナフトール誘導体、あるいは、化学式（５）で示される親水性フェノール誘導体を加えて反応することで、軸比の小さい粒子となる。これを冷却しながら一定時間攪拌した後、そのまま熱をかけて顔料化させる。その後、ｐＨを調整して、濾過、水洗、乾燥を行った後、粉砕して本発明に係るナフトールレッドを得ることができる。 The naphthol red according to the present invention 10 reacts by continuously injecting and stirring the naphthol cooling solution represented by the chemical formula (13) into the aromatic amine azonium salt cooling solution represented by the chemical formula (12). Before completion, particles having a small axial ratio are obtained by adding a hydrophilic naphthol derivative represented by the chemical formula (4) or a hydrophilic phenol derivative represented by the chemical formula (5) for reaction. The mixture is stirred for a certain period of time while being cooled, and then heated 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.
　芳香族アミンのジアゾニウム塩冷却溶液をナフトール冷却溶液に加えて製造される方法を正カップリングといい、ジアゾニウム塩を用いたカップリングでは、最も一般的である。正カップリングにおいては、活性種であるジアゾニウム塩冷却液が、徐々にナフトール冷却液に加えられ、逐次に反応するため、反応性が高く、副反応が起こりにくい。 A method produced by 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.
　ナフトール冷却溶液を芳香族アミンのジアゾニウム塩冷却溶液に加えて製造される方法を逆カップリングといい、ジアゾニウム塩を用いたカップリングでは、よく採用されている。この場合、正カップリングほど反応性は高くはないが、ナフトール冷却液の反応性が低い場合、ジアゾニウム塩冷却液大過剰の状態で反応できるため、反応が進行しやすい。 A method 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.
　カップリングの方法においては、正カップリング、逆カップリングのどちらかが優れているというわけではなく、化学種、求められる品質などによって、選ばれる。 In the coupling method, either forward coupling or reverse coupling is not excellent, but it is selected depending on chemical species, required quality, and the like.
　芳香族アミンのジアゾニウム塩冷却溶液は、化学式（１２）で示される芳香族アミンを酸の冷却水溶液に溶解し、これに、亜硝酸ナトリウム水溶液などを加えることにより調製される。また、過剰な亜硝酸塩を除くため、微量のスルファミン酸を加えて亜硝酸塩を除くことが好ましい。その後、酸、塩基、緩衝液などで所定のｐＨに調整して用いられる。ジアゾニウム塩調製および、保存、反応においては、ジアゾニウム塩が熱に極めて弱いため、０～５℃にて行われる。０℃以下では凍ってしまう可能性があり、使いづらい。１０℃よりも温度が高くなるとジアゾニウム塩が分解してしまう。 The diazonium salt cooling solution of the aromatic amine is prepared by dissolving the aromatic amine represented by the chemical formula (12) in an acid cooling aqueous solution, and adding a sodium nitrite aqueous 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 vulnerable 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.
　酸としては、塩酸、硫酸、硝酸、リン酸などの無機酸、蟻酸、酢酸、クエン酸、アジピン酸、パラトルエンスルホン酸などの有機酸が挙げられる。 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.
　ナフトール冷却溶液は、化学式（１３）で示されるナフトールを塩基水溶液に懸濁し、これを８０℃加熱することで溶解し、０～５℃に冷却することが好ましい。保存、反応は０～５℃にて行われる。０℃以下では凍ってしまう可能性があり、使いづらい。５℃よりも温度が高くなると反応するジアゾニウム塩が分解してしまう。また、ナフトールは、溶解させず用いることもできる。 The naphthol cooling solution is preferably obtained by suspending naphthol represented by the chemical formula (13) in an aqueous base solution, dissolving the naphthol by heating at 80 ° C., and cooling to 0 to 5 ° C. Storage and reaction are carried out 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. Naphthol can also be used without being dissolved.
　塩基としては、水酸化ナトリウム、水酸化カリウム、アンモニアなどの無機塩基、メチルアミン、トリエチルアミンなどの有機塩基が挙げられる。 Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia, and organic bases such as methylamine and triethylamine.
　反応温度は、特に限定されるものではないが、アゾカップリング反応は０～１０℃、好ましくは、０～５℃で反応させればよい。 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.
　親水性ナフトール誘導体、あるいは、親水性フェノール誘導体の添加量は、合成されるナフトールレッドに対して、１～１０重量％である。より好ましくは、１～５重量％である。 The addition amount of the hydrophilic naphthol derivative or the hydrophilic phenol derivative is 1 to 10% by weight with respect to the naphthol red to be synthesized. More preferably, it is 1 to 5% by weight.
　親水性ナフトール誘導体、あるいは、親水性フェノール誘導体は、水、あるいは、メタノール、エタノール、イソプロパノール、ジメチルホルムアミド、Ｎ－メチルピロリドン、などの親水性溶媒に溶解し、０～５℃に冷却して添加することが好ましい。 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 cooled to 0 to 5 ° C. and added. It is preferable.
また、アゾカップリング反応終了後、顔料化させるため、攪拌しながら、９０℃まで加熱することが好ましい。 Further, after completion of the azo coupling reaction, it is preferably heated to 90 ° C. with stirring in order to form a pigment.
　ｐＨは酸剤、あるいは、アルカリ剤を加えることにより、４．０～９．０の範囲に調整されることが好ましい。さらに好ましくは、ｐＨ４．０～８．０の範囲である。 The pH is preferably adjusted to a range of 4.0 to 9.0 by adding an acid agent or an alkali agent. More preferably, the pH is in the range of 4.0 to 8.0.
　酸剤としては、無機化合物、有機化合物のいずれかでもよい。無機化合物としては、塩酸、硫酸、硝酸、リン酸などの無機酸が挙げられ、有機化合物としては、蟻酸、酢酸、クエン酸、アジピン酸、パラトルエンスルホン酸などが挙げられる。 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.
　アルカリ剤としては、無機化合物、有機化合物のいずれでもよい。無機化合物としては、水酸化ナトリウムや水酸化カリウムなどの水酸化アルカリ金属や炭酸ナトリウムなどの炭酸塩などが挙げられ、有機化合物としては、トリエタノールアミンやトリイソプロパノールアミンなどのトリアルカノールアミンなどが挙げられる。 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.
　ｐＨを調整した後、常法によって濾過、水洗し、乾燥、粉砕すれば、目的の本発明に係るナフトールレッドを得ることができる。 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.
　次に、本発明に係る樹脂組成物について述べる。 Next, the resin composition according to the present invention will be described.
　本発明に係る樹脂組成物は、本発明に係るナフトールレッド、周知の熱可塑性樹脂、必要により、滑剤、可塑剤、酸化防止剤、紫外線吸収剤、各種安定剤などの添加物が配合され構成される。 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
　本発明に係る樹脂組成物中におけるナフトールレッドの配合割合は、構成基剤１００重量部に対し０．０１～２００重量部の範囲内で使用することができ、樹脂組成物のハンドリングを考慮すれば、好ましくは０．０５～１００重量部、さらに、好ましくは０．１～５０重量部である。 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.
　添加物の量は、ナフトールレッドと熱可塑性樹脂との総和に対して５０重量％以下であればよい。添加物の含有量が５０重量％を超える場合には、成形性が低下する。 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.
　本発明に係る樹脂組成物の色相は、後述する評価方法によって測定した表色指数のうち、Ｌ＊値、ａ＊値、ｂ＊値、ｃ＊値を指す。 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.
　次に、本発明に係る樹脂組成物の製造方法について述べる。 Next, a method for producing the resin composition according to the present invention will be described.
　本発明に係る樹脂組成物は、樹脂原料とナフトールレッドとをあらかじめよく混合し、次に、混練機もしくは押出機を用いて加熱下で強いせん断作用を加えて、ナフトールレッドの凝集体を破壊し、樹脂中にナフトールレッドを均一に分散させた後、目的に応じた形状に成形加工して使用する。 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.
　次に、本発明に係る水系分散体について述べる。 Next, the aqueous dispersion according to the present invention will be described.
　本発明に係る水系分散体は、本発明に係るナフトールレッド、水、必要に応じて体質顔料、水系溶剤、界面活性剤、顔料分散剤、樹脂、ｐＨ調整剤、消泡剤などが配合され、構成される。 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.
　本発明に係る水系分散体におけるナフトールレッドの配合割合は、分散体構成基材１００重量部に対し、０．１～２００重量部の範囲で使用することができ、分散体のハンドリングを考慮すれば、好ましくは０．１～１００重量部、さらに、好ましくは０．１～５０重量部である。 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 base material, and considering the handling of the dispersion. The amount is preferably 0.1 to 100 parts by weight, more preferably 0.1 to 50 parts by weight.
　体質顔料としては、シリカ、酸化チタン、硫酸バリウム、酸化亜鉛、酸化マグネシウムなどの無機顔料、アクリル微粒子、ポリエステル微粒子などのポリマーなどが挙げられる。 Examples of extender pigments include inorganic pigments such as silica, titanium oxide, barium sulfate, zinc oxide and magnesium oxide, polymers such as acrylic fine particles and polyester fine particles.
　水系溶剤としては、エタノール、イソプロパノール、ブチルアルコール、グリセリン、ブチルセロソルブ等を使用することができる。 As the aqueous solvent, ethanol, isopropanol, butyl alcohol, glycerin, butyl cellosolve, or the like can be used.
　界面活性剤としては、ドデシルベンゼンスルホン酸、アルキルポリオキシエチレンスルホン酸などのアニオン系界面活性剤、アルキルポリオキシエチレンなどのノニオン系界面活性剤、ドデシルアミン塩酸塩などのカチオン系界面活性剤などが挙げられる。 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.
　顔料分散剤としては、高分子アニオン顔料分散剤、高分子ノニオン顔料分散剤、高分子カチオン顔料分散剤などが挙げられる。 Examples of the pigment dispersant include a polymer anion pigment dispersant, a polymer nonionic pigment dispersant, and a polymer cationic pigment dispersant.
　樹脂としては、通常使用される水溶性アルキッド樹脂、水溶性メラミン樹脂、水溶性アクリル樹脂、各種エマルジョン樹脂を用いることができる。 As the resin, commonly used water-soluble alkyd resins, water-soluble melamine resins, water-soluble acrylic resins, and various emulsion resins can be used.
　消泡剤としては、ノプコ８０３４（商品名）、ＳＮデフォーマー４７７（商品名）、ＳＮデフォーマー５０１３（商品名）、ＳＮデフォーマー２４７（商品名）、ＳＮデフォーマー３８２（商品名）（以上、いずれもサンノプコ製）、アンチホーム０８（商品名）、エマルゲン９０３（商品名）（以上、いずれも花王製）等の市販品を使用することができる。 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.
　本発明に係る水系分散体の粘度は、２０．０ｍＰａ・ｓ以下であることが好ましく、より好ましくは１５．０ｍＰａ・ｓ以下である。さらに、より好ましくは１０．０ｍＰａ・ｓ以下である。分散体の粘度が２０ｍＰａ・ｓを越える場合には、発色性に劣る。水系分散体の粘度の下限値は１．０ｍＰａ・ｓ程度である。 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.
　本発明に係る水系分散体の保存安定性評価は、後述する評価方法によって測定した粘度変化率において±１０％未満が好ましく、より好ましくは±６％以下、更により好ましくは±５％以下である。 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. .
　本発明に係る水系分散体の色相は、後述する評価方法によって測定した表色指数のうち、Ｌ＊値、ａ＊値、ｂ＊値、ｃ＊値を指す。 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.
　次に、本発明に係る水系分散体の製造方法について述べる。 Next, a method for producing an aqueous dispersion according to the present invention will be described.
　本発明に係る水系分散体は、ナフトールレッド、水、添加剤を混合し、ビーズミルなどのメディア分散機、あるいは、クレアミックス、フィルミクックス、超音波ホモジナイザイーなどのメディアレス分散機を用いて分散され、濾過などの後処理をされて製造される。分散安定性を高めるために、自己分散処理や、マイクロカプセル処理をして製造されてもよい。 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.
　次に、本発明係る溶剤系分散体について述べる。 Next, the solvent dispersion according to the present invention will be described.
　本発明に係る溶剤系分散体は、本発明の係るナフトールレッド、樹脂、溶剤、必要に応じて、体質顔料、乾燥促進剤、界面活性剤、硬化促進剤、助剤などが配合され、構成される。 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
　本発明に係る溶剤系分散体におけるナフトールレッドの配合割合は、分散体構成基材１００重量部に対し、０．１～２００重量部の範囲で使用することができ、分散体のハンドリングを考慮すれば、好ましくは０．１～１００重量部、さらに好ましくは、０．１～５０重量部である。 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 base material, considering the handling of the dispersion. For example, it is preferably 0.1 to 100 parts by weight, and more preferably 0.1 to 50 parts by weight.
　樹脂としては、通常使用されるアクリル樹脂、アルキッド樹脂、ポリエステル樹脂、ポリウレタン樹脂、エポキシ樹脂、フェノール樹脂、メラミン樹脂、アミノ樹脂などを用いることができる。 As the resin, commonly used acrylic resin, alkyd resin, polyester resin, polyurethane resin, epoxy resin, phenol resin, melamine resin, amino resin and the like can be used.
　溶剤としては、通常使用されるトルエン、キシレン、テトラヒドロフラン、酢酸メチル、酢酸エチル、酢酸ブチル、アセトン、２－ブタノン、メチルイソブチルケトン、エチルソロソルブ、ブチルセロソルブ、プロピレングリコールモノメチルエーテルアセテート、脂肪族炭化水素などを用いることができる。 Solvents include 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.
　本発明に係る溶剤系分散体の粘度は、２０．０ｍＰａ・ｓ以下であることが好ましく、より好ましくは１０．０ｍＰａ・ｓ以下である。２０ｍＰａ・ｓを越える場合には、分散性が劣り発色性が劣る。溶剤系分散体の粘度の下限値は２．０ｍＰａ・ｓ程度である。 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.
　本発明に係る溶剤系分散体の保存安定性評価は、後述する評価方法によって測定した粘度変化率において±１５％未満が好ましく、より好ましくは±１２％以下、更により好ましくは±１０％以下である。 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.
　本発明に係る溶剤系分散体の色相は、後述する評価方法によって測定した表色指数のうち、Ｌ＊値、ａ＊値、ｂ＊値、ｃ＊値を指す。 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.
　次に、本発明に係る溶剤系分散体の製造方法について述べる。 Next, a method for producing a solvent dispersion according to the present invention will be described.
　本発明に係る溶剤系分散体は、ナフトールレッド、溶剤、添加剤、樹脂を混合し、ビーズミルなどのメディア分散機、あるいは、クレアミックス、フィルミックス、超音波ホモジナイザーなどのメディアレス分散機を用いて分散され、濾過などの後処理をされて製造される。分散安定性を高めるために、自己分散処理や、マイクロカプセル処理をして製造してもよい。 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.
＜作用＞
　本発明に係るナフトールレッドは一次粒子の軸比が小さく、分散性、発色性に優れたナフトールレッドとして好適である。 <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 developability.
　本発明に係るナフトールレッドは、その最表面に親水性ナフトール誘導体、あるいは、親水性フェノール誘導体が表面処理されており、顔料表面が極性を持ち、分散性に優れている。また、その処理により、結晶成長が抑えられているため、一次粒子の軸比が小さい粒子となっており、軸比が小さいので、分散性に優れる効果がある。この２つの分散性に優れる効果のため、発色性、透明性に優れたナフトールレッドとなっている。 The naphthol red according to the present invention has a surface treated with a hydrophilic naphthol derivative or a hydrophilic phenol derivative on the outermost surface thereof, has a polar pigment surface, and is excellent in dispersibility. In addition, since the crystal growth is suppressed by the treatment, the primary particles are particles having a small axial ratio, and the axial ratio is small, so that the dispersibility is excellent. Because of these two excellent dispersibility effects, naphthol red has excellent color development and transparency.
　本発明に係るナフトールレッドの第一形態の製造方法は、芳香族アミンのジアゾニウム塩冷却溶液とナフトール冷却溶液との添加混合方法を制御し、アゾカップリング反応が微小領域で進行するため、一次粒子の軸比が小さい粒子が得られるものである。軸比が小さいので、分散性、発色性に優れており、発色性、透明性に優れたナフトールレッドの製造方法として好適である。 The production method of the first form of naphthol red according to the present invention controls the addition and mixing method of a diazonium salt cooling solution of an aromatic amine and a naphthol cooling solution, and the azo coupling reaction proceeds in a minute region. Particles having a small 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.
　本発明に係るナフトールレッドの第二形態の製造方法は、アゾカップリング反応の終盤で親水性ナフトール誘導体、あるいは、親水性フェノール誘導体を表面処理することによって、顔料表面が極性を持ち、結晶成長が抑えられるため、一次粒子の軸比が小さい粒子が得られるものである。軸比が小さいので、分散性、発色性に優れており、発色性、透明性に優れたナフトールレッドの製造方法として好適である。 In the method for producing the second form of naphthol red according to the present invention, the surface of the naphthol derivative or hydrophilic phenol derivative is surface-treated at the end of the azo coupling reaction, so that the pigment surface has polarity and crystal growth is reduced. Therefore, 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.
　本発明に係るナフトールレッドによって着色した樹脂組成物は、分散性、発色性に優れるので樹脂組成物として好適である。また、本発明に係るナフトールレッドによって着色した水系分散体、および、溶剤系分散体は、分散性、発色性に優れるので、各種分散体として好適である。 The resin composition colored with 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.
　本発明の代表的な実施の形態は、次の通りである。 A typical embodiment of the present invention is as follows.
　一次粒子の平均長軸径と平均短軸径は、いずれも透過型電子顕微鏡ＪＥＭ－１２００ＥＸ　ＩＩ（日本分光製）による顕微鏡写真に示される一次粒子３５０個の粒子径の長軸径と短軸径をそれぞれ測定し、その平均値で示した。 The average major axis diameter and the minor minor axis diameter of the primary particles are both the major axis diameter and 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.
　一次粒子の軸比は前出の平均長軸径の平均短軸径に対する比（平均長軸径／平均短軸径）として示した。 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).
　一次粒子の平均粒径は、平均長軸径と平均短軸径の平均値で示した。 The average particle diameter of primary particles is indicated by the average value of the average major axis diameter and the average minor axis diameter.
　粉体ｐＨ値は、試料５ｇを３００ｍｌの三角フラスコには秤取り、煮沸した純水１００ｍｌを加え、加熱して煮沸状態を約５分間保持した後、栓をして常温まで放冷し、減量に相当する水を加えて再び栓をして１分間振り混ぜ、５分間静置した後、得られた上澄み液のｐＨをＪＩＳ　Ｚ８８０２－７に従って測定し、得られた値を粉体ｐＨ値とした。 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.
　ヘイズ値は、後述実施例で作製した溶剤系分散体をキャスコート紙上にＷＥＴ膜厚２４μｍのバーコーターを用いて塗布した塗布片（塗膜厚み：約３μｍ）を作製し、該塗布片について、ヘイズメーター（日本電色工業製Ｈａｚｅ　Ｍｅｔｅｒ　ＮＤＨ４０００）を用いてヘイズ値を測定した値で示した。 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. The haze value was measured using a haze meter (Haze Meter NDH4000 manufactured by Nippon Denshoku Industries Co., Ltd.).
　本発明に係るナフトールレッドの分散性の判定は、ヘイズ値により、１０％以上１５％未満のものを◎、１５％以上２０％未満のものを○、２０％以上２５％未満のものを△、２５％以上のものを×とした。 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.
　色相は、後述実施例で調製した溶剤系分散体をキャスコート紙上にＷＥＴ膜厚２４μｍのバーコーターを用いて塗布した塗布片（塗膜厚み：約３μｍ）を作製し、該塗布片について、分光測色計Ｘ－Ｒｉｔｅ９３９（Ｘ－Ｒｉｔｅ製）を用いてＪＩＳ　Ｚ８７２９に定めるところに従って表色指数Ｌ＊値、ａ＊値、ｂ＊値をそれぞれ測定した値で示した。彩度ｃ＊はａ＊値、ｂ＊値を用い、下記数１で求めた。 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.
＜数１＞
ｃ＊＝（（ａ＊）２＋（ｂ＊）２）１／２ <Equation 1>
c * = ((a * ) 2 + (b * ) 2 ) 1/2
　本発明に係るナフトールレッドの発色性の判定は、彩度ｃ＊により、６５以上のものを◎、６０以上６５未満のものを○、５５以上６０未満ものを△、５５未満のものを×とした。 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.
　本発明に係る樹脂組成物の分散性は、後述する組成の樹脂組成物を下記組成にてエポキシモノマーに分散して６０℃、２４時間静置硬化して、ペレットを作製した。
（エポキシ樹脂包埋）
　樹脂組成物　１ｍｇ
　電子顕微鏡用エポキシ樹脂包埋剤Ｑｕｅｔｏｌ－８１２　　３．０ｇ
（日新ＥＭ製）
　ＤＤＳＡ（硬化剤）　　　　　　　　　　　　　　　　　　１．０ｇ
（日新ＥＭ製）
　ＭＮＡ（硬化剤）　　　　　　　　　　　　　　　　　　　２．０ｇ
（日新ＥＭ製）
　ＤＭＰ－３０（重合加速剤）　　　　　　　　　　　　　　０．０１ｇ
（日新ＥＭ製）
そして、このペレットをこのＲＭＣウルトラミクロトームＭＴ２Ｃ（盟和商事）にて２μｍの膜厚にスライスして、これを透過型電子顕微鏡にて観察し、下記４段階で分散性を評価した。
　　◎：未分散物が認められない。
　　○：１００μｍ２当たりに未分散物が１～１０個認められる。
　　△：１００μｍ２当たりに未分散物が１１～５０個認められる。
　　×：１００μｍ２当たりに未分散物が５１個以上認められる。 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) 0.01g
(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.
○: 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 .
　本発明に係る樹脂組成物の発色性は、樹脂組成物を粉砕後、２．０ｇ秤量し、８．０ｇのテトラヒドロフランに浸漬して、キャストコート紙上にＷＥＴ膜厚２４μｍのバーコーターを用いて塗布した塗付片（膜厚：約３μｍ）を作製し、該塗付片について、分光測色機Ｘ－Ｒｉｔｅ９３９（Ｘ－Ｒｉｔｅ製）を用いてＪＩＳ　Ｚ８７２９に定めるところに従って表色指数Ｌ＊値、ａ＊値、ｂ＊値をそれぞれ測定した値で示した。彩度ｃ＊はａ＊値、ｂ＊値を用い、下記数２で求めた。彩度ｃ＊が６０以上の樹脂組成物は実用上問題なく使用できるものである。 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, 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.
＜数２＞
ｃ＊＝（（ａ＊）２＋（ｂ＊）２）１／２ <Equation 2>
c * = ((a * ) 2 + (b * ) 2 ) 1/2
　本発明に係る水系分散体の粘度は、Ｅ型粘度計ＴＶ－３０（東機産業社製）を用いて測定した。 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.).
　本発明に係る水系分散体の保存安定性評価は、初期粘度と、２５℃で１週間後の経時粘度をＥ型粘度計ＴＶ－３０（東機産業社製）を用いて測定した。この初期粘度から経時粘度への変化率を下記数３で算出し、下記３段階で評価した。 In the storage stability evaluation of the aqueous dispersion according to the present invention, the initial viscosity and the viscosity with time after one 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.
　＜数３＞
　［粘度変化率］＝（［経時粘度］－［初期粘度］）／［初期粘度］×１００ <Equation 3>
[Viscosity change rate] = ([viscosity with time] − [initial viscosity]) / [initial viscosity] × 100
　　○：粘度変化率が±１０％未満
　　△：粘度変化率が±１０％以上±３０％未満
　　×：粘度変化率が±３０％以上 ○: 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
　本発明に係る水系分散体の分散性については、後述実施例で作製した水系分散体をキャスコート紙上にＷＥＴ膜厚２４μｍのバーコーターを用いて塗布した塗布片（塗膜厚み：約３μｍ）を作製し、該塗布片について、ヘイズメーター（日本電色工業製Ｈａｚｅ　Ｍｅｔｅｒ　ＮＤＨ４０００）を用いてヘイズ値を測定した値で示した。分散性の判定は、ヘイズ値が、１０％以上１５％未満のものを◎、１５％以上２０％未満のものを○、２０％以上２５％未満のものを△、２５％以上のものを×とした。 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 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.
　本発明に係る水系分散体の色相については、後述実施例で作製した水系分散体を用いた塗布膜の色相を、分光測色計Ｘ－Ｒｉｔｅ９３９（Ｘ－Ｒｉｔｅ製）を用いてＪＩＳ　Ｚ８７２９に定めるところに従って表色指数Ｌ＊値、ａ＊値、ｂ＊値をそれぞれ測定した値で示した。彩度ｃ＊はａ＊値、ｂ＊値を用い、下記数４で求めた。彩度ｃ＊が６０以上の水系分散体は実用上問題なく使用できるもので有る。 Regarding the hue of the aqueous dispersion according to the present invention, the hue of the coating film using the aqueous dispersion prepared in Examples described later is defined in JIS Z8729 using a spectrocolorimeter X-Rite 939 (manufactured by 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 saturation c * of 60 or more can be used practically without any problem.
＜数４＞
ｃ＊＝（（ａ＊）２＋（ｂ＊）２）１／２ <Equation 4>
c * = ((a * ) 2 + (b * ) 2 ) 1/2
　本発明に係る溶剤系分散体の粘度はＥ型粘度計ＴＶ－３０（東機産業社製）を用いて測定した。 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.).
　本発明に係る溶剤系分散体の保存安定性評価は、初期粘度と、２５℃で１週間後の経時粘度をＥ型粘度計ＴＶ－３０（東機産業社製）を用いて測定した。この初期粘度から経時粘度への変化率を下記数５で算出し、下記３段階で評価した。 In the storage stability evaluation of the solvent-based dispersion according to the present invention, the initial viscosity and the viscosity with time after one 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.
　＜数５＞
［粘度変化率］＝（［経時粘度］－［初期粘度］）／［初期粘度］×１００ <Equation 5>
[Viscosity change rate] = ([viscosity with time] − [initial viscosity]) / [initial viscosity] × 100
　　○：粘度変化率が±１５％未満
　　△：粘度変化率が±１５％以上±３０％未満
　　×：粘度変化率が±３０％以上 ○: 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
　本発明に係る溶剤系分散体の分散性については、後述実施例で作製した溶剤系分散体をキャスコート紙上にＷＥＴ膜厚２４μｍのバーコーターを用いて塗布した塗布片（塗膜厚み：約３μｍ）を作製し、該塗布片について、ヘイズメーター（日本電色工業製Ｈａｚｅ　Ｍｅｔｅｒ　ＮＤＨ４０００）を用いてヘイズ値を測定した値で示した。分散性の判定は、ヘイズ値が、１０％以上１５％未満のものを◎、１５％以上２０％未満のものを○、２０％以上２５％未満のものを△、２５％以上のものを×とした。 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 of the coated piece 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.
　本発明に係る溶剤系分散体の色相については、後述実施例で作製した溶剤系分散体を用いた塗布膜の色相を、分光測色計Ｘ－Ｒｉｔｅ９３９（Ｘ－Ｒｉｔｅ製）を用いてＪＩＳ　Ｚ８７２９に定めるところに従って表色指数Ｌ＊値、ａ＊値、ｂ＊値をそれぞれ測定した値で示した。彩度ｃ＊はａ＊値、ｂ＊値を用い、下記数６で求めた。彩度ｃ＊が６０以上の溶剤系分散体は実用上問題なく使用できるものである。 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.
＜数６＞
ｃ＊＝（（ａ＊）２＋（ｂ＊）２）１／２ <Equation 6>
c * = ((a * ) 2 + (b * ) 2 ) 1/2
　本発明に係るナフトールレッドの表面に存在する親水性ナフトール誘導体、あるいは、親水性フェノール誘導体の同定と定量は、下記の手順で行った。
　まず、本発明に係るナフトールレッド１０ｍｇをメタノール１０ｍＬ中に浸し、超音波洗浄機（１００Ｗ、３０分）にて、超音波を照射して、表面処理されている成分を抽出し、固形分を濾過除去して表面からの抽出液とした。
この抽出液を、逆相カラムを用いた高速液体クロマトグラフにかけて、ピーク位置とピーク強度から、親水性ナフトール誘導体、あるいは、親水性フェノール誘導体の同定と定量を行い、この操作を表面に含まれている物質の同定と定量と定義した。
測定条件を下記に示す。
高速液体クロマトグラフ：ＬａＣｈｒｏｍ　Ｅｌｉｔｅ（日立ハイテクノロジーズ製）
検出器：ＵＶ－ｖｉｓ（２５８ｎｍ）
逆相カラム：ＴＳＫｇｅｌＯＤＳ－１００Ｚ（４．６ｍｍＩＤ×１５ｃｍ）
（東ソー株式会社製）
溶離液：６０％メタノール水溶液　
流速：０．５ｍｌ／ｍｉｎ
オーブン温度：４０．０℃
試料注入量：２０μＬ Identification and quantification of the hydrophilic naphthol derivative or hydrophilic phenol derivative present on the surface of the naphthol red according to the present invention were performed by the following procedure.
First, 10 mg of naphthol red according to the present invention is soaked in 10 mL of methanol, and ultrasonic components are extracted with an ultrasonic cleaner (100 W, 30 minutes) to extract the surface-treated components, and the solid content is filtered. This was removed to obtain an extract from the surface.
This extract is subjected to high performance liquid chromatography using a reversed phase column to identify and quantify hydrophilic naphthol derivatives or hydrophilic phenol derivatives from the peak position and peak intensity. It was defined as the identification and quantification of the substance.
The measurement conditions are shown below.
High performance liquid chromatograph: LaChrom Elite (manufactured by Hitachi High-Technologies)
Detector: UV-vis (258 nm)
Reversed phase column: TSKgel ODS-100Z (4.6 mm ID × 15 cm)
(Tosoh Corporation)
Eluent: 60% methanol aqueous solution
Flow rate: 0.5 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 20 μL
　以下の実施例では、ナフトールレッド、それを用いた樹脂組成物、水系分散体、溶剤系分散体について示す。実施例１－１～１－３２は化学式（１１）で示されるナフトールレッドを第一形態の製造方法（本発明７）で製造した場合の例であり、実施例２－１～２－３２は化学式（１１）で示されるナフトールレッドを第二形態の製造方法（本発明８）で製造した場合の例であり、実施例３－１～３－６４は化学式（１）で示されるナフトールレッドを第一形態の製造方法（本発明７）および第二形態の製造方法（本発明８）で製造した場合の例であり、実施例４－１～４－３２は本発明１０に関する化学式（１１）で示されるナフトールレッドの例である。 In the following examples, naphthol red, a resin composition using the same, an aqueous dispersion, and a solvent dispersion will be described. Examples 1-1 to 1-32 are examples in which naphthol red represented by the chemical formula (11) was produced by the production method of the first embodiment (present invention 7). Examples 2-1 to 2-32 This is an example in which the naphthol red represented by the chemical formula (11) is produced by the production method of the second form (present invention 8), and Examples 3-1 to 3-64 are naphthol red represented by the chemical formula (1). This is an example of the case of production by the production method of the first form (Invention 7) and the production method of the second form (Invention 8). Examples 4-1 to 4-32 are the chemical formulas (11) relating to the Invention 10. It is an example of naphthol red shown by.
＜ナフトールレッドの製造＞
　実施例１－１（シリンジインジェクション）
　３５％ＨＣｌ水溶液１２．５重量部を氷水１８７．５重量部中に加え攪拌し、温度を５℃以下に調節した。これに、３－アミノ－４－メトキシベンズアニライド８重量部加えて攪拌して、３－アミノ－４－メトキシベンズアニライドの溶解と、３－アミノ－４－メトキシベンズアニライドの塩酸塩の析出を確認し、３０分間５℃以下で攪拌した。その後、３０％亜硝酸ナトリウム水溶液７．８重量部を加えて６０分間５℃以下で攪拌し、スルファミン酸０．３重量部を加えて亜硝酸を消去した。さらに、酢酸ナトリウム８重量部、９０％酢酸１２重量部を添加し、ジアゾニウム塩冷却溶液とした。また、別にＮ－（５－クロロ－２－メトキシフェニル）－３－ヒドロキシ－２－ナフタレンカルボキシアミド１２重量部を秤量し、純水１５０ｇ、水酸化ナトリウム４重量部を加え、攪拌しながら９０℃まで加熱して、溶解した。さらにこれを攪拌しながら、５℃まで冷却してナフトール冷却溶液とした。そして、ジアゾニウム塩冷却溶液を０．５ｍｍのシリンジを搭載したシリンジポンプに入れ、１０℃以下でナフトール冷却溶液攪拌液中に１５重量部／分の割合で液中へインジェクションし、５℃以下で１時間１２００ｒｐｍにて高速攪拌した。その後、９０℃まで加熱して、そのまま１時間１２００ｒｐｍにて高速攪拌した。さらに、１Ｎ塩酸、あるいは、１Ｎ水酸化ナトリウム水溶液を用いてｐＨを６．０に調整し、濾過、水洗をして、８０℃にて１０時間乾燥し、粉砕して、本発明に係るナフトールレッドを得た。（赤色顔料－１－１） <Manufacture of naphthol red>
Example 1-1 (syringe injection)
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, 12 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 mixture was stirred at a high speed for 1200 hours. Then, it heated to 90 degreeC and stirred at 1200 rpm for 1 hour as it was at high speed. 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 1-1)
　実施例１－２（ミストインジェクション）
　薬剤の量、水の量を変更した以外は、実施例１－１と同様にして、ジアゾニウム塩冷却溶液、ナフトール冷却溶液を得た。
　そして、ジアゾニウム塩冷却溶液を０．５ｍｍのノズルを搭載した噴霧器に入れ、１０℃以下でナフトール冷却溶液攪拌液中に１５重量部／分の割合で液中へインジェクションし、５℃以下で１時間１２００ｒｐｍにて攪拌した。その後、９０℃まで加熱して、そのまま１時間１２００ｒｐｍにて攪拌した。さらに、１Ｎ塩酸、あるいは、１Ｎ水酸化ナトリウム水溶液を用いてｐＨを６．０に調整し、濾過、水洗をして、８０℃にて１０時間乾燥し、粉砕して、本発明に係るナフトールレッドを得た。（赤色顔料－１－２） Example 1-2 (mist injection)
A diazonium salt cooling solution and a naphthol cooling solution were obtained in the same manner as in Example 1-1 except that the amount of the drug and the amount of water were changed.
Then, the diazonium salt cooling solution is put into a sprayer equipped with a 0.5 mm nozzle and injected into the naphthol cooling solution stirring liquid at a rate of 15 parts by weight / min. Stir at 1200 rpm. Then, 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-1-2)
　実施例１－３（超音波）
　薬剤の量、水の量を変更した以外は、実施例１－１と同様にして、ジアゾニウム塩冷却溶液、ナフトール冷却溶液を得た。
　そして、連続式破砕アダプターを装着した超音波ホモジナイザー（ＢＲＡＮＳＯＮ製ＳＯＮＩＦＥＲＩＩｍｏｄｅｌ２５０Ｄ）とペリスタリックポンプ、冷却ユニット付きベッセルを連結し、ナフトール冷却溶液を１５０重量部／分、５℃以下で循環した。また、超音波ホモジナイザー破砕ホーンの下部１ｃｍの部分に０．５ｍｍのシリンジを取り付け、その先に、ジアゾニウム塩冷却溶液を入れたシリンジポンプを取り付けた。その後、超音波を１００Ｗの出力で照射しながら、ジアゾニウム塩冷却溶液を１５重量部／分、５℃以下でインジェクションし、破砕ホーンの鼻先で超音波に照射されながら、ナフトール冷却溶液とジアゾニウム塩冷却溶液が、拡散接触して反応した。ジアゾニウム塩冷却溶液をインジェクションし終わってから５分間継続してペリスタリックポンプ循環ながら、超音波を照射して停止した。その後、この反応液をベッセルに戻し、１時間５℃以下で１２００ｒｐｍにて攪拌した。その後、９０℃まで加熱して、そのまま１時間１２００ｒｐｍにて攪拌した。さらに、１Ｎ塩酸、あるいは、１Ｎ水酸化ナトリウム水溶液を用いてｐＨを６．０に調整し、濾過、水洗をして、８０℃にて１０時間乾燥し、粉砕して、本発明に係るナフトールレッドを得た。（赤色顔料－１－３） Example 1-3 (ultrasound)
A diazonium salt cooling solution and a naphthol cooling solution were obtained in the same manner as in Example 1-1 except that the amount of the drug and the amount of water were changed.
Then, an ultrasonic homogenizer equipped with a continuous crushing adapter (BRANSON-made SOFIFER II model 250D), a peristaltic pump, and a vessel with a cooling unit were connected, and the naphthol cooling solution was circulated at 150 parts by weight / min at 5 ° C. or less. In addition, a 0.5 mm syringe was attached to the lower 1 cm portion of the ultrasonic homogenizer crushing horn, and a syringe pump containing a diazonium salt cooling solution was attached to the tip. Then, while irradiating with ultrasonic waves at an output of 100 W, the diazonium salt cooling solution was injected at 15 parts by weight / minute at 5 ° C. or lower, and the naphthol cooling solution and the diazonium salt cooling were performed while irradiating ultrasonic waves at the nose of the crushing horn. The solution reacted in diffusion contact. The injection was stopped by irradiating with ultrasonic waves while continuously circulating the peristaltic pump for 5 minutes after the injection of the diazonium salt cooling solution. Then, this reaction liquid was returned to the vessel and stirred at 1200 rpm at 5 ° C. or lower for 1 hour. Then, 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 1-3)
　実施例１－４（ラインミル）
　薬剤の量、水の量を変更した以外は、実施例１－１と同様にして、ジアゾニウム塩冷却溶液、ナフトール冷却溶液を得た。
　そして、原料供給槽と循環攪拌槽を付けたラインミル（プライミクス製Ｔ．Ｋ．パイプラインホモミクサーＰＬ－２Ｓ）を用意し、循環攪拌槽にナフトール冷却溶液を１５０重量部／分、５℃以下で循環した。また、原料供給槽にジアゾニウム塩冷却溶液を入れた。その後、ラインミルを５０００ｒｐｍの出力で攪拌しながら、ジアゾニウム塩冷却溶液を１５重量部／分、５℃以下でラインミルに投入し、ラインミルの鼻先で攪拌されながら、ナフトール冷却溶液とジアゾニウム塩冷却溶液が、拡散接触して反応した。ジアゾニウム塩冷却溶液を投入し終わってから５分間継続して循環攪拌を行ってから停止した。その後、この反応液を別のベッセルに移し、１時間５℃以下で１２００ｒｐｍにて攪拌した。その後、９０℃まで加熱して、そのまま１時間１２００ｒｐｍにて攪拌した。さらに、１Ｎ塩酸、あるいは、１Ｎ水酸化ナトリウム水溶液を用いてｐＨを６．０に調整し、濾過、水洗をして、８０℃にて１０時間乾燥し、粉砕して、本発明に係るナフトールレッドを得た。（赤色顔料－１－４） Example 1-4 (line mill)
A diazonium salt cooling solution and a naphthol cooling solution were obtained in the same manner as in Example 1-1 except that the amount of the drug and the amount of water were changed.
Then, a line mill (Primix TK Pipeline Homomixer PL-2S) equipped with a raw material supply tank and a circulation stirring tank was prepared, and a naphthol cooling solution was added to the circulation stirring tank at 150 parts by weight / min at 5 ° C. or less. Circulated. Moreover, the diazonium salt cooling solution was put into the raw material supply tank. Thereafter, while stirring the line mill at an output of 5000 rpm, the diazonium salt cooling solution was added to the line mill at 15 parts by weight / min and 5 ° C. or less, and the naphthol cooling solution and the diazonium salt cooling solution were stirred at the nose of the line mill. Reacted by diffusion contact. After the cooling of the diazonium salt cooling solution was completed, the mixture was continuously stirred for 5 minutes and then stopped. Thereafter, the reaction solution was transferred to another vessel and stirred at 1200 rpm at 5 ° C. or less for 1 hour. Then, 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-1-4)
　実施例１－５（シリンジインジェクション）
　薬剤の量、水の量を変更した以外は、実施例１－１と同様にして、ジアゾニウム塩冷却溶液、ナフトール冷却溶液を得た。
　そして、ナフトール冷却溶液を０．５ｍｍのノズルを搭載したシリンジポンプに入れ、１０℃以下でジアゾニウム塩冷却溶液攪拌液中に１５重量部／分の割合で液中へインジェクションし、５℃以下で１時間１２００ｒｐｍにて攪拌した。その後、９０℃まで加熱して、そのまま１時間１２００ｒｐｍにて攪拌した。さらに、１Ｎ塩酸、あるいは、１Ｎ水酸化ナトリウム水溶液を用いてｐＨを６．０に調整し、濾過、水洗をして、８０℃にて１０時間乾燥し、粉砕して、本発明に係るナフトールレッドを得た。（赤色顔料－１－５） Example 1-5 (syringe injection)
A diazonium salt cooling solution and a naphthol cooling solution were obtained in the same manner as in Example 1-1 except that the amount of the drug and the amount of water were changed.
Then, the naphthol cooling solution is put into a syringe pump equipped with a 0.5 mm nozzle, and injected into the liquid at a rate of 15 parts by weight / min into the diazonium salt cooling solution stirring liquid at 10 ° C. or lower, and 1 at 5 ° C. or lower. Stir for 1200 hours at time. Then, 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-1-5)
　実施例１－６（ミストインジェクション）
　薬剤の量、水の量を変更した以外は、実施例１－１と同様にして、ジアゾニウム塩冷却溶液、ナフトール冷却溶液を得た。
　そして、ナフトール冷却溶液を０．５ｍｍのノズルを搭載した噴霧器に入れ、１０℃以下でジアゾニウム塩冷却溶液攪拌液中に１５重量部／分の割合で液中へインジェクションし、５℃以下で１時間１２００ｒｐｍにて攪拌した。その後、９０℃まで加熱して、そのまま１時間１２００ｒｐｍにて攪拌した。さらに、１Ｎ塩酸、あるいは、１Ｎ水酸化ナトリウム水溶液を用いてｐＨを６．０に調整し、濾過、水洗をして、８０℃にて１０時間乾燥し、粉砕して、本発明に係るナフトールレッドを得た。（赤色顔料－１－６） Example 1-6 (mist injection)
A diazonium salt cooling solution and a naphthol cooling solution were obtained in the same manner as in Example 1-1 except that the amount of the drug and the amount of water were changed.
Then, the naphthol cooling solution is put into a sprayer 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 1200 rpm. Then, 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-1-6)
　実施例１－７（超音波）
　薬剤の量、水の量を変更した以外は、実施例１－１と同様にして、ジアゾニウム塩冷却溶液、ナフトール冷却溶液を得た。
　そして、連続式破砕アダプターを装着した超音波ホモジナイザー（ＢＲＡＮＳＯＮ製ＳＯＮＩＦＥＲＩＩｍｏｄｅｌ２５０Ｄ）とペリスタリックポンプ、冷却ユニット付きベッセルを連結し、ジアゾニウム塩冷却溶液を１５０重量部／分、５℃以下で循環した。また、超音波ホモジナイザー破砕ホーンの下部１ｃｍの部分に０．５ｍｍのシリンジを取り付け、その先に、ナフトール冷却溶液を入れたシリンジポンプを取り付けた。その後、超音波を１００Ｗの出力で照射しながら、ナフトール冷却溶液を１５重量部／分、５℃以下でインジェクションし、破砕ホーンの鼻先で超音波に照射されながら、ナフトール冷却溶液とジアゾニウム塩冷却溶液が、拡散接触して反応した。ナフトール冷却溶液をインジェクションし終わってから５分間継続してペリスタリックポンプ循環ながら超音波を照射して停止した。その後、この反応液をベッセルに戻し、１時間５℃以下で１２００ｒｐｍにて攪拌した。その後、９０℃まで加熱して、そのまま１時間１２００ｒｐｍにて攪拌した。さらに、１Ｎ塩酸、あるいは、１Ｎ水酸化ナトリウム水溶液を用いてｐＨを６．０に調整し、濾過、水洗をして、８０℃にて１０時間乾燥し、粉砕して、本発明に係るナフトールレッドを得た。（赤色顔料－１－７） Example 1-7 (ultrasound)
A diazonium salt cooling solution and a naphthol cooling solution were obtained in the same manner as in Example 1-1 except that the amount of the drug and the amount of water were changed.
Then, an ultrasonic homogenizer equipped with a continuous crushing adapter (BRANSON made SOFIFER II model 250D), a peristaltic pump, and a vessel with a cooling unit were connected, and the diazonium salt cooling solution was circulated at 150 ° C./min at 5 ° C. or less. Moreover, a 0.5 mm syringe was attached to a 1 cm lower part of the ultrasonic homogenizer crushing horn, and a syringe pump containing a naphthol cooling solution was attached to the tip. Then, while irradiating ultrasonic waves at an output of 100 W, the naphthol cooling solution was injected at 15 parts by weight / minute at 5 ° C. or lower, and radiated with ultrasonic waves at the tip of the crushing horn, while the naphthol cooling solution and the diazonium salt cooling solution were applied. Reacted by diffusion contact. The injection was stopped by irradiating ultrasonic waves while circulating the peristaltic pump continuously for 5 minutes after the injection of the naphthol cooling solution. Then, this reaction liquid was returned to the vessel and stirred at 1200 rpm at 5 ° C. or lower for 1 hour. Then, 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-1-7)
　実施例１－８（ラインミル）
　薬剤の量、水の量を変更した以外は、実施例１－１と同様にして、ジアゾニウム塩冷却溶液、ナフトール冷却溶液を得た。
　そして、原料供給槽と循環攪拌槽を付けたラインミル（プライミクス製Ｔ．Ｋ．パイプラインホモミクサーＰＬ－２Ｓ）を用意し、循環攪拌槽にジアゾニウム塩冷却溶液を１５０重量部／分、５℃以下で循環した。また、原料供給槽にナフトール冷却溶液を入れた。その後、ラインミルを５０００ｒｐｍの出力で攪拌しながら、ジアゾニウム塩冷却溶液を１５重量部／分、５℃以下でラインミルに投入し、ラインミルの鼻先で攪拌されながら、ナフトール冷却溶液とジアゾニウム塩冷却溶液が、拡散接触して反応した。ナフトール冷却溶液を投入し終わってから５分間継続して循環攪拌を行い、停止した。その後、この反応液を別のベッセルに移し、１時間５℃以下で１２００ｒｐｍにて攪拌した。その後、９０℃まで加熱して、そのまま１時間１２００ｒｐｍにて攪拌した。さらに、１Ｎ塩酸、あるいは、１Ｎ水酸化ナトリウム水溶液を用いてｐＨを６．０に調整し、濾過、水洗をして、８０℃にて１０時間乾燥し、粉砕して、本発明に係るナフトールレッドを得た。（赤色顔料－１－８） Example 1-8 (line mill)
A diazonium salt cooling solution and a naphthol cooling solution were obtained in the same manner as in Example 1-1 except that the amount of the drug and the amount of water were changed.
Then, a line mill (Primix TK Pipeline Homomixer PL-2S) equipped with a raw material supply tank and a circulation stirring tank is prepared, and a diazonium salt cooling solution is 150 parts by weight / minute, 5 ° C. or less in the circulation stirring tank. It circulated in. Moreover, the naphthol cooling solution was put into the raw material supply tank. Thereafter, while stirring the line mill at an output of 5000 rpm, the diazonium salt cooling solution was added to the line mill at 15 parts by weight / min and 5 ° C. or less, and the naphthol cooling solution and the diazonium salt cooling solution were stirred at the nose of the line mill. Reacted by diffusion contact. After the addition of the naphthol cooling solution, circulation stirring was continued for 5 minutes and stopped. Thereafter, the reaction solution was transferred to another vessel and stirred at 1200 rpm at 5 ° C. or less for 1 hour. Then, 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-1-8)
　このときの製造条件を表１－１に、得られたナフトールレッドの諸特性を表１－２に示す。 The production conditions at this time are shown in Table 1-1, and various characteristics of the obtained naphthol red are shown in Table 1-2.
　比較例１－１（特開平１１－２７２０１４号公報の製造例１の追試実験）
　３－アミノ－４－メトキシベンズアニライド５０重量部を水１０００重量部に分散させ、氷を加えて０～５℃の温度条件に設定し、３５％ＨＣｌ水溶液６０重量部を加えて２０分間攪拌した。その後、３０％亜硝酸ソーダ水溶液５０重量部を加えて６０分間攪拌後、スルファミン酸２重量部を加えて亜硝酸を消去した。更に酢酸ソーダ５０重量部、９０％酢酸７５重量部を添加し、ジアゾニウム溶液とした。これとは別にＮ－（５－クロロ－２－メトキシフェニル）－３－ヒドロキシ－２－ナフタレンカルボキシアミド６８重量部を水１０００重量部、苛性ソーダ２５重量部と共に８０℃以下で溶解させ、（Ａ）成分としてミネライト１００を３重量部添加し、カップラー溶液とした。この溶液を１０℃以下の温度条件で上記ジアゾニウム塩溶液に添加し、カップリング反応を行い、９０℃の加熱処理を行った。次に、濾過、水洗を行った後、１００℃で乾燥し、粉砕を行って、モノアゾ系顔料を得た。（赤色顔料－１－９） Comparative Example 1-1 (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 at 0-5 ° 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 caustic soda. 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-1-9)
　このときの製造条件を表１－１に、得られたモノアゾ系顔料の諸特性を表１－２に示す。 The production conditions at this time are shown in Table 1-1, and the characteristics of the obtained monoazo pigment are shown in Table 1-2.
　比較例１－２（特開２０００－１８６２４１号公報の製造例１の追試実験）
　３－アミノ－４－メトキシベンズアニリド６０重量部を水１０００重量部に分散させ、氷を加えて０～５℃の温度条件に設定し、３５％ＨＣｌ水溶液７２重量部を加えて２０分間攪拌した。その後、３０％亜硝酸ソーダ水溶液６０重量部を加えて６０分間攪拌後、スルファミン酸２．３重量部を加えて亜硝酸を消去した。更に酢酸ソーダ６０重量部、９０％酢酸８９重量部を添加し、ジアゾニウム塩溶液とした。これとは別に、Ｎ－（５－クロロ－２－メトキシフェニル）－３－ヒドロキシ－２－ナフタレンカルボキシアミド８２重量部を水１０００重量部、苛性ソーダ３０重量部と共に温度８０℃以下で溶解させ、（Ａ）成分としてネオペレックスＦ－２５を１２重量部（顔料に対して２．１６重量％）添加し、カップラー溶液とした。この溶液を１０℃以下の温度条件で上記ジアゾニウム塩溶液に添加し、カップリング反応を行い、９０℃の加熱処理を行った。次に、濾過、水洗を行った後、１００℃で乾燥し、粉砕を行い、モノアゾ系顔料を得た。（赤色顔料－１－１０） Comparative Example 1-2 (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 a temperature condition of 0 to 5 ° C., 72 parts by weight of 35% HCl aqueous solution was added and 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 was 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-1-10)
　このときの製造条件を表１－１に、得られたモノアゾ系顔料の諸特性を表１－２に示す。 The production conditions at this time are shown in Table 1-1, and the characteristics of the obtained monoazo pigment are shown in Table 1-2.
　比較例１－３（特開２００５－３１２７５号公報の実施例２の追試実験）
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ１２２　５０重量部とＣ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ２６９　５０重量部を室温にて硫酸に溶解し、顔料の硫酸溶液を溶液に対し８倍量の１０℃の冷水に添加して加水分解することにより、混晶顔料を得た。（赤色顔料－１－１１） Comparative Example 1-3 (Additional 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-1-11)
　このときの製造条件を表１－１に、得られた混晶顔料の諸特性を表１－２に示す。 The production conditions at this time are shown in Table 1-1, and the characteristics of the obtained mixed crystal pigment are shown in Table 1-2.
　比較例１－４（特開２０００－２４８１９１号公報の実施例１の追試実験）
　３－アミノ－４－メトキシベンズアニライド５０重量部を水１０００重量部に分散させ、氷を加えて０～５℃の温度条件に設定し、３５％ＨＣｌ水溶液５５重量部を加えて３０分攪拌した。その後、３０％亜硝酸ソーダ水溶液５０重量部を加えて６０分間攪拌後、スルファミン酸２重量部を加えて過剰の亜硝酸を消去した。更に、酢酸ソーダ４０重量部、９０％酢酸５８重量部を添加して、ジアゾニウム塩溶液とした。これとは別に、Ｎ－（５－クロロ－２－メトキシフェニル－３－ヒドロキシ－２－ナフタレンカルボキシアミド５９重量部と３－ヒドロキシナフトエ酸５重量部を水１０００重量部、苛性ソーダ２５重量部と共に温度８０℃以下で溶解させ、カップラー溶液とした。この溶液を１０℃以下の温度条件で上記ジアゾニウム塩溶液に添加し、カップリング反応を行い、９０℃で加熱処理した。この反応混合物を濾過し、水洗を行った後、１００℃で乾燥し、粉砕を行い、モノアゾ系赤色顔料を得た。（赤色顔料－１－１２） Comparative Example 1-4 (Follow-up experiment 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 to 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-1-12).
　このときの製造条件を表１－１に、得られたモノアゾ系赤色顔料の諸特性を表１－２に示す。 The production conditions at this time are shown in Table 1-1, and various characteristics of the obtained monoazo red pigment are shown in Table 1-2.
Figure JPOXMLDOC01-appb-T000035
Figure JPOXMLDOC01-appb-T000035
Figure JPOXMLDOC01-appb-T000036
Figure JPOXMLDOC01-appb-T000036
　以上のように、実施例のナフトールレッドは、いずれも、軸比が１．０～２．０の範囲であり、分散性、発色性に優れることは明らかである。 As described above, the naphthol reds of the examples all have an axial ratio in the range of 1.0 to 2.0, and are clearly excellent in dispersibility and color developability.
＜樹脂組成物の製造＞
　実施例１－９
　実施例１－１で得た赤色顔料－１－１　３．０重量部とポリエステル樹脂ＤＩＡＣＲＯＮ　ＥＲ５６１（三菱レイヨン製）５７．０重量部を秤量し、サンプルミルにて粉砕した。これをラボプラストミル（東洋精機製）にて１２０℃、２５ｒｐｍで１０分間混練し、取り出した後、室温まで冷却した。この後、超遠心粉砕機（レッチェ製ＺＭ２００）を用いて１２０００ｒｐｍにて粉砕し、樹脂組成物を得た。 <Manufacture of resin composition>
Example 1-9
3.0 parts by weight of the red pigment 1-1 obtained in Example 1-1 and 57.0 parts by weight of the polyester resin DIACRON ER561 (manufactured by Mitsubishi Rayon) were weighed and ground 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.
　実施例１－１０～１－１６、比較例１－５～１－８
　ナフトールレッドの種類を種々変化させた以外は、前記実施例１－９と同様にして樹脂組　成物を得た。 Examples 1-10 to 1-16, Comparative Examples 1-5 to 1-8
A resin composition was obtained in the same manner as in Example 1-9 except that various types of naphthol red were used.
　このときに得られた樹脂組成物の諸特性を表１－３に示す。 The characteristics of the resin composition obtained at this time are shown in Table 1-3.
Figure JPOXMLDOC01-appb-T000037
Figure JPOXMLDOC01-appb-T000037
　以上のように、実施例の樹脂組成物は、分散性に優れ、発色性に優れることは明らかである。 As described above, it is clear that the resin compositions of the examples are excellent in dispersibility and color developability.
＜水系分散体の製造＞
　実施例１－１７
　１４０ｍｌのガラスビンに、実施例１－１で得たナフトールレッド０．５重量部を用い、水系分散体組成を下記割合で配合して１．５ｍｍφガラスビーズ５０重量部とともにペイントシェーカーで６０分間混合分散し、水系分散体を得た。 <Production of aqueous dispersion>
Example 1-17
Using 0.5 parts by weight of naphthol red obtained in Example 1-1 in a 140 ml glass bottle, the aqueous dispersion composition was blended in the following proportions 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.
　水系分散体は、下記の割合で配合した。
　ナフトールレッド　　　　　　　　　　　　　　　　０．５０重量部、
　アニオン系界面活性剤　　　　　　　　　　　　　　０．０５重量部、
　　（ネオペレックスＧＳ：花王製）
アクリルエマルジョン（固形分３３％）　　　　　　２８．７９重量部、
　　（ニカゾールＲＸ－３００２Ｅ：日本カーバイド製）
　消泡剤　　　　　　　　　　　　　　　　　　　　　０．０５重量部、
　　（エンバイロジェムＡＤ－０１　：日信化学工業製）
　純水　　　　　　　　　　　　　　　　　　　　　２０．６１重量部。 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.
　実施例１－１８～１－２４、比較例１－９～１－１２
　ナフトールレッドの種類を種々変化させた以外は、前記実施例１－１７と同様にして水系分散体を得た。 Examples 1-18 to 1-24, Comparative Examples 1-9 to 1-12
An aqueous dispersion was obtained in the same manner as in Example 1-17 except that the type of naphthol red was variously changed.
　このときに得られた水系分散体の諸特性を表１－４に示す。 The characteristics of the aqueous dispersion obtained at this time are shown in Table 1-4.
Figure JPOXMLDOC01-appb-T000038
Figure JPOXMLDOC01-appb-T000038
　以上のように、実施例の水系分散体は、保存安定性に優れ、分散性に優れ、発色性に優れることは明らかである。 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.
＜溶剤系分散体の製造＞
　実施例１－２５
　１４０ｍｌのガラスビンに、実施例１－１で得たナフトールレッド０．５０重量部を用い、溶剤系分散体組成を下記割合で配合して１．５ｍｍφガラスビーズ５０重量部とともにペイントシェーカーで６０分間混合分散し溶剤系分散体を得た。 <Production of solvent-based dispersion>
Example 1-25
Using 0.50 parts by weight of naphthol red obtained in Example 1-1 in a 140 ml glass bottle, the solvent-based dispersion composition was blended in the following proportions and mixed with a paint shaker for 60 minutes together with 50 parts by weight of 1.5 mmφ glass beads. Dispersion was performed to obtain a solvent-based dispersion.
　溶剤系分散体は、下記の組成で配合した。
　ナフトールレッド　　　　　　　　　　　　　　　　０．５０重量部、
　ポリエステル樹脂ＤＩＡＣＲＯＮ　ＥＲ５６１　　　９．５０重量部、
（三菱レイヨン製）
　テトラヒドロフラン　　　　　　　　　　　　　　４０．００重量部。 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.
　実施例１－２６～１－３２、比較例１－１３～１－１６
　ナフトールレッドの種類を種々変化させた以外は、前記実施例１－２５と同様にして溶剤系分散体を得た。 Examples 1-26 to 1-32 and Comparative Examples 1-13 to 1-16
A solvent-based dispersion was obtained in the same manner as in Example 1-25 except that the type of naphthol red was variously changed.
　このときに得られた溶剤系分散体の諸特性を表１－５に示す。 The properties of the solvent dispersion obtained at this time are shown in Table 1-5.
Figure JPOXMLDOC01-appb-T000039
Figure JPOXMLDOC01-appb-T000039
　以上のように、実施例の溶剤系分散体は、保存安定性に優れ、分散性に優れ、発色性に優れることは明らかである。 As described above, it is clear that the solvent-based dispersions of the examples have excellent storage stability, excellent dispersibility, and excellent color developability.
＜ナフトールレッドの製造＞
　実施例２－１
　３５％ＨＣｌ水溶液１２．５重量部を氷水１８７．５重量部中に加え攪拌し、温度を５℃以下に調節した。これに、３－アミノ－４－メトキシベンズアニライド８重量部加えて攪拌して、３－アミノ－４－メトキシベンズアニライドの溶解と、３－アミノ－４－メトキシベンズアニライドの塩酸塩の析出を確認し、３０分間５℃以下で攪拌した。その後、３０％亜硝酸ナトリウム水溶液７．８重量部を加えて６０分間５℃以下で攪拌し、スルファミン酸０．３重量部を加えて亜硝酸を消去した。さらに、酢酸ナトリウム８重量部、９０％酢酸１２重量部を添加し、ジアゾニウム塩冷却溶液とした。また、別にＮ－（５－クロロ－２－メトキシフェニル）－３－ヒドロキシ－２－ナフタレンカルボキシアミド１１重量部を秤量し、純水１５０ｇ、水酸化ナトリウム４重量部を加え、攪拌しながら９０℃まで加熱して、溶解した。さらにこれを攪拌しながら、５℃まで冷却してナフトール冷却溶液とした。そして、ジアゾニウム塩冷却溶液を０．５ｍｍのシリンジを搭載したシリンジポンプに入れ、１０℃以下でナフトール冷却溶液攪拌液中に１５重量部／分の割合で液中へインジェクションし、５℃以下で３０分３００ｒｐｍにて反応液を攪拌した。その後、２－ナフトール－３カルボン酸、０．４重量部を氷水２０重量部に溶解した溶液を調製し、それを、５℃以下まで冷却した。そして、その溶液を、５℃以下で反応液に添加し、さらに１時間３００ｒｐｍにて攪拌した。その後、９０℃まで加熱して、そのまま１時間３００ｒｐｍにて攪拌した。さらに、１Ｎ塩酸、あるいは、１Ｎ水酸化ナトリウム水溶液を用いてｐＨを６．０に調整し、濾過、水洗をして、８０℃にて１０時間乾燥し、粉砕して、本発明に係るナフトールレッドを得た。（赤色顔料－２－１） <Manufacture of naphthol red>
Example 2-1
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. Thereafter, a solution in which 0.4 part by weight of 2-naphthol-3carboxylic acid was dissolved in 20 parts by weight of ice water was prepared and cooled to 5 ° C. or lower. 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-2-1)
　実施例２－２～２－４
　追加添加する親水性ナフトール誘導体、あるいは、親水性フェノール誘導体の種類と量、反応条件を種々変化させた以外は、前記実施例２－１と同様にして本発明に係るナフトールレッドを得た。（赤色顔料－２－２～４） Examples 2-2 to 2-4
A naphthol red according to the present invention was obtained in the same manner as in Example 2-1, 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 -2-2 to 4)
　実施例２－５
　実施例２－１と同様にして、ジアゾニウム塩冷却溶液、ナフトール冷却溶液を得た。
　そして、ナフトール冷却溶液を０．５ｍｍのノズルを搭載したシリンジポンプに入れ、１０℃以下でジアゾニウム塩冷却溶液攪拌液中に１５重量部／分の割合で液中へインジェクションし、５℃以下で３０分３００ｒｐｍにて攪拌した。その後、２－ナフトール－３カルボキシアミド、０．４重量部を氷水２０重量部に溶解した溶液を調製し、それを、５℃以下まで冷却した。そして、その溶液を、５℃以下で反応液に添加し、さらに１時間３００ｒｐｍにて攪拌した。そして、９０℃まで加熱して、そのまま１時間１２００ｒｐｍにて攪拌した。さらに、１Ｎ塩酸、あるいは、１Ｎ水酸化ナトリウム水溶液を用いてｐＨを６．０に調整し、濾過、水洗をして、８０℃にて１０時間乾燥し、粉砕して、本発明に係るナフトールレッドを得た。（赤色顔料－２－５） Example 2-5
In the same manner as in Example 2-1, 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. Thereafter, a solution in which 0.4 parts by weight of 2-naphthol-3carboxamide was dissolved in 20 parts by weight of ice water was prepared, and the solution was cooled to 5 ° C. or lower. 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-2-5)
　実施例２－６～２－８
　追加添加する親水性ナフトール誘導体、あるいは、親水性フェノール誘導体の種類と量、反応条件を種々変化させた以外は、前記実施例２－５と同様にして本発明に係るナフトールレッドを得た。（赤色顔料－２－６～８） Examples 2-6 to 2-8
A naphthol red according to the present invention was obtained in the same manner as in Example 2-5 except that the hydrophilic naphthol derivative to be additionally added or the kind and amount of the hydrophilic phenol derivative and the reaction conditions were variously changed. (Red pigments 2-6 to 8)
　このときの製造条件を表２－１に、得られたナフトールレッドの諸特性を表２－２に示す。 The production conditions at this time are shown in Table 2-1, and the characteristics of the obtained naphthol red are shown in Table 2-2.
　比較例２－１（特開平１１－２７２０１４号公報の製造例１の追試実験）
　上記比較例１－１と同一である（赤色顔料－２－９）。このときの製造条件を表２－１に、得られたモノアゾ系顔料の諸特性を表２－２に示す。 Comparative Example 2-1 (Additional Experiment of Production Example 1 of JP-A-11-272014)
Same as Comparative Example 1-1 (Red Pigment-2-9). The production conditions at this time are shown in Table 2-1, and the characteristics of the obtained monoazo pigment are shown in Table 2-2.
　比較例２－２（特開２０００－１８６２４１号公報の製造例１の追試実験）
　上記比較例１－２と同一である（赤色顔料－２－１０）。このときの製造条件を表２－１に、得られたモノアゾ系顔料の諸特性を表２－２に示す。 Comparative Example 2-2 (Follow-up experiment of Production Example 1 of JP 2000-186241 A)
Same as Comparative Example 1-2 above (Red Pigment-2-10). The production conditions at this time are shown in Table 2-1, and the characteristics of the obtained monoazo pigment are shown in Table 2-2.
　比較例２－３（特開２００５－３１２７５号公報の実施例２の追試実験）
　上記比較例１－３と同一である（赤色顔料－２－１１）。このときの製造条件を表２－１に、得られた混晶顔料の諸特性を表２－２に示す。 Comparative Example 2-3 (Follow-up experiment of Example 2 of JP-A-2005-3275)
Same as Comparative Example 1-3 (Red Pigment-2-11). The production conditions at this time are shown in Table 2-1, and the characteristics of the obtained mixed crystal pigment are shown in Table 2-2.
　比較例２－４（特開２０００－２４８１９１号公報の実施例１の追試実験）
　上記比較例１－４と同一である（赤色顔料－２－１２）。このときの製造条件を表２－１に、得られたモノアゾ系赤色顔料の諸特性を表２－２に示す。 Comparative Example 2-4 (Follow-up experiment of Example 1 of JP 2000-248191 A)
Same as Comparative Example 1-4 (Red Pigment-2-12). The production conditions at this time are shown in Table 2-1, and the characteristics of the obtained monoazo red pigment are shown in Table 2-2.
Figure JPOXMLDOC01-appb-T000040
Figure JPOXMLDOC01-appb-T000040
Figure JPOXMLDOC01-appb-T000041
Figure JPOXMLDOC01-appb-T000041
　以上のように、実施例のナフトールレッドは、いずれも、軸比が１．０～２．０の範囲であり、分散性、発色性に優れることは明らかである。 As described above, the naphthol reds of the examples all have an axial ratio in the range of 1.0 to 2.0, and are clearly excellent in dispersibility and color developability.
＜樹脂組成物の製造＞
　実施例２－９
　実施例２－１で得た赤色顔料－２－１　３．０重量部とポリエステル樹脂ＤＩＡＣＲＯＮ　ＥＲ５６１（三菱レイヨン製）５７．０重量部を秤量し、サンプルミルにて粉砕した。これをラボプラストミル（東洋精機製）にて１２０℃、２５ｒｐｍで１０分間混練し、取り出した後、室温まで冷却した。この後、超遠心粉砕機（レッチェ製ＺＭ２００）を用いて１２０００ｒｐｍにて粉砕し、樹脂組成物を得た。 <Manufacture of resin composition>
Example 2-9
3.0 parts by weight of the red pigment 2-1 obtained in Example 2-1 and 57.0 parts by weight of the polyester resin DIACRON ER561 (manufactured by Mitsubishi Rayon) were weighed and ground 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.
　実施例２－１０～２－１６、比較例２－５～２－８
　ナフトールレッドの種類を種々変化させた以外は、前記実施例２－９と同様にして樹脂組成物を得た。 Examples 2-10 to 2-16, Comparative Examples 2-5 to 2-8
A resin composition was obtained in the same manner as in Example 2-9 except that the type of naphthol red was variously changed.
　このときに得られた樹脂組成物の諸特性を表２－３に示す。 The various properties of the resin composition obtained at this time are shown in Table 2-3.
Figure JPOXMLDOC01-appb-T000042
Figure JPOXMLDOC01-appb-T000042
　以上のように、実施例の樹脂組成物は、分散性に優れ、発色性に優れることは明らかである。 As described above, it is clear that the resin compositions of the examples are excellent in dispersibility and color developability.
＜水系分散体の製造＞
　実施例２－１７
　１４０ｍｌのガラスビンに、実施例２－１で得たナフトールレッド０．５重量部を用い、水系分散体組成を下記割合で配合して１．５ｍｍφガラスビーズ５０重量部とともにペイントシェーカーで６０分間混合分散し、水系分散体を得た。 <Production of aqueous dispersion>
Example 2-17
Using 0.5 parts by weight of naphthol red obtained in Example 2-1 in a 140 ml glass bottle, the aqueous dispersion composition was blended in the following proportions 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.
　水系分散体は、下記の割合で配合した。
　ナフトールレッド　　　　　　　　　　　　　　　　０．５０重量部、
　アニオン系界面活性剤　　　　　　　　　　　　　　０．０５重量部、
　　（ネオペレックスＧＳ：花王製）
　アクリルエマルジョン（固形分３３％）　　　　　２８．７９重量部、
　　（ニカゾールＲＸ－３００２Ｅ：日本カーバイド製）
　消泡剤　　　　　　　　　　　　　　　　　　　　　０．０５重量部、
　　（エンバイロジェムＡＤ－０１　：日信化学工業製）
　純水　　　　　　　　　　　　　　　　　　　　　２０．６１重量部。 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.
　実施例２－１８～２－２４、比較例２－９～２－１２
　ナフトールレッドの種類を種々変化させた以外は、前記実施例２－１７と同様にして水系分散体を得た。 Examples 2-18 to 2-24, Comparative Examples 2-9 to 2-12
An aqueous dispersion was obtained in the same manner as in Example 2-17 except that the type of naphthol red was variously changed.
　このときに得られた水系分散体の諸特性を表２－４に示す。 The characteristics of the aqueous dispersion obtained at this time are shown in Table 2-4.
Figure JPOXMLDOC01-appb-T000043
Figure JPOXMLDOC01-appb-T000043
　以上のように、実施例の水系分散体は、保存安定性に優れ、分散性に優れ、発色性に優れることは明らかである。 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.
＜溶剤系分散体の製造＞
　実施例２－２５
　１４０ｍｌのガラスビンに、実施例２－１で得たナフトールレッド０．５０重量部を用い、溶剤系分散体組成を下記割合で配合して１．５ｍｍφガラスビーズ５０重量部とともにペイントシェーカーで６０分間混合分散し溶剤系分散体を作製した。 <Production of solvent-based dispersion>
Example 2-25
Using 0.50 parts by weight of naphthol red obtained in Example 2-1 in a 140 ml glass bottle, the solvent-based dispersion composition was blended at the following ratio and mixed with a paint shaker for 60 minutes together with 50 parts by weight of 1.5 mmφ glass beads. A solvent dispersion was prepared by dispersion.
　溶剤系分散体は、下記の組成で配合した。
　ナフトールレッド　　　　　　　　　　　　　　　　０．５０重量部、
　ポリエステル樹脂ＤＩＡＣＲＯＮ　ＥＲ５６１　　　９．５０重量部、
　（三菱レイヨン製）
　テトラヒドロフラン　　　　　　　　　　　　　　４０．００重量部。 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.
　実施例２－２６～２－３２、比較例２－１３～２－１６
　ナフトールレッドの種類を種々変化させた以外は、前記実施例２－２５と同様にして溶剤系分散体を得た。 Examples 2-26 to 2-32, Comparative Examples 2-13 to 2-16
A solvent-based dispersion was obtained in the same manner as in Example 2-25 except that the type of naphthol red was variously changed.
　このときに得られた溶剤系分散体の諸特性を表２－５に示す。 The properties of the solvent dispersion obtained at this time are shown in Table 2-5.
Figure JPOXMLDOC01-appb-T000044
Figure JPOXMLDOC01-appb-T000044
　以上のように、実施例の溶剤系分散体は、保存安定性に優れ、分散性に優れ、発色性に優れることは明らかである。 As described above, it is clear that the solvent-based dispersions of the examples have excellent storage stability, excellent dispersibility, and excellent color developability.
＜ナフトールレッドの第一形態の製造＞
　実施例３－１（シリンジインジェクション）
　実施例１－１と同じ手法で本発明に係るナフトールレッド（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　２６９）を得た。（赤色顔料－３－１） <Manufacture of the first form of naphthol red>
Example 3-1 (syringe injection)
Naphthol red (CI Pigment Red 269) according to the present invention was obtained in the same manner as in Example 1-1. (Red pigment-3-1)
　実施例３－２（ミストインジェクション）
　芳香族アミン、ナフトール、薬剤の量、水の量を変更した以外は、実施例３－１と同様にして、ジアゾニウム塩冷却溶液、ナフトール冷却溶液を得た。
　そして、ジアゾニウム塩冷却溶液を０．５ｍｍのノズルを搭載した噴霧器に入れ、１０℃以下でナフトール冷却溶液攪拌液中に１５重量部／分の割合で液中へインジェクションし、５℃以下で１時間１２００ｒｐｍにて攪拌した。その後、９０℃まで加熱して、そのまま１時間１２００ｒｐｍにて攪拌した。さらに、１Ｎ塩酸、あるいは、１Ｎ水酸化ナトリウム水溶液を用いてｐＨを６．０に調整し、濾過、水洗をして、８０℃にて１０時間乾燥し、粉砕して、本発明に係るナフトールレッド（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　５）を得た。（赤色顔料－３－２） Example 3-2 (mist injection)
A diazonium salt cooling solution and a naphthol cooling solution were obtained in the same manner as in Example 3-1, except that the amounts of aromatic amine, naphthol, drug, and water were changed.
Then, the diazonium salt cooling solution is put into a sprayer equipped with a 0.5 mm nozzle and injected into the naphthol cooling solution stirring liquid at a rate of 15 parts by weight / min. Stir at 1200 rpm. Then, 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. (C.I. Pigment Red 5) was obtained. (Red pigment-3-2)
　実施例３－３（超音波）
　芳香族アミン、ナフトール、薬剤の量、水の量を変更した以外は、実施例３－１と同様にして、ジアゾニウム塩冷却溶液、ナフトール冷却溶液を得た。
　そして、連続式破砕アダプターを装着した超音波ホモジナイザー（ＢＲＡＮＳＯＮ製ＳＯＮＩＦＥＲＩＩｍｏｄｅｌ２５０Ｄ）とペリスタリックポンプ、冷却ユニット付きベッセルを連結し、ナフトール冷却溶液を１５０重量部／分、５℃以下で循環した。また、超音波ホモジナイザー破砕ホーンの下部１ｃｍの部分に０．５ｍｍのシリンジを取り付け、その先に、ジアゾニウム塩冷却溶液を入れたシリンジポンプを取り付けた。その後、超音波を１００Ｗの出力で照射しながら、ジアゾニウム塩冷却溶液を１５重量部／分、５℃以下でインジェクションし、破砕ホーンの鼻先で超音波に照射されながら、ナフトール冷却溶液とジアゾニウム塩冷却溶液が、拡散接触して反応した。ジアゾニウム塩冷却溶液をインジェクションし終わってから５分間継続してペリスタリックポンプ循環ながら、超音波を照射して停止した。その後、この反応液をベッセルに戻し、１時間５℃以下で１２００ｒｐｍにて攪拌した。その後、９０℃まで加熱して、そのまま１時間１２００ｒｐｍにて攪拌した。さらに、１Ｎ塩酸、あるいは、１Ｎ水酸化ナトリウム水溶液を用いてｐＨを６．０に調整し、濾過、水洗をして、８０℃にて１０時間乾燥し、粉砕して、本発明に係るナフトールレッド（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　１７）を得た。（赤色顔料－３－３） Example 3-3 (ultrasound)
A diazonium salt cooling solution and a naphthol cooling solution were obtained in the same manner as in Example 3-1, except that the amounts of aromatic amine, naphthol, drug, and water were changed.
Then, an ultrasonic homogenizer equipped with a continuous crushing adapter (BRANSON-made SOFIFER II model 250D), a peristaltic pump, and a vessel with a cooling unit were connected, and the naphthol cooling solution was circulated at 150 parts by weight / min at 5 ° C. or less. In addition, a 0.5 mm syringe was attached to the lower 1 cm portion of the ultrasonic homogenizer crushing horn, and a syringe pump containing a diazonium salt cooling solution was attached to the tip. Then, while irradiating with ultrasonic waves at an output of 100 W, the diazonium salt cooling solution was injected at 15 parts by weight / minute at 5 ° C. or lower, and the naphthol cooling solution and the diazonium salt cooling were performed while irradiating ultrasonic waves at the nose of the crushing horn. The solution reacted in diffusion contact. The injection was stopped by irradiating with ultrasonic waves while continuously circulating the peristaltic pump for 5 minutes after the injection of the diazonium salt cooling solution. Then, this reaction liquid was returned to the vessel and stirred at 1200 rpm at 5 ° C. or lower for 1 hour. Then, 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. (C.I. Pigment Red 17) was obtained. (Red pigment-3-3)
　実施例３－４（ラインミル）
　芳香族アミン、ナフトール、薬剤の量、水の量を変更した以外は、実施例３－１と同様にして、ジアゾニウム塩冷却溶液、ナフトール冷却溶液を得た。
　そして、原料供給槽と循環攪拌槽を付けたラインミル（プライミクス製Ｔ．Ｋ．パイプラインホモミクサーＰＬ－２Ｓ）を用意し、循環攪拌槽にナフトール冷却溶液を１５０重量部／分、５℃以下で循環した。また、原料供給槽にジアゾニウム塩冷却溶液を入れた。その後、ラインミルを５０００ｒｐｍの出力で攪拌しながら、ジアゾニウム塩冷却溶液を１５重量部／分、５℃以下でラインミルに投入し、ラインミルの鼻先で攪拌されながら、ナフトール冷却溶液とジアゾニウム塩冷却溶液が、拡散接触して反応した。ジアゾニウム塩冷却溶液を投入し終わってから５分間継続して循環攪拌を行ってから停止した。その後、この反応液を別のベッセルに移し、１時間５℃以下で１２００ｒｐｍにて攪拌した。その後、９０℃まで加熱して、そのまま１時間１２００ｒｐｍにて攪拌した。さらに、１Ｎ塩酸、あるいは、１Ｎ水酸化ナトリウム水溶液を用いてｐＨを６．０に調整し、濾過、水洗をして、８０℃にて１０時間乾燥し、粉砕して、本発明に係るナフトールレッド（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　２２）を得た。（赤色顔料－３－４） Example 3-4 (line mill)
A diazonium salt cooling solution and a naphthol cooling solution were obtained in the same manner as in Example 3-1, except that the amounts of aromatic amine, naphthol, drug, and water were changed.
Then, a line mill (Primix TK Pipeline Homomixer PL-2S) equipped with a raw material supply tank and a circulation stirring tank was prepared, and a naphthol cooling solution was added to the circulation stirring tank at 150 parts by weight / min at 5 ° C. or less. Circulated. Moreover, the diazonium salt cooling solution was put into the raw material supply tank. Thereafter, while stirring the line mill at an output of 5000 rpm, the diazonium salt cooling solution was added to the line mill at 15 parts by weight / min and 5 ° C. or less, and the naphthol cooling solution and the diazonium salt cooling solution were stirred at the nose of the line mill. Reacted by diffusion contact. After the cooling of the diazonium salt cooling solution was completed, the mixture was continuously stirred for 5 minutes and then stopped. Thereafter, the reaction solution was transferred to another vessel and stirred at 1200 rpm at 5 ° C. or less for 1 hour. Then, 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. (C.I. Pigment Red 22) was obtained. (Red pigment-3-4)
　実施例３－５（シリンジインジェクション）
　芳香族アミン、ナフトール、薬剤の量、水の量を変更した以外は、実施例３－１と同様にして、ジアゾニウム塩冷却溶液、ナフトール冷却溶液を得た。
　そして、ナフトール冷却溶液を０．５ｍｍのノズルを搭載したシリンジポンプに入れ、１０℃以下でジアゾニウム塩冷却溶液攪拌液中に１５重量部／分の割合で液中へインジェクションし、５℃以下で１時間１２００ｒｐｍにて攪拌した。その後、９０℃まで加熱して、そのまま１時間１２００ｒｐｍにて攪拌した。さらに、１Ｎ塩酸、あるいは、１Ｎ水酸化ナトリウム水溶液を用いてｐＨを６．０に調整し、濾過、水洗をして、８０℃にて１０時間乾燥し、粉砕して、本発明に係るナフトールレッド（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　１４６）を得た。（赤色顔料－３－５） Example 3-5 (syringe injection)
A diazonium salt cooling solution and a naphthol cooling solution were obtained in the same manner as in Example 3-1, except that the amounts of aromatic amine, naphthol, drug, and water were changed.
Then, the naphthol cooling solution is put into a syringe pump equipped with a 0.5 mm nozzle, and injected into the liquid at a rate of 15 parts by weight / min into the diazonium salt cooling solution stirring liquid at 10 ° C. or lower, and 1 at 5 ° C. or lower. Stir for 1200 hours at time. Then, 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. (C.I. Pigment Red 146) was obtained. (Red pigment-3-5)
　実施例３－６（ミストインジェクション）
　芳香族アミン、ナフトール、薬剤の量、水の量を変更した以外は、実施例３－１と同様にして、ジアゾニウム塩冷却溶液、ナフトール冷却溶液を得た。
　そして、ナフトール冷却溶液を０．５ｍｍのノズルを搭載した噴霧器に入れ、１０℃以下でジアゾニウム塩冷却溶液攪拌液中に１５重量部／分の割合で液中へインジェクションし、５℃以下で１時間１２００ｒｐｍにて攪拌した。その後、９０℃まで加熱して、そのまま１時間１２００ｒｐｍにて攪拌した。さらに、１Ｎ塩酸、あるいは、１Ｎ水酸化ナトリウム水溶液を用いてｐＨを６．０に調整し、濾過、水洗をして、８０℃にて１０時間乾燥し、粉砕して、本発明に係るナフトールレッド（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　１５０）を得た。（赤色顔料－３－６） Example 3-6 (mist injection)
A diazonium salt cooling solution and a naphthol cooling solution were obtained in the same manner as in Example 3-1, except that the amounts of aromatic amine, naphthol, drug, and water were changed.
Then, the naphthol cooling solution is put into a sprayer 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 1200 rpm. Then, 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. (C.I. Pigment Red 150) was obtained. (Red pigment-3-6)
　実施例３－７（超音波）
　芳香族アミン、ナフトール、薬剤の量、水の量を変更した以外は、実施例３－１と同様にして、ジアゾニウム塩冷却溶液、ナフトール冷却溶液を得た。
　そして、連続式破砕アダプターを装着した超音波ホモジナイザー（ＢＲＡＮＳＯＮ製ＳＯＮＩＦＥＲＩＩｍｏｄｅｌ２５０Ｄ）とペリスタリックポンプ、冷却ユニット付きベッセルを連結し、ジアゾニウム塩冷却溶液を１５０重量部／分、５℃以下で循環した。また、超音波ホモジナイザー破砕ホーンの下部１ｃｍの部分に０．５ｍｍのシリンジを取り付け、その先に、ナフトール冷却溶液を入れたシリンジポンプを取り付けた。その後、超音波を１００Ｗの出力で照射しながら、ナフトール冷却溶液を１５重量部／分、５℃以下でインジェクションし、破砕ホーンの鼻先で超音波に照射されながら、ナフトール冷却溶液とジアゾニウム塩冷却溶液が、拡散接触して反応した。ナフトール冷却溶液をインジェクションし終わってから５分間継続してペリスタリックポンプ循環ながら超音波を照射して停止した。その後、この反応液をベッセルに戻し、１時間５℃以下で１２００ｒｐｍにて攪拌した。その後、９０℃まで加熱して、そのまま１時間１２００ｒｐｍにて攪拌した。さらに、１Ｎ塩酸、あるいは、１Ｎ水酸化ナトリウム水溶液を用いてｐＨを６．０に調整し、濾過、水洗をして、８０℃にて１０時間乾燥し、粉砕して、本発明に係るナフトールレッド（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　１７０）を得た。（赤色顔料－３－７） Example 3-7 (ultrasound)
A diazonium salt cooling solution and a naphthol cooling solution were obtained in the same manner as in Example 3-1, except that the amounts of aromatic amine, naphthol, drug, and water were changed.
Then, an ultrasonic homogenizer equipped with a continuous crushing adapter (BRANSON made SOFIFER II model 250D), a peristaltic pump, and a vessel with a cooling unit were connected, and the diazonium salt cooling solution was circulated at 150 ° C./min at 5 ° C. or less. Moreover, a 0.5 mm syringe was attached to a 1 cm lower part of the ultrasonic homogenizer crushing horn, and a syringe pump containing a naphthol cooling solution was attached to the tip. Then, while irradiating ultrasonic waves at an output of 100 W, the naphthol cooling solution was injected at 15 parts by weight / minute at 5 ° C. or lower, and radiated with ultrasonic waves at the tip of the crushing horn, while the naphthol cooling solution and the diazonium salt cooling solution were applied. Reacted by diffusion contact. The injection was stopped by irradiating ultrasonic waves while circulating the peristaltic pump continuously for 5 minutes after the injection of the naphthol cooling solution. Then, this reaction liquid was returned to the vessel and stirred at 1200 rpm at 5 ° C. or lower for 1 hour. Then, 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. (C.I. Pigment Red 170) was obtained. (Red pigment-3-7)
　実施例３－８（ラインミル）
　芳香族アミン、ナフトール、薬剤の量、水の量を変更した以外は、実施例３－１と同様にして、ジアゾニウム塩冷却溶液、ナフトール冷却溶液を得た。
　そして、原料供給槽と循環攪拌槽を付けたラインミル（プライミクス製Ｔ．Ｋ．パイプラインホモミクサーＰＬ－２Ｓ）を用意し、循環攪拌槽にジアゾニウム塩冷却溶液を１５０重量部／分、５℃以下で循環した。また、原料供給槽にナフトール冷却溶液を入れた。その後、ラインミルを５０００ｒｐｍの出力で攪拌しながら、ジアゾニウム塩冷却溶液を１５重量部／分、５℃以下でラインミルに投入し、ラインミルの鼻先で攪拌されながら、ナフトール冷却溶液とジアゾニウム塩冷却溶液が、拡散接触して反応した。ナフトール冷却溶液を投入し終わってから５分間継続して循環攪拌を行い、停止した。その後、この反応液を別のベッセルに移し、１時間５℃以下で１２００ｒｐｍにて攪拌した。その後、９０℃まで加熱して、そのまま１時間１２００ｒｐｍにて攪拌した。さらに、１Ｎ塩酸、あるいは、１Ｎ水酸化ナトリウム水溶液を用いてｐＨを６．０に調整し、濾過、水洗をして、８０℃にて１０時間乾燥し、粉砕して、本発明に係るナフトールレッド（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　２６８）を得た。（赤色顔料－３－８） Example 3-8 (line mill)
A diazonium salt cooling solution and a naphthol cooling solution were obtained in the same manner as in Example 3-1, except that the amounts of aromatic amine, naphthol, drug, and water were changed.
Then, a line mill (Primix TK Pipeline Homomixer PL-2S) equipped with a raw material supply tank and a circulation stirring tank is prepared, and a diazonium salt cooling solution is 150 parts by weight / minute, 5 ° C. or less in the circulation stirring tank. It circulated in. Moreover, the naphthol cooling solution was put into the raw material supply tank. Thereafter, while stirring the line mill at an output of 5000 rpm, the diazonium salt cooling solution was added to the line mill at 15 parts by weight / min and 5 ° C. or less, and the naphthol cooling solution and the diazonium salt cooling solution were stirred at the nose of the line mill. Reacted by diffusion contact. After the addition of the naphthol cooling solution, circulation stirring was continued for 5 minutes and stopped. Thereafter, the reaction solution was transferred to another vessel and stirred at 1200 rpm at 5 ° C. or less for 1 hour. Then, 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. (C.I. Pigment Red 268) was obtained. (Red pigment-3-8)
　このときの製造条件を表３－１に、得られたナフトールレッドの諸特性を表３－２に示す。 The production conditions at this time are shown in Table 3-1, and the characteristics of the obtained naphthol red are shown in Table 3-2.
Figure JPOXMLDOC01-appb-T000045
Figure JPOXMLDOC01-appb-T000045
Figure JPOXMLDOC01-appb-T000046
Figure JPOXMLDOC01-appb-T000046
＜ナフトールレッドの第二形態の製造＞
　実施例３－９
　実施例２－１と同じ手法で、本発明に係るナフトールレッド（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　２６９）を得た。（赤色顔料－３－９） <Manufacture of the second form of naphthol red>
Example 3-9
In the same manner as in Example 2-1, naphthol red (CI Pigment Red 269) according to the present invention was obtained. (Red pigment-3-9)
　実施例３－１０～３－１２
　芳香族アミン、ナフトール、追加添加する親水性ナフトール誘導体、あるいは、親水性フェノール誘導体の種類と量、反応条件を種々変化させた以外は、前記実施例３－９と同様にして本発明に係るナフトールレッドを得た。（赤色顔料－３－１０～１２） Examples 3-10 to 3-12
The naphthol according to the present invention was the same as in Example 3-9, except that the kind and amount of the aromatic amine, naphthol, additionally added hydrophilic naphthol derivative, or hydrophilic phenol derivative, and the reaction conditions were variously changed. I got red. (Red pigment-3-10 to 12)
　実施例３－１３
　芳香族アミン、ナフトールを変更した以外は、実施例３－９と同様にして、ジアゾニウム塩冷却溶液、ナフトール冷却溶液を得た。
　そして、ナフトール冷却溶液を０．５ｍｍのノズルを搭載したシリンジポンプに入れ、１０℃以下でジアゾニウム塩冷却溶液攪拌液中に１５重量部／分の割合で液中へインジェクションし、５℃以下で３０分３００ｒｐｍにて攪拌した。その後、２－ナフトール－３カルキシアミド、０．４重量部を氷水２０重量部に溶解した溶液を調製し、それを、５℃以下まで冷却した。そして、その溶液を、５℃以下で反応液に添加し、さらに１時間３００ｒｐｍにて攪拌した。そして、９０℃まで加熱して、そのまま１時間１２００ｒｐｍにて攪拌した。さらに、１Ｎ塩酸、あるいは、１Ｎ水酸化ナトリウム水溶液を用いてｐＨを６．０に調整し、濾過、水洗をして、８０℃にて１０時間乾燥し、粉砕して、本発明に係るナフトールレッド（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　１４６）を得た。（赤色顔料－３－１３） Example 3-13
A diazonium salt cooling solution and a naphthol cooling solution were obtained in the same manner as in Example 3-9 except that the aromatic amine and naphthol were changed.
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. Thereafter, a solution in which 0.4 part by weight of 2-naphthol-3 carxamide was dissolved in 20 parts by weight of ice water was prepared and cooled to 5 ° C. or lower. 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. (C.I. Pigment Red 146) was obtained. (Red pigment-3-13)
　実施例３－１４～３－１６
　芳香族アミン、ナフトール、追加添加する親水性ナフトール誘導体、あるいは、親水性フェノール湯導体の種類と量、反応条件を種々変化させた以外は、前記実施例３－１３と同様にして本発明に係るナフトールレッドを得た。（赤色顔料－３－１４～１６） Examples 3-14 to 3-16
According to the present invention, the same procedure as in Example 3-13 was conducted, except that the type and amount of the aromatic amine, naphthol, the additionally added hydrophilic naphthol derivative, or the hydrophilic phenol hot water conductor and the reaction conditions were variously changed. Naphthol red was obtained. (Red pigment-3-14 to 16)
　このときの製造条件を表３－３に、得られたナフトールレッドの諸特性を表３－４に示す。 The production conditions at this time are shown in Table 3-3, and the characteristics of the obtained naphthol red are shown in Table 3-4.
Figure JPOXMLDOC01-appb-T000047
Figure JPOXMLDOC01-appb-T000047
Figure JPOXMLDOC01-appb-T000048
Figure JPOXMLDOC01-appb-T000048
　比較例３－１（特開平１１－２７２０１４号公報の製造例１の追試実験）
　上記比較例１－１と同一である。モノアゾ系顔料（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　２６９）を得た（赤色顔料－３－１７）。このときの製造条件を表３－５に、得られたモノアゾ系顔料の諸特性を表３－６に示す。 Comparative Example 3-1 (Additional Experiment of Production Example 1 of JP-A-11-272014)
The same as Comparative Example 1-1 above. A monoazo pigment (CI Pigment Red 269) was obtained (red pigment-3-17). The production conditions at this time are shown in Table 3-5, and the properties of the obtained monoazo pigment are shown in Table 3-6.
　比較例３－２（特開２０００－１８６２４１号公報の製造例１の追試実験）
　上記比較例１－２と同一である。モノアゾ系顔料（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　２６９）を得た（赤色顔料－３－１８）。このときの製造条件を表３－５に、得られたモノアゾ系顔料の諸特性を表３－６に示す。 Comparative Example 3-2 (Follow-up experiment of Production Example 1 of JP 2000-186241 A)
Same as Comparative Example 1-2 above. A monoazo pigment (CI Pigment Red 269) was obtained (red pigment-3-18). The production conditions at this time are shown in Table 3-5, and the properties of the obtained monoazo pigment are shown in Table 3-6.
　比較例３－３（特開２００５－３１２７５号公報の実施例２の追試実験）
　上記比較例１－３と同一である。混晶顔料を得た（赤色顔料－３－２０）。このときの製造条件を表３－５に、得られた混晶顔料の諸特性を表３－６に示す。 Comparative Example 3-3 (Follow-up experiment of Example 2 of JP-A-2005-3275)
Same as Comparative Example 1-3 above. A mixed crystal pigment was obtained (red pigment-3-20). The production conditions at this time are shown in Table 3-5, and the characteristics of the obtained mixed crystal pigment are shown in Table 3-6.
　比較例３－４（特開２０００－２４８１９１号公報の実施例１の追試実験）
　上記比較例１－４と同一である。モノアゾ系赤色顔料を得た（赤色顔料－３－２１）。このときの製造条件を表３－５に、得られたモノアゾ系赤色顔料の諸特性を表３－６に示す。 Comparative Example 3-4 (Follow-up experiment of Example 1 of JP 2000-248191 A)
The same as Comparative Example 1-4 above. A monoazo red pigment was obtained (red pigment-3-21). The production conditions at this time are shown in Table 3-5, and the characteristics of the obtained monoazo red pigment are shown in Table 3-6.
Figure JPOXMLDOC01-appb-T000049
Figure JPOXMLDOC01-appb-T000049
Figure JPOXMLDOC01-appb-T000050
Figure JPOXMLDOC01-appb-T000050
　以上のように、実施例のナフトールレッドは、いずれも、軸比が１．０～２．０の範囲であり、分散性、発色性に優れることは明らかである。 As described above, the naphthol reds of the examples all have an axial ratio in the range of 1.0 to 2.0, and are clearly excellent in dispersibility and color developability.
＜樹脂組成物の製造＞
　実施例３－１７
　実施例３－１で得た赤色顔料－３－１　３．０重量部とポリエステル樹脂ＤＩＡＣＲＯＮ　ＥＲ５６１（三菱レイヨン製）５７．０重量部を秤量し、サンプルミルにて粉砕した。これをラボプラストミル（東洋精機製）にて１２０℃、２５ｒｐｍで１０分間混練し、取り出した後、室温まで冷却した。この後、超遠心粉砕機（レッチェ製ＺＭ２００）を用いて１２０００ｒｐｍにて粉砕し、樹脂組成物を得た。 <Manufacture of resin composition>
Example 3-17
3.0 parts by weight of the red pigment-3-1 obtained in Example 3-1 and 57.0 parts by weight of the polyester resin DIACRON ER561 (manufactured by Mitsubishi Rayon) were weighed and ground 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.
　実施例３－１８～３－３２、比較例３－５～３－８
　ナフトールレッドの種類を種々変化させた以外は、前記実施例３－１７と同様にして樹脂組成物を得た。 Examples 3-18 to 3-32, Comparative Examples 3-5 to 3-8
A resin composition was obtained in the same manner as in Example 3-17 except that the type of naphthol red was variously changed.
　このときに得られた樹脂組成物の諸特性を表３－７に示す。 The properties of the resin composition obtained at this time are shown in Table 3-7.
Figure JPOXMLDOC01-appb-T000051
Figure JPOXMLDOC01-appb-T000051
　以上のように、実施例の樹脂組成物は、分散性に優れ、発色性に優れることは明らかである。 As described above, it is clear that the resin compositions of the examples are excellent in dispersibility and color developability.
＜水系分散体の製造＞
　実施例３－３３
　１４０ｍｌのガラスビンに、実施例３－１で得たナフトールレッド０．５重量部を用い、水系分散体組成を下記割合で配合して１．５ｍｍφガラスビーズ５０重量部とともにペイントシェーカーで６０分間混合分散し、水系分散体を得た。 <Production of aqueous dispersion>
Example 3-33
Using 0.5 parts by weight of naphthol red obtained in Example 3-1 in a 140 ml glass bottle, the aqueous dispersion composition is blended in the following proportions 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.
　水系分散体は、下記の割合で配合した。
　ナフトールレッド　　　　　　　　　　　　　　　　０．５０重量部、
　アニオン系界面活性剤　　　　　　　　　　　　　　０．０５重量部、
　　（ネオペレックスＧＳ：花王製）
　アクリルエマルジョン（固形分３３％）　　　　　２８．７９重量部、
　　（ニカゾールＲＸ－３００２Ｅ：日本カーバイド製）
　消泡剤　　　　　　　　　　　　　　　　　　　　　０．０５重量部、
　　（エンバイロジェムＡＤ－０１　：日信化学工業製）
　純水　　　　　　　　　　　　　　　　　　　　　２０．６１重量部。 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.
　実施例３－３３～３－４８、比較例３－９～３－１２
　ナフトールレッドの種類を種々変化させた以外は、前記実施例３－１７と同様にして水系分散体を得た。 Examples 3-33 to 3-48, Comparative Examples 3-9 to 3-12
An aqueous dispersion was obtained in the same manner as in Example 3-17 except that various types of naphthol red were used.
このときに得られた水系分散体の諸特性を表３－８に示す。 Various characteristics of the aqueous dispersion obtained at this time are shown in Table 3-8.
Figure JPOXMLDOC01-appb-T000052
Figure JPOXMLDOC01-appb-T000052
　以上のように、実施例の水系分散体は、保存安定性に優れ、分散性に優れ、発色性に優れることは明らかである。 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.
＜溶剤系分散体の製造＞
　実施例３－４９
　１４０ｍｌのガラスビンに、実施例３－１で得たナフトールレッド０．５０重量部を用い、溶剤系分散体組成を下記割合で配合して１．５ｍｍφガラスビーズ５０重量部とともにペイントシェーカーで６０分間混合分散し溶剤系分散体を得た。 <Production of solvent-based dispersion>
Example 3-49
Using 0.50 parts by weight of naphthol red obtained in Example 3-1 in a 140 ml glass bottle, the solvent-based dispersion composition was blended in the following proportions and mixed with a paint shaker for 60 minutes together with 50 parts by weight of 1.5 mmφ glass beads. Dispersion was performed to obtain a solvent dispersion.
　溶剤系分散体は、下記の組成で配合した。
　ナフトールレッド　　　　　　　　　　　　　　　　０．５０重量部、
　ポリエステル樹脂ＤＩＡＣＲＯＮ　ＥＲ５６１　　　９．５０重量部、
（三菱レイヨン製）
　テトラヒドロフラン　　　　　　　　　　　　　　４０．００重量部。 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.
　実施例３－５０～３－６４、比較例３－１６～３－２０
　ナフトールレッドの種類を種々変化させた以外は、前記実施例３－４９と同様にして溶剤系分散体を得た。 Examples 3-50 to 3-64, Comparative Examples 3-16 to 3-20
A solvent dispersion was obtained in the same manner as in Example 3-49 except that the type of naphthol red was variously changed.
　このときに得られた溶剤系分散体の諸特性を表３－９に示す。 The properties of the solvent dispersion obtained at this time are shown in Table 3-9.
Figure JPOXMLDOC01-appb-T000053
Figure JPOXMLDOC01-appb-T000053
　以上のように、実施例の溶剤系分散体は、保存安定性に優れ、分散性に優れ、発色性に優れることは明らかである。 As described above, it is clear that the solvent-based dispersions of the examples have excellent storage stability, excellent dispersibility, and excellent color developability.
＜ナフトールレッドの製造＞
　実施例４－１
　３５％ＨＣｌ水溶液１２．５重量部を氷水１８７．５重量部中に加え攪拌し、温度を５℃以下に調節した。これに、３－アミノ－４－メトキシベンズアニライド８重量部加えて攪拌して、３－アミノ－４－メトキシベンズアニライドの溶解と、３－アミノ－４－メトキシベンズアニライドの塩酸塩の析出を確認し、３０分間５℃以下で攪拌した。その後、３０％亜硝酸ナトリウム水溶液７．８重量部を加えて６０分間５℃以下で攪拌し、スルファミン酸０．３重量部を加えて亜硝酸を消去した。さらに、酢酸ナトリウム８重量部、９０％酢酸１２重量部を添加し、ジアゾニウム塩冷却溶液とした。また、別にＮ－（５－クロロ－２－メトキシフェニル）－３－ヒドロキシ－２－ナフタレンカルボキシアミド１１重量部を秤量し、純水１５０ｇ、水酸化ナトリウム４重量部を加え、攪拌しながら９０℃まで加熱して、溶解した。さらにこれを攪拌しながら、５℃まで冷却してナフトール冷却溶液とした。そして、ジアゾニウム塩冷却溶液を０．５ｍｍのシリンジを搭載したシリンジポンプに入れ、１０℃以下でナフトール冷却溶液攪拌液中に１５重量部／分の割合で液中へインジェクションし、５℃以下で３０分３００ｒｐｍにて反応液を攪拌した。その後、２－ナフトール－３カルボン酸、０．４重量部を氷水２０重量部に溶解した溶液を調製し、それを、５℃以下まで冷却した。そして、その溶液を、５℃以下で反応液に添加し、さらに１時間３００ｒｐｍにて攪拌した。その後、９０℃まで加熱して、そのまま１時間３００ｒｐｍにて攪拌した。さらに、１Ｎ塩酸、あるいは、１Ｎ水酸化ナトリウム水溶液を用いてｐＨを６．０に調整し、濾過、水洗をして、８０℃にて１０時間乾燥し、粉砕して、本発明に係るナフトールレッドを得た。（赤色顔料－４－１） <Manufacture of naphthol red>
Example 4-1
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. Thereafter, a solution in which 0.4 part by weight of 2-naphthol-3carboxylic acid was dissolved in 20 parts by weight of ice water was prepared and cooled to 5 ° C. or lower. 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-4-1)
　実施例４－２～４－４
　追加添加する親水性ナフトール誘導体、あるいは、親水性フェノール誘導体の種類と量、反応条件を種々変化させた以外は、前記実施例４－１と同様にして本発明に係るナフトールレッドを得た。（赤色顔料－４－２～４） Examples 4-2 to 4-4
A naphthol red according to the present invention was obtained in the same manner as in Example 4-1, except that the type and amount of the hydrophilic naphthol derivative or hydrophilic phenol derivative to be added and the reaction conditions were variously changed. (Red pigment -4-2 to 4)
　実施例４－５
　実施例４－１と同様にして、ジアゾニウム塩冷却溶液、ナフトール冷却溶液を得た。
　そして、ナフトール冷却溶液を０．５ｍｍのノズルを搭載したシリンジポンプに入れ、１０℃以下でジアゾニウム塩冷却溶液攪拌液中に１５重量部／分の割合で液中へインジェクションし、５℃以下で３０分３００ｒｐｍにて攪拌した。その後、２－ナフトール－３カルボキシアミド、０．４重量部を氷水２０重量部に溶解した溶液を調製し、それを、５℃以下まで冷却した。そして、その溶液を、５℃以下で反応液に添加し、さらに１時間３００ｒｐｍにて攪拌した。そして、９０℃まで加熱して、そのまま１時間１２００ｒｐｍにて攪拌した。さらに、１Ｎ塩酸、あるいは、１Ｎ水酸化ナトリウム水溶液を用いてｐＨを６．０に調整し、濾過、水洗をして、８０℃にて１０時間乾燥し、粉砕して、本発明に係るナフトールレッドを得た。（赤色顔料－４－５） Example 4-5
In the same manner as in Example 4-1, 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. Thereafter, a solution in which 0.4 parts by weight of 2-naphthol-3carboxamide was dissolved in 20 parts by weight of ice water was prepared, and the solution was cooled to 5 ° C. or lower. 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-4-5)
　実施例４－６～４－８
　追加添加する親水性ナフトール誘導体、あるいは、親水性フェノール誘導体の種類と量、反応条件を種々変化させた以外は、前記実施例４－５と同様にして本発明に係るナフトールレッドを得た。（赤色顔料－４－６～８） Examples 4-6 to 4-8
A naphthol red according to the present invention was obtained in the same manner as in Example 4-5 except that the hydrophilic naphthol derivative to be additionally added or the kind and amount of the hydrophilic phenol derivative and the reaction conditions were variously changed. (Red pigment-4-6-8)
このときの製造条件を表４－１に、得られたナフトールレッドの諸特性を表４－２に示す。 The production conditions at this time are shown in Table 4-1, and the characteristics of the obtained naphthol red are shown in Table 4-2.
　比較例４－１（特開平１１－２７２０１４の製造例１の追試実験）
　上記比較例１－１と同一である（赤色顔料－４－９）。このときの製造条件を表４－１に、得られたモノアゾ系顔料の諸特性を表４－２に示す。 Comparative Example 4-1 (Follow-up Experiment of Production Example 1 of JP-A-11-272014)
Same as Comparative Example 1-1 (Red Pigment-4-9). The production conditions at this time are shown in Table 4-1, and the characteristics of the obtained monoazo pigment are shown in Table 4-2.
　比較例４－２（特開２０００－１８６２４１号公報の製造例１の追試実験）
　上記比較例１－２と同一である（赤色顔料－４－１０）。このときの製造条件を表４－１に、得られたモノアゾ系顔料の諸特性を表４－２に示す。 Comparative Example 4-2 (Follow-up Experiment of Production Example 1 of JP 2000-186241 A)
Same as Comparative Example 1-2 above (red pigment-4-10). The production conditions at this time are shown in Table 4-1, and the characteristics of the obtained monoazo pigment are shown in Table 4-2.
　比較例４－３（特開２００５－３１２７５公報の実施例２の追試実験）
　上記比較例１－３と同一である（赤色顔料－４－１１）。このときの製造条件を表４－１に、得られた混晶顔料の諸特性を表４－２に示す。 Comparative Example 4-3 (Follow-up experiment of Example 2 of JP-A-2005-3275)
Same as Comparative Example 1-3 above (Red Pigment-4-11). The production conditions at this time are shown in Table 4-1, and the characteristics of the obtained mixed crystal pigment are shown in Table 4-2.
　比較例４－４（特開２０００－２４８１９１公報の実施例１の追試実験）
　上記比較例１－４と同一である（赤色顔料－４－１２）。このときの製造条件を表４－１に、得られたモノアゾ系赤色顔料の諸特性を表４－２に示す。 Comparative Example 4-4 (Follow-up experiment of Example 1 of JP 2000-248191 A)
Same as Comparative Example 1-4 (Red Pigment-4-12). The production conditions at this time are shown in Table 4-1, and the characteristics of the obtained monoazo red pigment are shown in Table 4-2.
Figure JPOXMLDOC01-appb-T000054
Figure JPOXMLDOC01-appb-T000054
Figure JPOXMLDOC01-appb-T000055
Figure JPOXMLDOC01-appb-T000055
　以上のように、実施例のナフトールレッドは親水性ナフトール誘導体、あるいは、親水性フェノール誘導体が０．０１～０．３重量％表面処理されており、分散性、発色性に優れることは明らかである。 As described above, the naphthol red of the example is surface-treated with a hydrophilic naphthol derivative or a hydrophilic phenol derivative in an amount of 0.01 to 0.3% by weight, and is clearly excellent in dispersibility and color development. .
＜樹脂組成物の製造＞
　実施例４－９
　実施例４－１で得た赤色顔料－４－１　３．０重量部とポリエステル樹脂ＤＩＡＣＲＯＮ　ＥＲ５６１（三菱レイヨン製）５７．０重量部を秤量し、サンプルミルにて粉砕した。これをラボプラストミル（東洋精機製）にて１２０℃、２５ｒｐｍで１０分間混練し、取り出した後、室温まで冷却した。この後、超遠心粉砕機（レッチェ製ＺＭ２００）を用いて１２０００ｒｐｍにて粉砕し、樹脂組成物を得た。 <Manufacture of resin composition>
Example 4-9
3.0 parts by weight of the red pigment-4-1 obtained in Example 4-1 and 57.0 parts by weight of the polyester resin DIACRON ER561 (manufactured by Mitsubishi Rayon) were weighed and ground 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.
実施例４－１０～４－１６、比較例４－５～４－８
　ナフトールレッドの種類を種々変化させた以外は、前記実施例４－９と同様にして樹脂組成物を得た。 Examples 4-10 to 4-16, Comparative Examples 4-5 to 4-8
A resin composition was obtained in the same manner as in Example 4-9 except that the type of naphthol red was variously changed.
　このときに得られた樹脂組成物の諸特性を表４－３に示す。 The various properties of the resin composition obtained at this time are shown in Table 4-3.
Figure JPOXMLDOC01-appb-T000056
Figure JPOXMLDOC01-appb-T000056
　以上のように、実施例の樹脂組成物は、分散性に優れ、発色性に優れることは明らかである。 As described above, it is clear that the resin compositions of the examples are excellent in dispersibility and color developability.
＜水系分散体の製造＞
　実施例４－１７
　１４０ｍｌのガラスビンに、実施例４－１で得たナフトールレッド０．５重量部を用い、水系分散体組成を下記割合で配合して１．５ｍｍφガラスビーズ５０重量部とともにペイントシェーカーで６０分間混合分散し、水系分散体を得た。 <Production of aqueous dispersion>
Example 4-17
Using 0.5 parts by weight of naphthol red obtained in Example 4-1 in a 140 ml glass bottle, the aqueous dispersion composition was blended in the following proportions 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.
　水系分散体は、下記の割合で配合した。
　ナフトールレッド　　　　　　　　　　　　　　　　０．５０重量部、
　アニオン系界面活性剤　　　　　　　　　　　　　　０．０５重量部、
　　（ネオペレックスＧＳ：花王製）
　アクリルエマルジョン（固形分３３％）　　　　　２８．７９重量部、
　　（ニカゾールＲＸ－３００２Ｅ：日本カーバイド製）
　消泡剤　　　　　　　　　　　　　　　　　　　　　０．０５重量部、
　　（エンバイロジェムＡＤ－０１：日信化学工業製）
　純水　　　　　　　　　　　　　　　　　　　　　２０．６１重量部。 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: manufactured by Nissin Chemical Industry)
Pure water 20.61 parts by weight.
　実施例４－１８～４－２４、比較例４－９～４－１２
　ナフトールレッドの種類を種々変化させた以外は、前記実施例４－１７と同様にして水系分散体を得た。 Examples 4-18 to 4-24, Comparative Examples 4-9 to 4-12
An aqueous dispersion was obtained in the same manner as in Example 4-17 except that the type of naphthol red was variously changed.
　このときに得られた水系分散体の諸特性を表４－４に示す。 The characteristics of the aqueous dispersion obtained at this time are shown in Table 4-4.
Figure JPOXMLDOC01-appb-T000057
Figure JPOXMLDOC01-appb-T000057
　以上のように、実施例の水系分散体は、保存安定性に優れ、分散性に優れ、発色性に優れることは明らかである。 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.
＜溶剤系分散体の製造＞
　実施例４－２５
　１４０ｍｌのガラスビンに、実施例４－１で得たナフトールレッド０．５０重量部を用い、溶剤系分散体組成を下記割合で配合して１．５ｍｍφガラスビーズ５０重量部とともにペイントシェーカーで６０分間混合分散し溶剤系分散体を得た。 <Production of solvent-based dispersion>
Example 4-25
Using 0.50 parts by weight of naphthol red obtained in Example 4-1 in a 140 ml glass bottle, the solvent-based dispersion composition was blended in the following proportions and mixed with a paint shaker for 60 minutes together with 50 parts by weight of 1.5 mmφ glass beads. Dispersion was performed to obtain a solvent dispersion.
　溶剤系分散体は、下記の組成で配合した。
　ナフトールレッド　　　　　　　　　　　　　　　　０．５０重量部、
　ポリエステル樹脂ＤＩＡＣＲＯＮ　ＥＲ５６１　　　９．５０重量部、
（三菱レイヨン製）
　テトラヒドロフラン　　　　　　　　　　　　　　４０．００重量部。 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.
　実施例４－２６～４－３２、比較例４－１３～４－１６
　ナフトールレッドの種類を種々変化させた以外は、前記実施例４－２５と同様にして溶剤系分散体を得た。 Examples 4-26 to 4-32, Comparative Examples 4-13 to 4-16
A solvent dispersion was obtained in the same manner as in Example 4-25 except that the type of naphthol red was variously changed.
このときに得られた溶剤系分散体の諸特性を表４－５に示す。 Various characteristics of the solvent dispersion obtained at this time are shown in Table 4-5.
Figure JPOXMLDOC01-appb-T000058
Figure JPOXMLDOC01-appb-T000058
　以上のように、実施例の溶剤系分散体は、保存安定性に優れ、分散性に優れ、発色性に優れることは明らかである。 As described above, it is clear that the solvent-based dispersions of the examples have excellent storage stability, excellent dispersibility, and excellent color developability.
　本発明に係るナフトールレッド、親水性ナフトール誘導体、あるいは、親水性フェノール誘導体が０．０１～０．３重量％表面処理されたナフトールレッドは、一次粒子の軸比が小さく、分散性、発色性に優れるので、電子写真用非磁性現像剤、インクジェットインク、液晶用カラーフィルターなどの電子機器などの分野や、塗料、印刷インキ、絵の具、ポスターカラー、プラスチック着色剤、化粧品などの各種用途として好適である。また、本発明に係るナフトールレッドの製造方法は、分散性、発色性に優れたナフトールレッドの製造方法として好適である。また、本発明に係るナフトールレッドを含んでなる樹脂組成物は、分散性、発色性に優れるので樹脂組成物として好適である。また、本発明に係るナフトールレッドによって着色した水系分散体、および、溶剤系分散体は、分散性、発色性に優れるので、各種分散体として好適である。 The naphthol red surface-treated with naphthol red, a hydrophilic naphthol derivative, or a hydrophilic phenol derivative according to the present invention has a small primary particle axial ratio and is excellent in dispersibility and color development. Excellent, suitable for fields such as non-magnetic developers for electrophotography, inkjet inks, color filters for liquid crystals, and various applications such as paints, printing inks, paints, poster colors, plastic colorants, cosmetics, etc. . The method for producing naphthol red according to the present invention is suitable as a method for producing naphthol red having excellent dispersibility and color developability. 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 (18)

  1. 　化学式（１）で示されるナフトールレッドであって、一次粒子の軸比（平均長軸径／平均短軸径）が１．０～２．０の範囲であるナフトールレッド。
    Figure JPOXMLDOC01-appb-C000001
         A naphthol red represented by the chemical formula (1), 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.
    Figure JPOXMLDOC01-appb-C000001
  2. 　一次粒子の平均粒径が０．０２μｍ～０．２０μｍである請求項１記載のナフトールレッド。 2. The naphthol red according to claim 1, wherein the average primary particle diameter is 0.02 μm to 0.20 μm.
  3. 　顔料濃度５％ポリエステル樹脂塗膜にて、膜厚３μｍでのヘイズ値が１０～２０％である請求項１または２記載のナフトールレッド。 3. The naphthol red according to claim 1 or 2, wherein the haze value at a film thickness of 3 μm is 10 to 20% with a polyester resin coating having a pigment concentration of 5%.
  4. 　顔料濃度５％ポリエステル樹脂塗膜にて、膜厚３μｍでの彩度ｃ＊が６０以上である請求項１～３のいずれかに記載のナフトールレッド。 The naphthol red according to any one of claims 1 to 3, wherein the saturation c * at a film thickness of 3 µm is 60 or more in a polyester resin coating having a pigment concentration of 5%.
  5. 　粉体ｐＨが４．０～９．０の範囲にある請求項１～４のいずれかに記載のナフトールレッド。 The naphthol red according to any one of claims 1 to 4, wherein the powder pH is in the range of 4.0 to 9.0.
  6. 　化学式（１）で示されるナフトールレッドが化学式（１１）で示される化合物（化合物ＰＲ２６９）である請求項１～５のいずれかに記載のナフトールレッド。
    Figure JPOXMLDOC01-appb-C000002
         The naphthol red according to any one of claims 1 to 5, wherein the naphthol red represented by the chemical formula (1) is a compound represented by the chemical formula (11) (compound PR269).
    Figure JPOXMLDOC01-appb-C000002
  7. 　化学式（２）で示される芳香族アミンのジアゾニウム塩冷却溶液を化学式（３）で示されるナフトール冷却溶液に加える際、微小領域で反応させることを含む操作、または化学式（３）で示されるナフトール冷却溶液を化学式（２）で示されるベンズアニリドのジアゾニウム塩冷却溶液に加える際、微小領域で反応させることを含む操作で製造される化学式（１）に示すナフトールレッドの製造方法。
    Figure JPOXMLDOC01-appb-C000003
    Figure JPOXMLDOC01-appb-C000004
    Figure JPOXMLDOC01-appb-C000005
         An operation including reacting in a micro region when adding a diazonium salt cooling solution of an aromatic amine represented by the chemical formula (2) to a naphthol cooling solution represented by the chemical formula (3), or a naphthol cooling represented by the chemical formula (3) A method for producing naphthol red represented by chemical formula (1), which is produced by an operation including reacting in a microregion when a solution is added to a cooled diazonium salt solution of benzanilide represented by chemical formula (2).
    Figure JPOXMLDOC01-appb-C000003
    Figure JPOXMLDOC01-appb-C000004
    Figure JPOXMLDOC01-appb-C000005
  8. 　化学式（２）で示される芳香族アミンのアゾニウム塩冷却溶液を、化学式（３）で示されるナフトール冷却溶液に注入攪拌させることによって反応させるか、又は化学式（３）で示されるナフトール冷却溶液を、化学式（２）で示される芳香族アミンのアゾニウム塩冷却溶液に注入攪拌させることによって反応させ、さらに化学式（４）で示される親水性ナフトール誘導体、あるいは、化学式（５）で示される親水性フェノール誘導体を加えて反応することで製造される化学式（１）に示すナフトールレッドの製造方法。
    Figure JPOXMLDOC01-appb-C000006
    Figure JPOXMLDOC01-appb-C000007
    Figure JPOXMLDOC01-appb-C000008
     ただし、Ｒｋは、－Ｈ、－ＯＨ、ＳＯ３Ｈ、－ＣＯＯＨ、－ＣＯＮＨ２、ＣＯＮＨ－Ｃ６Ｈ４－ＳＯ３Ｈから選択され、ｎ＝１～３である。
    Figure JPOXMLDOC01-appb-C000009
     ただし、Ｒｋは、－Ｈ、－ＯＨ、ＳＯ３Ｈ、－ＣＯＯＨ、－ＣＯＮＨ２、ＣＯＮＨ－Ｃ６Ｈ４－ＳＯ３Ｈから選択され、ｎ＝１～３である。
    Figure JPOXMLDOC01-appb-C000010
         The aromatic amine azonium salt cooling solution represented by the chemical formula (2) is reacted by injecting and stirring the naphthol cooling solution represented by the chemical formula (3), or the naphthol cooling solution represented by the chemical formula (3) Reaction is carried out by injecting and stirring into an azonium salt cooling solution of an aromatic amine represented by the chemical formula (2), and further a hydrophilic naphthol derivative represented by the chemical formula (4) or a hydrophilic phenol derivative represented by the chemical formula (5) The manufacturing method of the naphthol red shown to Chemical formula (1) manufactured by adding and reacting.
    Figure JPOXMLDOC01-appb-C000006
    Figure JPOXMLDOC01-appb-C000007
    Figure JPOXMLDOC01-appb-C000008
     However, R k is selected from —H, —OH, SO 3 H, —COOH, —CONH 2 , CONH—C 6 H 4 —SO 3 H, and n = 1 to 3.
    Figure JPOXMLDOC01-appb-C000009
     However, R k is selected from —H, —OH, SO 3 H, —COOH, —CONH 2 , CONH—C 6 H 4 —SO 3 H, and n = 1 to 3.
    Figure JPOXMLDOC01-appb-C000010
  9. 　芳香族アミンが化学式（１２）で示される芳香族アミンであり、ナフトールが化学式（１３）で示されるナフトールであり、ナフトールレッドが化学式（１１）で示される化合物（化合物ＰＲ２６９）である請求項７～８のいずれかに記載のナフトールレッドの製造方法。
    Figure JPOXMLDOC01-appb-C000011
    Figure JPOXMLDOC01-appb-C000012
    Figure JPOXMLDOC01-appb-C000013
         8. The aromatic amine is an aromatic amine represented by chemical formula (12), naphthol is naphthol represented by chemical formula (13), and naphthol red is a compound represented by chemical formula (11) (compound PR269). The method for producing naphthol red according to any one of 1 to 8.
    Figure JPOXMLDOC01-appb-C000011
    Figure JPOXMLDOC01-appb-C000012
    Figure JPOXMLDOC01-appb-C000013
  10. 　化学式（１１）で示されるナフトールレッドであって、化学式（４）で示される親水性ナフトール誘導体、あるいは、化学式（５）で示される親水性フェノール誘導体が０．０１～０．３重量％表面処理されたナフトールレッド。
    Figure JPOXMLDOC01-appb-C000014
    Figure JPOXMLDOC01-appb-C000015
     ただし、Ｒｋは、－Ｈ、－ＯＨ、ＳＯ３Ｈ、－ＣＯＯＨ、－ＣＯＮＨ２、ＣＯＮＨ－Ｃ６Ｈ４－ＳＯ３Ｈから選択され、ｎ＝１～３である。
    Figure JPOXMLDOC01-appb-C000016
     ただし、Ｒｋは、－Ｈ、－ＯＨ、ＳＯ３Ｈ、－ＣＯＯＨ、－ＣＯＮＨ２、ＣＯＮＨ－Ｃ６Ｈ４－ＳＯ３Ｈから選択され、ｎ＝１～３である。     Surface treatment with 0.01 to 0.3 wt% of naphthol red represented by chemical formula (11), which is a hydrophilic naphthol derivative represented by chemical formula (4) or a hydrophilic phenol derivative represented by chemical formula (5) Naphthol red.
    Figure JPOXMLDOC01-appb-C000014
    Figure JPOXMLDOC01-appb-C000015
     However, R k is selected from —H, —OH, SO 3 H, —COOH, —CONH 2 , CONH—C 6 H 4 —SO 3 H, and n = 1 to 3.
    Figure JPOXMLDOC01-appb-C000016
     However, R k is selected from —H, —OH, SO 3 H, —COOH, —CONH 2 , CONH—C 6 H 4 —SO 3 H, and n = 1 to 3.
  11. 　一次粒子の軸比（平均長軸径／平均短軸径）が１．０～２．０の範囲である請求項１０記載のナフトールレッド。 The naphthol red according to claim 10, 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.
  12. 　一次粒子の平均粒径が０．０２μｍ～０．２０μｍである請求項１０または１１記載のナフトールレッド。 The naphthol red according to claim 10 or 11, wherein the primary particles have an average particle size of 0.02 to 0.20 µm.
  13. 　顔料濃度５％ポリエステル樹脂塗膜にて、膜厚３μｍでのヘイズ値が１０～２０％である請求項１０～１２のいずれかに記載のナフトールレッド。 The naphthol red according to any one of claims 10 to 12, which has a pigment concentration of 5% and a polyester resin coating film having a haze value of 10 to 20% at a film thickness of 3 µm.
  14. 　顔料濃度５％ポリエステル樹脂塗膜にて、膜厚３μｍでの彩度ｃ＊が６０以上である請求項１０～１３のいずれかに記載のナフトールレッド。 The naphthol red according to any one of claims 10 to 13, wherein a saturation c * at a film thickness of 3 µm is 60 or more in a polyester resin coating having a pigment concentration of 5%.
  15. 　粉体ｐＨが４．０～９．０の範囲にある請求項１０～１４のいずれかに記載のナフトールレッド。 The naphthol red according to any one of claims 10 to 14, wherein the powder pH is in the range of 4.0 to 9.0.
  16. 　請求項１～６及び１０～１５のいずれかに記載のナフトールレッドを含んでなる樹脂組成物。 A resin composition comprising the naphthol red according to any one of claims 1 to 6 and 10 to 15.
  17. 　請求項１～６及び１０～１５のいずれかに記載のナフトールレッドを含んでなる水系分散体。 An aqueous dispersion comprising the naphthol red according to any one of claims 1 to 6 and 10 to 15.
  18. 　請求項１～６及び１０～１５のいずれかに記載のナフトールレッドを含んでなる溶剤系分散体。 A solvent-based dispersion comprising the naphthol red according to any one of claims 1 to 6 and 10 to 15.
PCT/JP2015/083991 2014-12-05 2015-12-03 Naphthol red, manufacturing method therefor, and resin composition, aqueous dispersion, and solvent dispersion using said naphthol red WO2016088828A1 (en)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP2014247272A JP6809774B2 (en) 2014-12-05 2014-12-05 Naphthol red and its production method, resin composition using the naphthol red, aqueous dispersion and solvent-based dispersion
JP2014-247272 2014-12-05
JP2014247273A JP6551645B2 (en) 2014-12-05 2014-12-05 Naphthol red, resin composition using the naphthol red, aqueous dispersion, and solvent-based dispersion
JP2014247274A JP2016108452A (en) 2014-12-05 2014-12-05 Naphthol red, manufacturing method therefor, and resin composition, aqueous dispersion and solvent dispersion using naphthol red
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09157559A (en) * 1995-12-01 1997-06-17 Toyo Ink Mfg Co Ltd Ink jet recording fluid and its production
JP2000186241A (en) * 1998-12-22 2000-07-04 Sanyo Shikiso Kk Magenta ink for ink jet and its preparation
JP2004083907A (en) * 2002-08-08 2004-03-18 Dainippon Ink & Chem Inc Pigment composition and method for producing the same
JP2010195909A (en) * 2009-02-25 2010-09-09 Toyo Ink Mfg Co Ltd Pigment composition and inkjet printing ink

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09157559A (en) * 1995-12-01 1997-06-17 Toyo Ink Mfg Co Ltd Ink jet recording fluid and its production
JP2000186241A (en) * 1998-12-22 2000-07-04 Sanyo Shikiso Kk Magenta ink for ink jet and its preparation
JP2004083907A (en) * 2002-08-08 2004-03-18 Dainippon Ink & Chem Inc Pigment composition and method for producing the same
JP2010195909A (en) * 2009-02-25 2010-09-09 Toyo Ink Mfg Co Ltd Pigment composition and inkjet printing ink

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