US20020004588A1 - Monoazo metal complex compound containing composition and production method thereof - Google Patents

Monoazo metal complex compound containing composition and production method thereof Download PDF

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Publication number
US20020004588A1
US20020004588A1 US09/871,539 US87153901A US2002004588A1 US 20020004588 A1 US20020004588 A1 US 20020004588A1 US 87153901 A US87153901 A US 87153901A US 2002004588 A1 US2002004588 A1 US 2002004588A1
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metal complex
complex compound
monoazo metal
compound containing
containing composition
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Inventor
Akihiro Tada
Tohru Tsuruhara
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Orient Chemical Industries Ltd
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Orient Chemical Industries Ltd
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Assigned to ORIENT CHEMICAL INDUSTRIES, LTD. reassignment ORIENT CHEMICAL INDUSTRIES, LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: TADA, AKIHIRO, TSURUHARA, TOHRU
Publication of US20020004588A1 publication Critical patent/US20020004588A1/en
Priority to US10/706,426 priority Critical patent/US7342062B2/en
Abandoned legal-status Critical Current

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    • 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
    • C09B45/00—Complex metal compounds of azo dyes
    • C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
    • C09B45/14—Monoazo 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
    • C09B45/00—Complex metal compounds of azo dyes
    • C09B45/01—Complex metal compounds of azo dyes characterised by the method of metallisation
    • 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
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0096—Purification; Precipitation; Filtration
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/09—Colouring agents for toner particles
    • G03G9/0906—Organic dyes
    • G03G9/091—Azo dyes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/097—Plasticisers; Charge controlling agents
    • G03G9/09783—Organo-metallic compounds

Definitions

  • the present invention relates to a monoazo metal complex compound containing composition exhibiting almost no skin sensitization potential, a production method therefor, a charge control agent comprising the monoazo metal complex compound containing composition, a toner for developing electrostatic images that contains the charge control agent, a coloring agent containing said monoazo metal complex compound containing composition, and a colored thermoplastic composition containing said monoazo metal complex compound containing composition as a coloring agent.
  • Skin sensitization is a contact allergic reaction induced by skin contact with a simple chemical substance, a metal, or the like, and is a form of skin allergy (e.g., allergic contact dermatitis).
  • allergy is defined as an inflammation reaction due to antibody production by the living body.
  • Sensitization refers to the entry of an antigen in the living body to cause an antibody to be produced.
  • an emphasis has been placed on the potential of compounds for inducing skin sensitization in view of their safety.
  • Examples of reported cases wherein the safety of chemical substances posed a problem include a case of a chlorinated phosgene compound produced from a reaction of sodium hypochlorite and a yellow dye in a DC brand sweater [Hifu/Skin 1989;31(Supple. 7):24-33], a case of the grounder naphthol AS remaining on cloth in a cotton flannel night clothes [Eiseikagaku/Journal of Hygienic Chemistry 1986;32(5):359-67], a case of the grounder naphthol AS-D remaining on cloth in a cotton flannel night clothes [Environ. Dermatol.
  • Monoazo metal complex compounds are used for various applications, occupying an important position in the industry.
  • Major applications include dyes used to impart colors for writing inks, recording inks (including inkjet inks), leather, plastics, etc.; coloring matters based on absorption of ultraviolet light, near infrared light, infrared light, etc.; and charge control or enhancement agents used in toners for developing electrostatic images and resin powder paints for electrostatic painting.
  • monoazo metal complex compounds have impurity substances from starting materials, and byproducts and impurity substances associated with metallization, resulting in problems to be solved in skin sensitization assessed using the maximization method.
  • the object of the present invention is to provide a monoazo metal complex compound containing composition characterized by high safety to the human body and a low incidence of skin sensitization in skin sensitization tests, especially the maximization method, a production method therefor, a charge control agent comprising the monoazo metal complex compound containing composition, a toner for developing electrostatic images that contains the charge control agent, a coloring agent containing said monoazo metal complex compound containing composition, and a colored thermoplastic composition containing the monoazo metal complex compound containing composition as a coloring agent.
  • the monoazo metal complex compound containing composition of the present invention contains a monoazo metal complex compound, the incidence of skin sensitization in a skin sensitization potential test, especially in a skin sensitization potential test based on the maximization method, of said composition being not more than 20%.
  • This monoazo metal complex compound containing composition is desirably such that the purity of the aforementioned monoazo metal complex compound is not less than 90% as determined by high performance liquid chromatography.
  • the production method of the present invention for a monoazo metal complex compound containing composition is a method for producing the aforementioned monoazo metal complex compound containing composition and comprises a step for removing impurity substances using an alcoholic organic solvent.
  • the charge control agent of the present invention comprises the aforementioned monoazo metal complex compound containing composition, and the toner of the present invention for developing electrostatic images contains this charge control agent.
  • the coloring agent of the present invention contains the aforementioned monoazo metal complex compound containing composition
  • the colored thermoplastic resin composition of the present invention contains the aforementioned monoazo metal complex compound containing composition as a coloring agent.
  • the monoazo metal complex compound containing composition of the present invention possesses good characteristics of monoazo metal complex compounds and is excellently safe to the human body with the incidence of skin sensitization in skin sensitization potential tests, especially in a skin sensitization potential test based on the maximization method, being not more than 20%.
  • the monoazo metal complex compound containing composition of the present invention can be produced using the production method of the present invention.
  • the charge control agent of the present invention is excellently safe to the human body with the ratio of guinea pigs with skin sensitization signs found in skin sensitization potential tests, especially in a skin sensitization potential test based on the maximization method, being not more than 20%, possesses a practically satisfactory charge characteristic.
  • the charge control agent of the present invention is of high purity with impurity substances removed previously, it is sharp in charge amount distribution, high in charge amount uniformity, excellent in charge rise profile, low in environmental dependency, and when used in toner, it is excellent in durability in multiple repeated use of toner, and does not adversely affect toner fixability and offset quality.
  • the toner of the present invention for developing electrostatic images contains the charge control agent of the present invention, it is excellently safe to the human body, possesses a practically satisfactory charge characteristic, is sharp in charge amount distribution, high in charge amount uniformity, excellent in charge rise profile, low in environmental dependency, excellent in durability in multiple repeated use, and good in fixability and offset quality.
  • the coloring agent of the present invention is excellently safe to the human body with the ratio of guinea pigs with skin sensitization signs found in skin sensitization potential tests, especially in a skin sensitization potential test based on the maximization method, being not more than 20%, possesses a practically satisfactory coloring characteristic.
  • the coloring agent of the present invention is of high purity with impurity substances removed previously, its solubility is very stable, it exhibits almost no transfer, such as bleeding due to impurity substances, its heat resistance and light fastness are excellent, and its fading is slow with almost no hue change during color fading.
  • the colored thermoplastic resin composition of the present invention contains as a coloring agent a monoazo metal complex compound containing composition that is excellently safe to the human body, is of high purity, and is good in dispersibility and/or solubility in thermoplastic resins, it is excellent in uniform colorability, light fastness, and heat resistance, and provides molded products with improved gloss and appearance.
  • FIG. 1 shows high performance liquid chromatography data for the monoazo metal complex compound obtained in Example 1.
  • FIG. 2 shows a TG/DTA chart of the monoazo metal complex compound obtained in Example 1.
  • FIG. 3 shows high performance liquid chromatography data for the monoazo metal complex compound obtained in Comparative Example 1.
  • FIG. 4 shows high performance liquid chromatography data for the monoazo metal complex compound obtained in Comparative Example 2.
  • FIG. 5 shows a TG/DTA chart of the monoazo metal complex compound obtained in Comparative Example 2.
  • FIG. 6 shows changes in the charge amounts of the toners of Examples 3 and 4 and Comparative Examples 3 and 4.
  • the monoazo metal complex compound containing composition (generally referred to as “monoazo metal complex compound”) of the present invention is characterized in that the incidence of skin sensitization in skin sensitization potential tests, especially in a skin sensitization potential test based on the maximization method, is not more than 20%.
  • the monoazo metal complex compound containing composition of the present invention possesses characteristics comparable to those of commercially available conventional monoazo metal complex compounds and can be used equivalently. In addition, it does not significantly affect the human body with a low incidence of skin sensitization in skin sensitization potential tests, especially in a skin sensitization potential test based on the maximization method.
  • Skin sensitization tests that can be used for the present invention include skin sensitization tests using adjuvants, such as the maximization test, the adjuvant and strip test, Freund's complete adjuvant test, the optimization test, and the split adjuvant test; and skin sensitization tests using no adjuvant, such as the Beuhler test, the Draize test, and the open epicutaneous test.
  • skin sensitization tests and simplified test methods based on the aforementioned test methods are also applicable. Providing high accuracy of sensitization measurement, the maximization test (maximization method) is particularly preferable.
  • a skin sensitization test based on the maximization method can typically be performed as described below.
  • a 1:1 mixture of Freund's complete adjuvant immunopotentiator
  • the test compound is injected intracutaneously for first induction.
  • 5% sodium lauryl sulfate (petrolatum base) is applied in an open state to increase the absorption of the test compound 7 days after the intracutaneous injection and is removed after 24 hours.
  • the test compound is then applied in a closed state to the open application site and removed after 48 hours.
  • test compound Two weeks after closed application of the test compound, the test compound is again applied to elicit the skin reaction; after 24 hours, the test compound is removed and the skin reaction status is examined. At least 10 guinea pigs are used for the treatment group and at least 5 for the control group; rating results are expressed as the ratio of guinea pigs with signs of skin sensitization by the test compound.
  • the production method of the present invention for a monoazo metal complex compound containing composition can comprise a step for removing impurity substances other than monoazo metal complex compounds using an alcoholic organic solvent, in, for example, the synthesis of a monoazo metal complex compound, or the purification of a monoazo metal complex compound.
  • Examples of the step for removing impurity substances other than monoazo metal complex compounds using an alcoholic organic solvent include, but are not limited to, the following.
  • the monoazo metal complex compound containing composition is dispersed in an alcoholic organic solvent; the resulting dispersion is stirred under heating and filtered, after which the cake filtered out is dried under reduced pressure.
  • a monoazo metal compound is synthesized in a non-alcoholic solvent and after the non-alcohol solvent is replaced with an alcoholic organic solvent, impurity substances are removed by filtration etc., followed by drying.
  • a monoazo metal compound is synthesized in an aqueous system and filtered, and the water in the thus-obtained wet cake is replaced with an alcoholic organic solvent, followed by drying with a warm wind.
  • a monoazo metal compound is synthesized in an alcoholic organic solvent, and impurity substances are removed by filtration etc., followed by drying.
  • Alcoholic organic solvents that can be used for the production method of the present invention for a monoazo metal complex compound containing composition include, for example, the following monohydric alcohols, polyhydric alcohols (glycols) and derivatives thereof and mixtures of two or more thereof.
  • alcohols such as methanol, ethanol, 1-propanol, 2-propanol, n-butanol, benzyl alcohol, 1-octanol, 2-octanol, and ⁇ -methylbenzyl alcohol, or derivatives thereof; and glycols such as ethylene glycol, diethylene glycol, propylene glycol, hexylene glycol, benzyl glycol, ethylene glycol monodibutyl ether, ethylene glycol monophenyl ether (phenyl glycol), diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol monophenyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl
  • the monoazo metal complex compound containing composition of the present invention is useful, provided that the monoazo metal complex compound is a compound of the following formula (1):
  • each of R 1 through R 4 and R 6 independently (whether identical or not) represents a hydrogen atom, a normal or branched alkyl group having 1 to 18 carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, undecyl, dodecyl), a normal or branched alkenyl group having 2 to 18 carbon atoms (e.g., vinyl, propenyl, butenyl), a sulfonamide group, a mesyl group, a sulfonic acid group, a hydroxy group, an alkoxy group having 1 to 18 carbon atoms (e.g., methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy), an acetylamino group, a benzoylamino group, a hal
  • R 7 represents a normal or branched alkyl group having 1 to 18 carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, undecyl, dodecyl) or an aryl group having 6 to 18 carbon atoms (e.g., phenyl, tolyl, xylyl, naphthyl);
  • R 5 represents a hydrogen atom, a halogen atom (e.g., Cl, Br, I), a nitro group, a carboxyl group, a normal or branched alkyl group having 1 to 18 carbon atoms (e.g., the same as those mentioned above), an alkenyl group having 2 to 18 carbon atoms (e.g., the same as those mentioned above), an alkoxy group having 1 to 18 carbon atoms (e.g., the same as those mentioned above), an aryl group having 6 to 18 carbon atoms (e.g., the same as those mentioned above), —COO—R 8 or
  • R 8 represents a normal or branched alkyl group having 1 to 18 carbon atoms (e.g., the same as those mentioned above) or an aryl group having 6 to 18 carbon atoms (e.g., the same as those mentioned above);
  • Y represents a hydrogen atom, a normal or branched alkyl group having 1 to 8 carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl), an alkoxy group having 1 to 5 carbon atoms (e.g., methoxy, ethoxy, propoxy, butoxy, pentyloxy), a nitro group, or a halogen atom (e.g., the same as those mentioned above);
  • a normal or branched alkyl group having 1 to 8 carbon atoms e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl
  • an alkoxy group having 1 to 5 carbon atoms e.g., methoxy, ethoxy, propoxy, butoxy, pentyloxy
  • m represents an integer from 1 to 3;
  • M represents a divalent or trivalent metal (e.g., Cr, Fe, Co, Ni, Cu, Ti, Al);
  • p 1 or 2;
  • (A) q+ represents H + , NH 4 + , a cation based on an alkali metal (Na, K, or the like), a cation based on an organic amine (aliphatic primary amine, aliphatic secondary amine, aliphatic tertiary amine, or the like), or a quaternary organic ammonium ion;
  • X represents 1 or 2.
  • the monoazo metal complex compound in the monoazo metal complex compound containing composition of the present invention is preferably such that (A) q+ in Formula (1) above is H + , whereby impurity substances that adversely affect the sensitization potential can be removed efficiently by controlling the alcohol solubility of the monoazo metal complex compound to minimize the loss of the monoazo metal complex compound.
  • the monoazo metal complex compound in the monoazo metal complex compound containing composition of the present invention is preferably such that R 2 is Cl;
  • each of R 1 and R 3 through R 5 is a hydrogen atom
  • R 6 is a hydrogen atom or a normal or branched alkyl group having 1 to 18 carbon atoms
  • M is Cr, Fe, or Cu
  • the production method of the present invention for a monoazo metal complex compound containing composition it is possible to produce the monoazo metal complex compound containing composition of the present invention, while remaining starting materials and impurity substances associated with monoazo dyes, byproducts and impurity substances associated with metallization of monoazo dyes, and other undesirable substances are removed efficiently.
  • naphthol AS products such as naphthol AS and naphthol AS-D, which are also used as coupling components of monoazo dyes, described with reference to the prior art above, can be removed so that a monoazo metal complex compound containing composition (generally referred to as “monoazo metal complex compound”) with almost no sensitizing potential is obtained.
  • the monoazo metal complex compound containing composition of the present invention is effective as a charge control agent.
  • it serves as a charge control agent such that the incidence of skin sensitization in skin sensitization potential tests, especially in a skin sensitization potential test based on the maximization method, is not more than 20%.
  • the charge control agent of the present invention possesses charge characteristics comparable to those of commercially available conventional charge control agents comprising monoazo metal complex compounds and can be used equivalently. In addition, it does not significantly affect the human body with a low incidence of skin sensitization in skin sensitization potential tests, especially in a skin sensitization potential test based on the maximization method.
  • the monoazo metal complex compound as the charge control agent of the present invention is a monoazo metal complex compound of high purity with impurity substances removed previously, it is sharper in charge amount distribution, higher in charge amount uniformity, better in charge rise profile (high in charge rise speed), lower in environmental dependency, and when used in toner, it is better in durability in multiple repeated use of toner, less influential on toner fixability and offset quality, and better in safety to the human body, as compared to commercially available conventional charge control agents comprising monoazo metal complex compounds.
  • the toner of the present invention for developing electrostatic images can comprise the charge control agent of the present invention, a resin, and a coloring agent.
  • the toner of the present invention for developing electrostatic images can serve well, as long as the charge control agent of the present invention is contained in an amount enabling the control of the toner charge.
  • Preferable amounts of the charge control agent of the present invention added are 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, of the aforementioned monoazo metal complex compound containing composition (charge control agent of the present invention), per 100 parts by weight of the resin.
  • useful resins include styrene resin, styrene-acrylic resin, styrene-butadiene resin, styrene-maleic acid resin, styrene-vinyl methyl ether resin, styrene-methacrylate copolymer, phenol resin, epoxy resin, polyester resin, polypropylene resin, and paraffin wax. These resins may be used singly or in blends of several kinds.
  • the toner of the present invention may incorporate various dyes or pigments as coloring agents.
  • useful dyes and pigments include the following. Specifically, there may be mentioned organic pigments such as Quinophthalone Yellow, Isoindolinone Yellow, Perinone Orange, Perylene Maroon, Rhodamine 6G Lake, Quinacridone Red, Rose Bengale, Copper Phthalocyanine Blue, Copper Phthalocyanine Green and diketopyrrolopyrrole pigments; inorganic pigments such as Carbon Black, Titanium White, Titanium Yellow, Ultramarine, Cobalt Blue and red iron oxide; various oil soluble dyes and disperse dyes such as azo dyes, quinophthalone dyes, anthraquinone dyes, phthalocyanine dyes, indophenol dyes and indoaniline dyes; and triarylmethane dyes and xanthene dyes modified with resins such as rosin, rosin-modified phenol, and rosin-modified
  • additives e.g., electroconductive particles, fluidity-improving agents and anti-image-peeling agents, can be added to the toner internally or externally.
  • the toner of the present invention for developing electrostatic images can, for example, be produced as described below.
  • a toner having a mean particle diameter of 1 to 15 ⁇ m can be obtained by thoroughly mixing a resin and a coloring agent as described above, and the charge control agent of the present invention, and, if necessary, a magnetic material, a fluidizing agent and other additives, using a ball mill or another mechanical mixer, subsequently kneading the mixture in a molten state using a hot kneader such as a heat roll, kneader or extruder, cooling and solidifying the mixture, then pulverizing the solid and classifying the resulting particles by size.
  • a hot kneader such as a heat roll, kneader or extruder
  • Other applicable methods include the method in which the starting materials other than the binder resin are dispersed in a binder resin solution and subsequently spray dried to yield the desired toner, and the polymerization method in which a given set of starting materials are mixed in a monomer to constitute a binder resin to yield an emulsified suspension, which is then polymerized to yield the desired toner.
  • the toner of the present invention for developing electrostatic images is used as a two-component developer
  • development can be achieved by the two-component magnetic brush developing process or the like using the toner of the present invention in mixture with carrier powder.
  • Usable carrier is not particularly limited. Any commonly known carrier can be used. Examples of usable carriers include iron powder, nickel powder, ferrite powder and glass beads about 50 to 200 ⁇ m in particle diameter, and such materials as coated with acrylate copolymer, styrene-acrylate copolymer, styrene-methacrylate copolymer, silicone resin, polyamide resin, ethylene fluoride resin or the like.
  • the toner of the present invention for developing electrostatic images is used as a one-component developer
  • an appropriate amount of a fine powder of a ferromagnetic material, such as iron powder, nickel powder or ferrite powder, may be added and dispersed in preparing the toner as described above.
  • the charge of the powder paint can be controlled or enhanced. Because a resin powder paint for electrostatic painting that contains the charge control agent of the present invention is excellent in heat resistance and good in charge enhancing characteristic, it exhibits high paint adhesion efficiency even without recovery and reuse (i.e. recycled use). Paint using the powder paint can be achieved using an electrostatic powder painting method such as the corona application method, the frictional charging method or the hybrid method.
  • a frictional charge providing element capable of providing a charge for a toner for developing electrostatic images, by coating the surface of a carrier, a cylindrical sleeve of a transportation member for a toner, a doctor blade or the like, with the monoazo metal complex compound containing composition of the present invention as a charge control agent, by dipping, spraying, brush application or the like.
  • This frictional charge providing element is capable of producing toner images of high quality comparable to that of initial images even after continuous copying because the monoazo metal complex compound containing composition used stably provides a positive charge for a toner.
  • this frictional charge providing element may also comprise a small amount of an auxiliary positive charge providing agent.
  • the monoazo metal complex compound containing composition of the present invention is used as an absorbent dye for ultraviolet light, visible light, infrared light, and the like. Specifically, it is used in dyes (coloring agents) for writing inks, recording inks (including inkjet inks), leather, plastics, etc, near infrared absorbent dyes. Because the monoazo metal complex compound containing composition of the present invention possesses a practically satisfactory coloring characteristic for a coloring agent, and because it is of high purity with impurity substances removed previously, its solubility is very stable, it exhibits almost no transfer, such as bleeding due to impurity substances, its heat resistance and light fastness are excellent, and its fading is slow with almost no hue change during color fading.
  • inks and dense solutions containing the monoazo metal complex compound containing composition of the present invention as a dye are excellently stable over time with no time-related thickening or dye deposition because the dye dissolution stability is good so that crystal deposition or dye association due to impurity substances does not occur.
  • the monoazo metal complex compound containing composition of the present invention is useful as, for example, a dye for coloring a thermoplastic resin composition.
  • a coloring agent for plastics especially as a coloring agent for plastic products used during a long time of direct contact with the human skin, e.g., plastic eyeglass frames, it is excellently harmless to the human body with almost no skin sensitizing potential as exhibited by conventional azo disperse dyes.
  • the colored thermoplastic resin composition of the present invention is excellent in uniform colorability, light fastness and heat resistance, and its molded product has improved gloss and appearance, because the monoazo metal complex compound containing composition of the present invention used as the coloring agent is of high purity and is good in dispersibility and/or solubility in thermoplastic resins.
  • thermoplastic resins for example, can be used for the colored thermoplastic resin composition of the present invention.
  • polyamide resin polyethylene resin, polypropylene resin, polyester resin (polyethylene terephthalate resin, polybutylene terephthalate resin, etc.), polyphenylene sulfide resin and polyether ether ketone resin.
  • polyamide resin polyethylene terephthalate resin, polybutylene terephthalate resin, etc.
  • polyphenylene sulfide resin polyether ether ketone resin.
  • thermoplastic resins polyamide resin, polyester resin (polyethylene terephthalate resin, polybutylene terephthalate resin, etc.) and polyphenylene sulfide resin are preferred.
  • These thermoplastic resins may be used singly or in combination of two or more kinds.
  • polyamide resins examples include nylon 6, nylon 66, nylon 46, nylon 11, nylon 12, nylon 69, nylon 610, nylon 612, nylon 96, amorphous nylon, nylon RIM, nylon MIX 6, and copolymers of two or more thereof, such as nylon 6/66 copolymer, nylon 6/66/610 copolymer, nylon 6/66/11/12 copolymer, and crystalline nylon/amorphous nylon copolymer.
  • the polyamide resin for the present invention may be a polymer alloy of polyamide resin and another synthetic resin.
  • Such alloys include polyamide/polyester alloy, polyamide/polyphenylene oxide alloy, polyamide/polycarbonate alloy, polyamide/polyolefin alloy, polyamide/styrene/acrylonitrile alloy, polyamide/acrylic acid ester alloy, and polyamide/silicone alloy. These polyamide resins may be used singly or in combination of two or more kinds.
  • the colored thermoplastic resin composition of the present invention may contain appropriate amounts of various fibrous reinforcing materials according to its use and purpose.
  • Any fibrous reinforcing material can be used for the colored thermoplastic resin composition and fiber-reinforced colored thermoplastic resin molded product of the present invention, as long as it can be used to reinforce conventional synthetic resins.
  • fibrous reinforcing materials include glass fiber, carbon fiber and various organic fibers.
  • glass fiber for example, its content is preferably set at 5 to 120% by weight relative to 100% by weight of the thermoplastic resin (preferably crystalline thermoplastic resin).
  • the glass fiber content is preferably 10 to 60% by weight, particularly preferably 20 to 50% by weight.
  • the colored thermoplastic resin composition of the present invention and the fiber-reinforced colored thermoplastic resin molded product of the present invention may be formulated with various commonly known additives to confer desired characteristics according to the objective.
  • additives include auxiliary colorants, modifiers, ultraviolet absorbents or light stabilizers, antioxidants, antibacterial/antifungal agents, flame retarders, inorganic fillers, dispersing agents, stabilizers, plasticizers, antistatic agents and elastomers for improved impact resistance.
  • Auxiliary colorants include, for example, inorganic pigments, organic pigments or organic dyes used in small amounts to enhance the coloring power, to improve the heat resistance and light fastness, or to adjust the color tone.
  • modifiers include silicon compounds such as amino-modified silicone oil and alkyl-modified silicone oil, and waxes.
  • ultraviolet absorbents or light stabilizers examples include benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, benzoate compounds, oxalide compounds, hindered amine compounds and niccolates.
  • antioxidants include phenol compounds, phosphorus compounds, sulfur compounds and thioether compounds.
  • antibacterial/antifungal agents examples include 2-(4′-thiazolyl)-benzimidazole, 10,10′-oxybisphenoxarsine, N-(fluorodichloromethylthio)phthalimide and bis(2-pyridylthio-1-oxide)zinc.
  • Examples of flame retarders include halogen containing compounds such as tetrabromobisphenol A derivatives, hexabromodiphenyl ether and tetrabromophthalic anhydride; phosphorus containing compounds such as triphenyl phosphate, triphenyl phosphite, red phosphorus and ammonium polyphosphate; nitrogen containing compounds such as urea and guanidine; silicon containing compounds such as silicone oil, organic silane and aluminum silicate; and antimony compounds such as antimony trioxide and antimony phosphate.
  • halogen containing compounds such as tetrabromobisphenol A derivatives, hexabromodiphenyl ether and tetrabromophthalic anhydride
  • phosphorus containing compounds such as triphenyl phosphate, triphenyl phosphite, red phosphorus and ammonium polyphosphate
  • nitrogen containing compounds such as urea and guanidine
  • silicon containing compounds such as
  • inorganic fillers include glass flake, glass beads, silica, quartz, amorphous silicic acid, talc, magnesium carbonate, calcium carbonate, alumina, metal powder, kaolin, calcium silicate, mica and wollastonite.
  • the colored thermoplastic resin composition of the present invention can be prepared by formulating the starting materials by an optionally chosen method of formulation. Normally, it is preferable to mix these components as uniformly as possible.
  • a colored thermoplastic resin composition can be prepared by uniformly mixing all starting materials in a mechanical mixer such as a blender, a kneader, a banbury mixer, a roll or an extruder. Alternatively, it can be obtained by mixing some starting materials in a mechanical mixer, and subsequently adding the remaining components and uniformly mixing them.
  • a master batch of the colored thermoplastic resin composition of the present invention can be obtained by an optionally chosen method.
  • it can be obtained by mixing a thermoplastic resin (preferably a crystalline thermoplastic resin) as the master batch base, in a powder or pellet form, and the monoazo metal complex compound containing composition of the present invention as a coloring agent, in a mechanical mixer such as a tumbler or a super-mixer, and pelletizing or coarsely granulating the mixture by the hot melt method using an extruder, a batch kneader, a roll kneader, or the like.
  • a master batch can also be obtained by adding the monoazo metal complex compound containing composition of the present invention as a coloring agent to a thermoplastic resin for master batch remaining in a molten state after synthesis, then removing the solvent.
  • the colored thermoplastic resin composition of the present invention can be molded by various procedures in common use. For example, it can be molded from colored pellets using a molding machine such as an extruder, an injection molding machine or a roll mill. In addition, it can be molded by mixing in an appropriate mixer a thermoplastic resin, in a pellet or powder form, the monoazo metal complex compound containing composition of the present invention in a pulverized form as a coloring agent, and various additives used as necessary, and molding this mixture using a molding machine.
  • the monoazo metal complex compound containing composition of the present invention as a coloring agent to a monomer containing an appropriate polymerization catalyst, polymerize this mixture into a desired crystalline thermoplastic resin, and mold this resin by an appropriate method.
  • Molding can be achieved by any molding methods in common use, including injection molding, extrusion molding, compression molding, foaming molding, blow molding, vacuum molding, injection blow molding, rotational molding, calendering and solution casting
  • Examples 1 and 2 and Comparative Examples 1 and 2 concern the production of the monoazo metal complex compound containing composition of the present invention.
  • composition containing a monoazo metal complex compound 60 g was dispersed in 120 g of methanol and stirred at 63 ⁇ for 1 hour, after which it was cooled to 30 ⁇ and filtered through Toyo Filter Paper No. 2. The wet cake obtained was further washed with 20 g of methanol on filter paper and dried at 50 ⁇ under reduced pressure to yield 56.4 g of a purified black product (monoazo metal complex compound containing composition 1).
  • the purified monoazo metal complex compound (monoazo metal complex compound containing composition 1) was analyzed by high performance liquid chromatography and its purity was determined to be 94.3% (high performance liquid chromatography data presented in FIG. 1). The incidence of skin sensitization in a skin sensitization potential test based on the maximization method was 10%.
  • a TG/DTA chart of the purified monoazo metal complex compound (monoazo metal complex compound containing composition 1) is shown in FIG. 2.
  • Eluent Mixture of 80 parts by volume of acetonitrile, 1 part by volume of triethylamine, 3 parts by volume of acetic acid, and 16 parts by volume of water
  • the purified monoazo metal complex compound (monoazo metal complex compound containing composition 2) was analyzed by high performance liquid chromatography and its purity was determined to be 95.9%. The incidence of skin sensitization in a skin sensitization potential test based on the maximization method was 10%.
  • This non-purified monoazo metal complex compound (composition containing a monoazo metal complex compound) was analyzed by high performance liquid chromatography, and its purity was determined to be 82.8% (high performance liquid chromatography data presented in FIG. 3). The incidence of skin sensitization in a skin sensitization potential test based on the maximization method was 90%.
  • This black powder was analyzed by high performance liquid chromatography, and its purity was determined to be 27.8% (high performance liquid chromatography data presented in FIG. 4). The incidence of skin sensitization in a skin sensitization potential test based on the maximization method was 100%. A TG/DTA chart of this black powder is shown in FIG. 5.
  • Examples 3 and 4 and Comparative Examples 3 and 4 concern toners for developing electrostatic images that incorporate the monoazo metal complex compound containing composition of the present invention as a charge control agent.
  • Example 2 In the same manner as in Example 3, except that the charge control agent used in Example 3 was replaced with the monoazo metal complex compound containing composition 2 obtained in Example 2, a toner was obtained, a developer was prepared, and the amount of blowoff charges was determined. The amount of saturated charges was determined to be ⁇ 54.6 ⁇ C/g. The results of determination are shown in Table 2 and FIG. 6.
  • Example 3 In the same manner as in Example 3, except that the charge control agent used in Example 3 was replaced with the non-purified monoazo metal complex compound (composition containing a monoazo metal complex compound) obtained in Comparative Example 1, a toner was obtained and a developer was prepared. When this developer was used to repeatedly form images, the charge rise profile, charge stability, and sustainability were good, the image density was stable from the initial time to completion of continuous copying, and high-quality black images with no fogging etc. were obtained. When the amount of blowoff charges was determined in the same manner as in Example 3, the amount of saturated charges was determined to be ⁇ 54.1 ⁇ C/g. The results of determination are shown in Table 2 and FIG. 6.
  • Example 2 In the same manner as in Example 3, except that the charge control agent used in Example 3 was replaced with the methanol-soluble black powder (composition containing a monoazo metal complex compound) obtained in Comparative Example 2, a toner was obtained and a developer was prepared. When this developer was used to repeatedly form images, fogging occurred and no satisfactory images were obtained with density reduction as compared to initial images. When the amount of blowoff charges was determined in the same manner as in Example 3, the amount of saturated charges was determined to be ⁇ 38.0 ⁇ C/g. The results of determination are shown in Table 2 and FIG. 6. TABLE 2 Amount of saturated charges after toner Toner Charge control agent formation ( ⁇ C/g) Example 3 Example 1 55.7 Example 4 Example 2 54.6 Comparative Example 3 Comparative Example 1 54.1 Comparative Example 4 Comparative Example 2 38.0
  • Examples 5 and 7 and Comparative Examples 5 and 6 concern colored polyamide resin compositions that incorporate the monoazo metal complex compound containing composition of the present invention as a dye.
  • This mixture was kneaded in a molten state at 300 ⁇ using a vent type extruding machine (produced by Enpura Sangyo, trade name: E30SV) and treated by a conventional method to yield colored pellets, which were vacuum-dried at 120 ⁇ for 6 hours.
  • a vent type extruding machine produced by Enpura Sangyo, trade name: E30SV
  • test piece was prepared at 280 to 300 ⁇ by an ordinary method using an injection molding machine (produced by Kawaguchi Tekko, trade name: KM-50C). A reddish black molded test piece with good compatibility between the resin and the dye [48 ⁇ 86 ⁇ 3 (mm)] was obtained.
  • test piece was examined visually under standard light C (JIS L0804) to evaluate its coloring condition.
  • test pieces rated lower are judged to have greater discoloration and fading.
  • Light fastness test conditions with Sunshine xenon long-life weather meter [Setting item] [Phase 1] [Phase 2] Irradiance (Wm/2) (E) 70 70 Black standard temperature ( ⁇ ) 63 50 Rainfall test No Yes Humidity (%) 60 — Time (min) 120 18
  • This mixture was kneaded in a molten state at 300 ⁇ using a vent type extruding machine (produced by Enpura Sangyo, trade name: E30SV) and treated by a conventional method to yield colored pellets, which were vacuum-dried at 120 ⁇ for 6 hours.
  • a vent type extruding machine produced by Enpura Sangyo, trade name: E30SV
  • a test piece was prepared at 280 to 300 ⁇ with the pellets by an ordinary method using an injection-molding machine (produced by Kawaguchi Tekko, trade name: KM50-C). A reddish black molded test piece with good compatibility between the resin and the dye [48 ⁇ 86 ⁇ 3 (mm)] was obtained.
  • Example 5 In the same manner as in Example 5, except that the monoazo metal complex compound containing composition 1 in Example 5 was replaced with 30 g of the non-purified monoazo metal complex compound (composition containing a monoazo metal complex compound) obtained in Comparative Example 1, a uniformly colored reddish black molded test piece [48 ⁇ 86 ⁇ 3 (mm)] was obtained.

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JP4344580B2 (ja) * 2003-10-15 2009-10-14 オリヱント化学工業株式会社 荷電制御剤の製造方法
KR100590853B1 (ko) * 2004-03-12 2006-06-19 오리엔트 가가쿠 고교 가부시키가이샤 레이저광 투과성 조성물 및 레이저 용착 방법
WO2008133241A1 (ja) * 2007-04-23 2008-11-06 Nippon Kayaku Kabushiki Kaisha モノアゾ金属錯体、アゾ型顔料分散剤およびこれを含んだ顔料組成物
JP5252180B2 (ja) * 2008-01-09 2013-07-31 株式会社リコー 静電荷像現像用トナー及び画像形成方法
JP5187326B2 (ja) * 2010-02-24 2013-04-24 東洋インキＳｃホールディングス株式会社 アゾ化合物、アゾ色素、および該アゾ化合物又は該アゾ色素を含む着色組成物及び着色物
KR101590812B1 (ko) 2013-05-21 2016-02-02 제일모직주식회사 컬러필터용 감광성 수지 조성물 및 이를 이용한 컬러필터
CN103242673A (zh) * 2013-05-22 2013-08-14 南通市争妍颜料化工有限公司 溶剂黑b的生产工艺
CN106397465B (zh) * 2015-07-29 2019-02-22 广西新晶科技有限公司 偶氮金属络合物、及其电荷控制剂应用和含有它的色调剂

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