WO2022255135A1 - フタロシアニン化合物 - Google Patents

フタロシアニン化合物 Download PDF

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Publication number
WO2022255135A1
WO2022255135A1 PCT/JP2022/021042 JP2022021042W WO2022255135A1 WO 2022255135 A1 WO2022255135 A1 WO 2022255135A1 JP 2022021042 W JP2022021042 W JP 2022021042W WO 2022255135 A1 WO2022255135 A1 WO 2022255135A1
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Prior art keywords
compound
mol
atom
group
iie
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PCT/JP2022/021042
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English (en)
French (fr)
Japanese (ja)
Inventor
シオンワン フー
博 江波戸
宗矩 櫻井
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DIC Corp
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DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Application filed by DIC Corp, Dainippon Ink and Chemicals Co Ltd filed Critical DIC Corp
Priority to CN202280028724.XA priority Critical patent/CN117222709A/zh
Priority to EP22815886.1A priority patent/EP4349923A4/en
Priority to JP2023525731A priority patent/JP7448093B2/ja
Publication of WO2022255135A1 publication Critical patent/WO2022255135A1/ja
Priority to US18/524,313 priority patent/US20240116953A1/en
Anticipated expiration legal-status Critical
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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
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/08—Copper compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
    • 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
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
    • 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
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/30—Metal-free phthalocyanines
    • C09B47/305—Metal-free phthalocyanines prepared by demetallizing metal Pc 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
    • C09B61/00—Dyes of natural origin prepared from natural sources, e.g. vegetable sources
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs

Definitions

  • the present invention relates to phthalocyanine compounds.
  • Phthalocyanine is an excellent pigment that exhibits a blue to green hue and has a wide range of uses.
  • phthalocyanines are generally synthesized from phthalic anhydride, phthalic acid or phthalonitrile. Synthetic approaches using phthalimide or 1,3-diiminoisoindoline are also available but less common. Since the types of phthalic acid derivatives, which are the starting materials for phthalocyanine synthesis, are limited, the derivatization method of the final product, phthalocyanine, is also limited. Therefore, industrially, phthalocyanines are generally produced without functional groups.
  • the functional group that binds to the phthalocyanine skeleton is very important because it can fine-tune the hue through its electron-donating and electron-withdrawing properties.
  • functionalized phthalocyanines also act as additives to control crystal growth during pigment formation. Because of this importance, methods have been developed to directly functionalize phthalocyanines. Particularly successful cases are the halogenation, sulfonation and imidization of phthalocyanines (US Pat. However, these methods still have the problem that the number and position of the functional groups cannot be controlled and the types of functional groups that can be used are very limited. Therefore, it is desired to develop a technique capable of controlling the number and positions of functional groups of phthalocyanine and introducing new functional groups.
  • the problem to be solved by the present invention is a phthalocyanine compound that can control the number and positions of various types of functional groups, can be produced from biomass raw materials, has performance equal to or higher than conventional ones, and can contribute to carbon neutrality. , and to provide a composition, pigment composition, printing ink, printed matter, laminate of printed matter, paint, painted matter, coloring composition for color filter, or color filter using the phthalocyanine compound.
  • the present inventors used a biomass-derived furan derivative and maleic anhydride as raw materials, obtained a DA intermediate by the Diels-Alder (DA) reaction, and obtained a DA intermediate.
  • the above problem can be solved by synthesizing a phthalic anhydride derivative by ring-opening dehydration of a phthalic anhydride derivative, synthesizing phthalocyanine using the phthalic anhydride derivative, and obtaining a phthalocyanine compound containing a radioactive carbon atom 14C .
  • the discovery led to the completion of the present invention.
  • the present invention includes the following aspects. [1] The following formulas (I), (II), (IA), (IIA), (IB), ( IIB ), (IC), (IIC), (ID), ( A compound selected from the group of compounds represented by IID), (IE), and (IIE).
  • R 1 to R 4 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyclohexyl group, or a phenyl group.
  • M represents a metal atom.
  • the metal atom represented by M is Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr
  • [4] The compound according to any one of [1] to [3], wherein all of R 1 to R 4 are hydrogen atoms.
  • [5] Formulas (I), (II), (IA), (IIA), (IB), (IIB), (IC), (IIC), (ID), and (IID) described in [1] A composition containing one or more compounds selected from the group of compounds represented by , (IE), or (IIE).
  • [6] A pigment composition containing the compound described in [1] or the composition described in [5].
  • [7] A printing ink containing the pigment composition described in [6].
  • [8] A printed matter printed with the printing ink according to [7].
  • [9] A laminate having the printed matter according to [8].
  • a color filter comprising the color filter coloring composition of [12].
  • a phthalocyanine compound that can control the number and positions of various types of functional groups, can be produced from biomass raw materials, has performance equal to or higher than conventional ones, and can contribute to carbon neutrality. .
  • FIG. 3 is a diagram showing the TEM observation results of the pigment of Comparative Example 1 before pigmentation.
  • 1 is a diagram showing the TEM observation results of the pigment of Comparative Example 1 after pigmentation.
  • FIG. 1 is a diagram showing a TEM observation result of the pigment of Example 1 before pigmentation.
  • FIG. 1 is a diagram showing a TEM observation result of the pigment of Example 1 after pigmentation.
  • FIG. 3 is a diagram showing the TEM observation results of the pigment of Example 2 before pigmentation.
  • FIG. 4 is a diagram showing the TEM observation results of the pigment of Example 2 after pigmentation.
  • the compounds of the invention contain the radioactive carbon atom 14C .
  • the compounds of the present invention have the following formulas (I), (II), (IA), (IIA), (IB), (IIB), (IC), (IIC), (ID), (IID), (IE ), and (IIE) (hereinafter also referred to as formulas (I) to (IIE)).
  • formulas (I) to (IIE) When the compound of the present invention is applied to printing inks, paints, colorants for color filters, etc., one or more compounds selected from the group of compounds represented by formulas (I) to (IIE) are used. It is preferably provided in the form of a containing composition.
  • one or more compounds selected from the group of compounds represented by compounds (I) and (II) are contained, and further compounds represented by formulas (IA), (IIA), (IB), (IIB), ( IC), (IIC), (ID), (IID), (IE), and (IIE) (hereinafter also referred to as formulas (IA) to (IIE)), or It is preferably provided in the form of a composition containing two or more.
  • Metal atoms represented by M are, for example, Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, In, Sn or Pb.
  • One or two or more metal atoms selected from the group may be mentioned.
  • R 1 to R 4 are more preferably hydrogen atoms.
  • the pMC (percent modern carbon) in the compounds represented by formulas (I) to (IIE) is preferably 20% or more, more preferably 40% or more, and even more preferably 60% or more. , 80% or more.
  • pMC percent modern carbon
  • R 1 to R 4 are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom, or a bromine atom, and are preferably a hydrogen atom or a carbon atom.
  • a linear or branched alkyl group having a number of 1 to 12, a chlorine atom, and a bromine atom are more preferable, and a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, and a bromine atom are more preferable, and a hydrogen atom and a bromine atom are more preferable. Atoms are particularly preferred.
  • M represents a metal atom
  • Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, In, Sn or Pb is preferred, Al, Fe, Cu and Zn are more preferred, and Cu and Zn are even more preferred.
  • the degree of biomass exhibited by compounds selected from the group of compounds represented by formulas (I) to (IIE) is, for example, 1% or more, 5% or more, 10% or more, and 15%. 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, 45% or more, 50% or more.
  • the biomass degree is, for example, more preferably 55% or more, more preferably 60% or more, more preferably 65% or more, and more preferably 70% or more.
  • the biomass degree is more preferably 75% or more, more preferably 80% or more, and even more preferably 85% or more.
  • it is particularly preferable that the degree of biomass is 90% or more, and particularly preferably 95% or more.
  • biomass refers to plants as an alternative energy source.
  • Biomass is mainly composed of two components: lignin and (hemi)cellulose. Both lignin and (hemi) cellulose are macromolecules, lignin is composed of aromatic monomers, and (hemi) cellulose is composed of 5-carbon sugars and 6-carbon sugars. In the above compounds, both lignin-derived raw materials and (hemi)cellulose-derived raw materials can be used as raw materials.
  • the degree of biomass refers to the content (% by mass) of biomass-derived carbon in the total carbon calculated by measurement according to ASTM-D6866-18.
  • Preferred embodiments of the compound represented by formula (I) include, for example, compounds represented by the following formulas (I-1) to (I-12).
  • R I has the same meaning as R 1 to R 4 above, and M has the same meaning as M above.
  • Examples of the compound represented by formula (I) include, but are not limited to, compounds represented by formulas (I-1) to (I-12-2) below.
  • Preferred embodiments of the compound represented by formula (I-1) include compounds represented by the following formulas (I-1-1) to (I-1-4).
  • Preferred embodiments of the compound represented by formula (II) include compounds represented by the following formulas (II-1) to (II-12).
  • R I has the same meaning as R 1 to R 4 above, and M has the same meaning as M above.
  • Examples of the compound represented by formula (II) include, but are not limited to, compounds represented by the following formulas (II-1) to (II-12-2).
  • Preferred embodiments of the compounds represented by formulas (IA), (IB), (IC), (ID) and (IE) include, for example, the following formulas (IA-1) to (IE-1) compound.
  • Compounds represented by formulas (IA-1-1) to (IE-1-4) include (IA-1-2), (IB-1-2), (IC-1-2), (ID -1-2) and (IE-1-2) are preferred. Among them, (IA-1-2) to (ID-1-2) are preferred, (IA-1-2) to (IC-1-2) are more preferred, and (IA-1-2) is even more preferred.
  • Preferred embodiments of the compounds represented by formulas (IIA), (IIB), (IIC), (IID) and (IIE) include, for example, the following formulas (IIA-1) to (IIE-1) compound.
  • the compounds represented by formulas (IIA-1) to (IIE-1) are preferably compounds represented by formulas (IIA-1) to (IID-1), and (IIA-1) to (IIC-1 ) is more preferable, and the compound represented by (IIA-1) is more preferable.
  • Pigment crystallization, resin dispersibility and hue can be controlled by the compounds represented by formulas (IA) to (IIE), and are selected from the group of compounds represented by formulas (I) to (IIE). It leads to high performance of a composition containing a compound (hereinafter also referred to as a phthalocyanine composition).
  • the compound selected from the group of compounds represented by formulas (IA) to (IIE) is preferably a compound selected from the group of compounds represented by (IA) to (IID), and (IA) to A compound selected from the compound group represented by (IIC) is more preferable, and a compound selected from the compound group represented by (IA) and (IIA) is more preferable.
  • a compound represented by formula (I) or (II) (also referred to as compound (I) or (II)) can be obtained by the method described below.
  • a compound represented by the following formula (PA-1) is obtained from the compound represented by the following formula (DA-1), and from the compound represented by the formula (PA-1) the formula (I) or ( A compound represented by II) can be obtained.
  • R 1 to R 4 have the same meaning as the above R 1 to R 4.
  • the compound represented by formula (DA-1) is not limited, but includes the following compounds (DA-1-1) to (DA-1-17).
  • the compound represented by formula (PA-1) is not limited, but includes the following compounds (PA-1-1) to (PA-1-17).
  • Any compound represented by the formula (DA-1) may be used as long as the reaction proceeds favorably, but the compound represented by the following formula (FR-1) may be reacted with maleic anhydride is preferred.
  • R 1 to R 4 have the same meaning as the above R 1 to R 4.
  • the compound represented by formula (FR-1) is not limited, but includes the following compounds (FR-1-1) to (FR-1-5).
  • any catalyst may be used as long as the reaction proceeds favorably, but it is preferable to use a catalyst.
  • Any catalyst may be used as long as the reaction proceeds favorably.
  • Hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, polyphosphoric acid, diphosphoric acid, trifluoroacetic acid, or A compound represented by the following formula (AC) is preferred.
  • X represents —OH, —ONa, —OK, —R 5 , R 5 has the same meaning as the above R 1 to R 4 , Y represents a sulfur atom or a phosphorus atom, Z represents a hydrogen atom, —COR 6 , —COH, or —CO—CF 3 , and R 6 has the same meaning as R 1 to R 4 above.
  • the amount of the catalyst is preferably 0.1 to 3000 mol%, preferably 0.5 to 2500 mol%, preferably 1 to 2000 mol%, and 5 to 1500 mol% with respect to the compound represented by formula (DA-1). preferably 10 to 1000 mol%, preferably 20 to 500 mol%, preferably 50 to 500 mol%, preferably 70 to 500 mol%, preferably 100 to 500 mol%, preferably 150 to 500 mol%, preferably 200 to 500 mol% , preferably 250 to 500 mol %, preferably 300 to 500 mol %.
  • the lower limit is preferably 0.1 mol% or more, preferably 0.5 mol% or more, preferably 1 mol% or more, preferably 5 mol% or more, preferably 10 mol% or more, preferably 20 mol% or more, preferably 50 mol% or more, and 70 mol. % or more, preferably 100 mol % or more, preferably 150 mol % or more, preferably 200 mol % or more, preferably 250 mol % or more, and preferably 300 mol % or more.
  • the upper limit is preferably 3000 mol% or less, preferably 2500 mol% or less, preferably 2000 mol% or less, preferably 1500 mol% or less, preferably 1000 mol% or less, and preferably 500 mol% or less. Any combination of these upper and lower limits can be used.
  • each of R 1 to R 4 preferably represents a hydrogen atom.
  • the maleic anhydride is preferably derived from biomass.
  • the compound represented by the formula (FR-1) is preferably derived from biomass. More preferably, both the maleic anhydride and the compound represented by the formula (FR-1) are derived from biomass.
  • the biomass content of the raw material used in the production method is preferably 1% or more, preferably 5% or more, preferably 10% or more, preferably 15% or more, preferably 20% or more, preferably 25% or more, and 30% or more. preferably 35% or more, preferably 40% or more, preferably 45% or more, preferably 50% or more, preferably 55% or more, preferably 60% or more, preferably 65% or more, preferably 70% or more, 75% or more is preferable, 80% or more is preferable, 85% or more is more preferable, 90% or more is still more preferable, and 95% or more is particularly preferable.
  • the biomass-derived maleic anhydride is obtained, for example, by cyclizing dehydration of maleic acid obtained by oxidizing FF or HMF obtained by the method described in Patent Document 4 or 5, or by direct oxidation. can also be obtained.
  • FF or HMF obtained by the method described in Patent Document 4 or 5 is subjected to an appropriate combination of decarbonylation reaction, reduction reaction, dehydration reaction, and the like. can be obtained by
  • Compound (DA-1) can be produced by subjecting compound (FR-1) and maleic anhydride to Diels-Alder reaction. Any reaction solvent may be used as long as it allows the reaction to proceed favorably, but chloroform, dioxane, ethyl acetate, alkylbenzene, toluene, xylene, and diethyl ether are preferred.
  • the reaction temperature may be any temperature as long as the reaction proceeds favorably, but is preferably -10 to 100°C, more preferably 0 to 80°C, further preferably 10 to 70°C, and 15 to 50°C. is particularly preferred.
  • the lower limit is preferably ⁇ 10° C. or higher, more preferably 0° C.
  • the upper limit is preferably 100°C or lower, more preferably 80°C or lower, still more preferably 70°C or lower, and particularly preferably 50°C or lower.
  • the reaction pressure may be any as long as the reaction proceeds suitably, but is preferably 0.1 to 5 MPa, more preferably 0.1 to 3 MPa, further preferably 0.1 to 1 MPa, and 0.1 to 0 0.5 MPa is particularly preferred.
  • the lower limit is preferably 0.1 MPa or more, preferably 0.2 MPa or more, preferably 0.3 MPa or more, and preferably 0.4 MPa or more.
  • the upper limit is preferably 5 MPa or less, preferably 3 MPa or less, preferably 1 MPa or less, preferably 0.9 MPa or less, preferably 0.8 MPa or less, preferably 0.7 MPa or less, preferably 0.6 MPa or less, and 0.5 MPa. The following are preferred.
  • Compound (PA-1) can be produced by subjecting compound (DA-1) obtained in Reaction A to a ring-opening dehydration reaction.
  • Any reaction solvent may be used as long as the reaction proceeds favorably, but water, acetonitrile, toluene, xylene, alkylbenzene, a mixed solvent thereof, or no solvent is preferred.
  • the reaction temperature may be any temperature as long as the reaction proceeds favorably, but is preferably 20 to 150.degree. C., more preferably 30 to 120.degree.
  • the lower limit is preferably 20°C or higher, preferably 25°C or higher, preferably 30°C or higher, preferably 35°C or higher, and preferably 40°C or higher.
  • the upper limit is preferably 150° C. or lower, preferably 140° C. or lower, preferably 130° C. or lower, preferably 120° C. or lower, preferably 110° C. or lower, and preferably 100° C. or lower.
  • a catalyst is preferably used for the above reaction. Any catalyst may be used as long as the reaction proceeds favorably.
  • X represents —OH, —ONa, —OK, —R 5 , R 5 has the same meaning as the above R 1 to R 4 , Y represents a sulfur atom or a phosphorus atom, Z represents a hydrogen atom, —COR 6 , —COH, or —CO—CF 3 , and R 6 has the same meaning as R 1 to R 4 above.
  • the amount of the catalyst is preferably 0.1 to 3000 mol%, preferably 0.5 to 2500 mol%, preferably 1 to 2000 mol%, and 5 to 1500 mol% with respect to the compound represented by formula (DA-1). is preferably 10 to 1000 mol%, preferably 20 to 500 mol%, preferably 50 to 500 mol%, preferably 70 to 500 mol%, preferably 100 to 500 mol%, preferably 150 to 500 mol%, preferably 200 to 500 mol% Preferably 250 to 500 mol %, preferably 300 to 500 mol %.
  • the lower limit is preferably 0.1 mol% or more, preferably 0.5 mol% or more, preferably 1 mol% or more, preferably 5 mol% or more, preferably 10 mol% or more, preferably 20 mol% or more, preferably 50 mol% or more, and 70 mol. % or more, preferably 100 mol % or more, preferably 150 mol % or more, preferably 200 mol % or more, preferably 250 mol % or more, and preferably 300 mol % or more.
  • the upper limit is preferably 3000 mol% or less, preferably 2500 mol% or less, preferably 2000 mol% or less, preferably 1500 mol% or less, preferably 1000 mol% or less, and preferably 500 mol% or less. Any combination of these upper and lower limits can be used.
  • Compound (I) can be produced by reacting compound (PA-1) obtained in Reaction B with urea and MX in the presence of a catalyst. Any reaction solvent may be used as long as it allows the reaction to proceed favorably, but solventless alkylbenzene is preferred.
  • the reaction temperature may be any temperature as long as the reaction proceeds favorably, but is preferably 100 to 250°C, preferably 110 to 240°C, preferably 120 to 230°C, preferably 130 to 220°C, and 140 to 210°C. °C, preferably 150 to 200°C.
  • the lower limit is preferably 100°C or higher, preferably 110°C or higher, preferably 120°C or higher, preferably 130°C or higher, preferably 140°C or higher, and preferably 150°C or higher.
  • the upper limit is preferably 250°C or lower, preferably 240°C or lower, preferably 230°C or lower, preferably 220°C or lower, preferably 210°C or lower, and preferably 200°C or lower.
  • M in the above MX represents a metal atom, which is Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, In, Sn or Pb.
  • Al, Fe, Cu and Zn are more preferred, and Cu and Zn are even more preferred.
  • X in the above MX represents a halogen atom, it is more preferably a chlorine atom.
  • Any catalyst may be used as long as it allows the reaction to proceed favorably, but a molybdenum catalyst is preferred, and ammonium molybdate (IV) tetrahydrate is more preferred.
  • Compounds represented by the following (i-1) to (i-5) can also be produced by this reaction.
  • R 1 to R 4 each independently have the same meaning as R 1 to R 4 in formula (I).
  • Compound (II) can be produced by demetallizing compound (I) obtained in Reaction C. Any demetallization reaction may be used as long as the reaction proceeds favorably. Examples thereof include the method described in Chemical Communication, 2009, 1970-1971.
  • the compounds represented by formulas (IA) to (IIE) can be obtained by producing a phthalocyanine composition by the method described below.
  • ⁇ Method for producing phthalocyanine composition> By optimizing the production method described in the section ⁇ Method for producing compound (I) or (II)>, one compound selected from the group of compounds represented by compounds (I) and (II) Alternatively, a composition containing two or more kinds and further containing one or more kinds selected from the group of compounds represented by formulas (IA) to (IIE) can be produced. Methods for producing compounds represented by formulas (IA), (IIA), (IB), (IIB), (IC), (IIC), (ID), (IID), (IE) or (IIE) are described below. described in
  • a compound represented by the following formula (PA-2) is obtained from the compound represented by the following formula (DA-2), and from the compound represented by the formula (PA-2), the formula (IA) of the present invention, ( IIA), (IB), (HB), (IC), (IIC), (ID), (IID), (IE) or (IIE) can be obtained.
  • R 1 to R 4 have the same meaning as the above R 1 to R 4.
  • R 1 to R 4 have the same meaning as the above R 1 to R 4.
  • the compound represented by formula (DA-2) is not limited, but includes the following compounds (DA-2-1) to (DA-2-7).
  • the compound represented by formula (PA-2) is not limited, but includes the following compounds (PA-2-1) to (PA-2-7).
  • the compound represented by the formula (DA-2) may be any compound as long as the reaction proceeds favorably, but the compound represented by the formula (FR-1) can be obtained by reacting maleic anhydride. is preferred. In this case, it is preferable to use the compound represented by the formula (FR-1) in an excess amount in molar ratio to maleic anhydride.
  • any reaction may be used as long as the reaction proceeds favorably, but it is preferable to use a catalyst.
  • Any catalyst may be used as long as the reaction proceeds favorably.
  • Hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, polyphosphoric acid, diphosphoric acid, trifluoroacetic acid, or A compound represented by the following formula (AC) is preferred.
  • X represents —OH, —ONa, —OK, —R 5 , R 5 has the same meaning as the above R 1 to R 4 , Y represents a sulfur atom or a phosphorus atom, Z represents a hydrogen atom, —COR 6 , —COH, or —CO—CF 3 , and R 6 has the same meaning as R 1 to R 4 above.
  • the amount of the catalyst is preferably 0.1 to 3000 mol%, preferably 0.5 to 2500 mol%, preferably 1 to 2000 mol%, and 5 to 1500 mol% with respect to the compound represented by formula (DA-2). preferably 10 to 1000 mol%, preferably 20 to 500 mol%, preferably 50 to 500 mol%, preferably 70 to 500 mol%, preferably 100 to 500 mol%, preferably 150 to 500 mol%, preferably 200 to 500 mol% , preferably 250 to 500 mol %, preferably 300 to 500 mol %.
  • the lower limit is preferably 0.1 mol% or more, preferably 0.5 mol% or more, preferably 1 mol% or more, preferably 5 mol% or more, preferably 10 mol% or more, preferably 20 mol% or more, preferably 50 mol% or more, and 70 mol. % or more, preferably 100 mol % or more, preferably 150 mol % or more, preferably 200 mol % or more, preferably 250 mol % or more, and preferably 300 mol % or more.
  • the upper limit is preferably 3000 mol% or less, preferably 2500 mol% or less, preferably 2000 mol% or less, preferably 1500 mol% or less, preferably 1000 mol% or less, and preferably 500 mol% or less. Any combination of these upper and lower limits can be used.
  • each of R 1 to R 4 preferably represents a hydrogen atom.
  • the maleic anhydride is preferably derived from biomass.
  • the compound represented by the formula (FR-1) is preferably derived from biomass. More preferably, both the maleic anhydride and the compound represented by the formula (FR-1) are derived from biomass.
  • R 1 to R 4 have the same meaning as the above R 1 to R 4.
  • a composition containing compounds (DA-1) and (DA-2) can be produced by subjecting compound (FR-1) and maleic anhydride to the Diels-Alder reaction.
  • Any reaction solvent may be used as long as it allows the reaction to proceed favorably, but chloroform, dioxane, ethyl acetate, alkylbenzene, toluene, xylene, and diethyl ether are preferred.
  • the reaction temperature may be any temperature as long as the reaction proceeds favorably, but is preferably -10 to 100°C, more preferably 0 to 80°C, further preferably 10 to 70°C, and 15 to 50°C. is particularly preferred.
  • the lower limit is preferably ⁇ 10° C.
  • the temperature is preferably 0 to 100°C, preferably 10 to 100°C, more preferably 15 to 100°C, still more preferably 20 to 100°C, particularly 25 to 100°C. preferable.
  • the lower limit is preferably 0°C or higher, preferably 10°C or higher, more preferably 15°C or higher, still more preferably 20°C or higher, and particularly preferably 25°C or higher.
  • -10 to 90°C is preferable, -10 to 80°C is preferable, -10 to 70°C is more preferable, -10 to 60°C is more preferable, -10 ⁇ 50°C is particularly preferred.
  • the upper limit is preferably 90°C or lower, preferably 80°C or lower, more preferably 70°C or lower, still more preferably 60°C or lower, and particularly preferably 50°C or lower.
  • the reaction pressure may be any as long as the reaction proceeds suitably, but is preferably 0.1 to 5 MPa, more preferably 0.1 to 3 MPa, further preferably 0.1 to 1 MPa, and 0.1 to 0 0.5 MPa is particularly preferred.
  • the lower limit is preferably 0.1 MPa or more, preferably 0.2 MPa or more, preferably 0.3 MPa or more, and preferably 0.4 MPa or more.
  • the upper limit is preferably 5 MPa or less, preferably 3 MPa or less, preferably 1 MPa or less, preferably 0.9 MPa or less, preferably 0.8 MPa or less, preferably 0.7 MPa or less, preferably 0.6 MPa or less, and 0.5 MPa. The following are preferred.
  • the lower limit is preferably 0.15 MPa or higher, more preferably 0.2 MPa or higher, even more preferably 0.25 MPa or higher, and particularly preferably 0.3 MPa or higher.
  • 0.1 to 3 MPa more preferably 0.1 to 1 MPa, even more preferably 0.1 to 0.5 MPa, and 0.1 to 0.4 MPa for suppressing the production of the compound (DA-2).
  • the upper limit is preferably 3 MPa or less, more preferably 1 MPa or less, still more preferably 0.5 MPa or less, and particularly preferably 0.4 MPa or less.
  • the production ratio of compound (DA-1) and compound (DA-2) can be controlled by changing the equivalents of compound (FR-1) and maleic anhydride.
  • any reaction may be used as long as it favorably progresses the reaction, but the equivalent of compound (FR-1) to maleic anhydride is 2.0 to 15.0. is preferred, 4.0 to 14.0 is more preferred, 6.0 to 13.0 is even more preferred, and 8.0 to 12.0 is particularly preferred.
  • the lower limit is preferably 2.0 or more, more preferably 4.0 or more, still more preferably 6.0 or more, and particularly preferably 8.0 or more.
  • the upper limit is preferably 15.0 or less, more preferably 14.0 or less, still more preferably 13.0 or less, and particularly preferably 12.0 or less.
  • any substance may be used as long as the reaction proceeds favorably, but the equivalent of the compound (FR-1) to maleic anhydride is 1.0 to 2.0. is preferred, 1.0 to 1.5 is more preferred, 1.0 to 1.4 is even more preferred, and 1.0 to 1.2 is particularly preferred.
  • the upper limit is preferably 2.0 or less, more preferably 1.5 or less, still more preferably 1.4 or less, and particularly preferably 1.2 or less.
  • a composition containing compounds (PA-1) and (PA-2) is produced by subjecting a composition containing compounds (DA-1) and (DA-2) obtained in Reaction A2 to a ring-opening dehydration reaction. can do.
  • Any reaction solvent may be used as long as the reaction proceeds favorably, but water, acetonitrile, toluene, xylene, alkylbenzene, a mixed solvent thereof, or no solvent is preferred.
  • the reaction temperature may be any temperature as long as the reaction proceeds favorably, but is preferably 20 to 150.degree. C., more preferably 30 to 120.degree.
  • the lower limit is preferably 20°C or higher, preferably 25°C or higher, preferably 30°C or higher, preferably 35°C or higher, and preferably 40°C or higher.
  • the upper limit is preferably 150° C. or lower, preferably 140° C. or lower, preferably 130° C. or lower, preferably 120° C. or lower, preferably 110° C. or lower, and preferably 100° C. or lower.
  • a catalyst is preferably used for the above reaction. Any catalyst may be used as long as the reaction proceeds favorably.
  • X represents —OH, —ONa, —OK, —R 5 , R 5 has the same meaning as the above R 1 to R 4 , Y represents a sulfur atom or a phosphorus atom, Z represents a hydrogen atom, —COR 6 , —COH, or —CO—CF 3 , and R 6 has the same meaning as R 1 to R 4 above.
  • the amount of the catalyst is preferably 0.1 to 3000 mol%, preferably 0.5 to 2500 mol%, and 1 to 2000 mol with respect to the total amount of the compounds represented by formulas (DA-1) and (DA-2). %, preferably 5 to 1500 mol%, preferably 10 to 1000 mol%, preferably 20 to 500 mol%, preferably 50 to 500 mol%, preferably 70 to 500 mol%, preferably 100 to 500 mol%, preferably 150 to 500 mol% is preferred, 200 to 500 mol % is preferred, 250 to 500 mol % is preferred, and 300 to 500 mol % is preferred.
  • the lower limit is preferably 0.1 mol% or more, preferably 0.5 mol% or more, preferably 1 mol% or more, preferably 5 mol% or more, preferably 10 mol% or more, preferably 20 mol% or more, preferably 50 mol% or more, and 70 mol. % or more, preferably 100 mol % or more, preferably 150 mol % or more, preferably 200 mol % or more, preferably 250 mol % or more, and preferably 300 mol % or more.
  • the upper limit is preferably 3000 mol% or less, preferably 2500 mol% or less, preferably 2000 mol% or less, preferably 1500 mol% or less, preferably 1000 mol% or less, and preferably 500 mol% or less. Any combination of these upper and lower limits can be used.
  • a compound selected from the group of compounds represented by formula (I) is produced by reacting the composition containing compounds (PA-1) and (PA-2) obtained in Reaction B2 with urea and MX in the presence of a catalyst.
  • a composition containing one or more compounds selected from the group of compounds represented by formulas (IA), (IB), (IC), (ID) and (IE) can manufacture things. Any reaction solvent may be used as long as it allows the reaction to proceed favorably, but solventless alkylbenzene is preferred.
  • the reaction temperature may be any temperature as long as the reaction proceeds favorably, but is preferably 100 to 250°C, preferably 110 to 240°C, preferably 120 to 230°C, preferably 130 to 220°C, and 140 to 210°C. °C, preferably 150 to 200°C.
  • the lower limit is preferably 100°C or higher, preferably 110°C or higher, preferably 120°C or higher, preferably 130°C or higher, preferably 140°C or higher, and preferably 150°C or higher.
  • the upper limit is preferably 250°C or lower, preferably 240°C or lower, preferably 230°C or lower, preferably 220°C or lower, preferably 210°C or lower, and preferably 200°C or lower.
  • M in the above MX represents a metal atom, which is Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, In, Sn or Pb.
  • Al, Fe, Cu and Zn are more preferred, and Cu and Zn are even more preferred.
  • X in the above MX represents a halogen atom, it is more preferably a chlorine atom.
  • Any catalyst may be used as long as it allows the reaction to proceed favorably, but a molybdenum catalyst is preferred, and ammonium molybdate (IV) tetrahydrate is more preferred.
  • Compounds represented by the following (i-1) to (i-5) can also be produced by this reaction.
  • R 1 to R 4 each independently have the same meaning as R 1 to R 4 in formula (I).
  • reaction D2>> Compounds represented by formulas (IA), (IB), (IC), (ID) and (IE) containing one or more compounds represented by formula (I) obtained in reaction C2
  • a composition containing one or more compounds selected from the group contains one or more compounds represented by the formula (II) by performing a demetallization reaction to obtain the compound represented by the formula (IIA) , (IIB), (IIC), (IID) and (IIE).
  • Any demetallization reaction may be used as long as the reaction proceeds favorably. Examples thereof include the method described in Chemical Communication, 2009, 1970-1971.
  • the content of the compounds represented by formulas (IA) to (IIE) in the composition obtained as described above is preferably 0.1 to 40% by weight, preferably 0.1 to 30% by weight. %, more preferably 0.1 to 20% by weight, even more preferably 0.1 to 15% by weight, particularly preferably 0.1 to 10% by weight.
  • the lower limit is preferably 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 1.0% by weight or more, and 1.5% by weight or more. is more preferable, and 2.0% by weight or more is particularly preferable.
  • the upper limit is preferably 40% by weight or less, preferably 30% by weight or less, more preferably 20% by weight or less, further preferably 15% by weight or less, and 10% by weight or less. is particularly preferred.
  • the compound represented by formula (I), (II) or (IA) to (IIE) produced by the above method is further purified by a known and commonly used method to obtain a compound represented by formula (I) or (II). It is also possible to extract only A compound represented by formula (I), (II) or (IA) to (IIE) produced by the above method, a compound represented by formula (I) or (II) isolated by the above purification, and a composition
  • the compounds contained therein can be further halogenated, sulfonated and imidated by known and commonly used methods.
  • the compounds of the present invention represented by formulas (I) to (IIE) obtained by the above method and containing a radioactive carbon atom 14 C have a small particle size and a fine particle size, as shown in the following examples. Since it is easy to disperse, it is possible to improve the dispersibility in the resin for dispersing the pigment. Moreover, since the compound of the present invention is obtained by the above production method, the number and position of various kinds of functional groups can be controlled, and the desired hue can be obtained. Furthermore, the compound of the present invention contains biomass-derived carbon, and contributes to reducing the environmental load by being carbon-neutral.
  • the compound of the present invention exhibits properties particularly as an organic pigment, and can be used more preferably by making the pigment particles finer.
  • Such treatments include, for example, an acid paste method, an acid slurry method, a dry milling method, a solvent method, a salt milling method, and the like, and one or more of these can be applied in combination.
  • the compound of the present invention may be used in combination with a coloring material such as an additional organic pigment, organic dye, or organic pigment derivative for the purpose of toning. These should be appropriately selected according to the above-mentioned uses, and depending on the uses, the compounds of the present invention may be used alone or in combination.
  • a coloring material that can be used in combination any one such as a known pigment dye may be used.
  • the compounds of the invention are applicable in a wide variety of applications.
  • it can be used as a pigment composition, and if necessary, it can be mixed with other resins, rubbers, additives, pigments, dyes, etc. to be used as a coating material for cosmetics, pharmaceuticals or agricultural chemicals, printing markers, stationery, writing instruments, printing inks, inkjet inks. , metal inks, paints, plastic colorants, color toners, color filters, organic semiconductor materials, and near-infrared absorbing agents for laser welding that make use of the strong near-infrared absorption.
  • An example of the above application is shown below.
  • the compounds of the invention can be used as cosmetics.
  • the cosmetics used are not particularly limited, and the compounds of the present invention can be used in various types of cosmetics.
  • the cosmetics may be of any type as long as they can effectively exhibit their functions.
  • the cosmetics may be lotions, cream gels, sprays and the like.
  • Examples of the cosmetics include skin care cosmetics such as face wash, makeup remover, lotion, serum, face pack, protective milky lotion, protective cream, whitening cosmetics, and UV protection cosmetics, foundation, white powder, makeup base, lipstick, eye makeup, Make-up cosmetics such as cheek rouge and nail enamel, hair care cosmetics such as shampoo, hair rinse, hair treatment, hair styling agents, permanent waving agents, hair dyes, and hair growth agents, body care cosmetics such as body wash cosmetics, deodorant cosmetics, and bath agents Cosmetics etc. can be mentioned.
  • the amount of the compound of the present invention used in the cosmetic can be appropriately set according to the type of cosmetic.
  • the content in the cosmetics is usually in the range of 0.1 to 99% by mass, and generally preferably in the range of 0.1 to 10% by mass.
  • the amount in makeup cosmetics intended for coloring is preferably in the range of 5 to 80% by mass, more preferably in the range of 10 to 70% by mass, and most preferably in the range of 20 to 60% by mass. is preferred.
  • the cosmetic may contain, in addition to the compound of the present invention, carriers, pigments, oils, sterols, amino acids, moisturizers, powders, colorants, pH adjusters, perfumes, which are acceptable as cosmetic components.
  • Essential oils cosmetic active ingredients, vitamins, essential fatty acids, sphingolipids, self-tanning agents, excipients, fillers, emulsifiers, antioxidants, surfactants, chelating agents, gelling agents, thickening agents, emollients, wetting agents.
  • Said cosmetics can be prepared by mixing the compounds of the present invention and other cosmetic ingredients.
  • cosmetics containing the compound of the present invention can be used in the same manner as ordinary
  • the compounds of the present invention can be used to produce low-viscosity inks with excellent fluidity, and are suitable as pigments for gravure printing inks and flexographic printing inks.
  • Ink consists of binder resin, solvent, pigment, and various additives.
  • binder resins include nitrocellulose resins, polyamide resins, polyurethane resins, and acrylic resins.
  • solvents examples include aromatic organic solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone and 3-heptanone, ethyl acetate, n-propyl acetate, isopropyl acetate and isobutyl acetate.
  • aromatic organic solvents such as toluene and xylene
  • ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone and 3-heptanone, ethyl acetate, n-propyl acetate, isopropyl acetate and isobutyl acetate.
  • Ester solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, alcohol solvents such as t-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl Ether, ethylene glycol mono-i-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-i-butyl ether, ethylene glycol mono-t-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono- n-propyl ether, propylene glycol mono-i-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-i-butyl ether, propylene glycol mono-t-butyl ether, ethylene glycol dimethyl ether
  • Additives include anionic, nonionic, cationic, and amphoteric surfactants, gum rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, maleated rosin, cured rosin, alkyd phthalate resin, etc. pigment derivatives, dispersants, wetting agents, adhesion aids, leveling agents, antifoaming agents, antistatic agents, trapping agents, antiblocking agents, wax components and the like.
  • the printing ink prepared as described above can be used for printing on paper, synthetic paper, thermoplastic resin films, plastic products, steel plates and the like. or as an ink for flexographic printing using a flexographic printing plate such as a resin plate.
  • the printing ink is obtained by once contacting and transferring the printing ink to a printing plate or printing pattern, then contacting only the ink again to the base material, and drying as necessary to obtain a printed matter.
  • the printed matter can also be used as a constituent element of a laminate with other base material or the like.
  • the compounds of the invention can be incorporated into paints as colorants.
  • Various resins such as acrylic resins, melamine resins, epoxy resins, polyester resins, polyurethane resins, polyamide resins, and phenol resins are used as paints.
  • Solvents used in paints include aromatic solvents such as toluene, xylene, and methoxybenzene; acetic ester solvents such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; Propionate solvents such as pionate, alcohol solvents such as methanol, ethanol, propanol, n-butanol, isobutanol, ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, methyl ethyl ketone, methyl isobutyl ketone , cyclohexanone and other ketone solvents, hexane and other aliphatic hydrocarbon solvents, N,N-dimethylformamide, ⁇ -butyrolactam, N-methyl-2-pyr
  • pigment additive and/or the pigment composition when dispersing or mixing the pigment additive and/or the pigment composition in a liquid resin to form a coating resin composition, conventional additives such as dispersants, fillers, and coatings Auxiliaries, desiccants, plasticizers and/or auxiliary pigments can be used. This is accomplished by dispersing or mixing each component, singly or some together, by collecting all components or adding them all at once.
  • Dispersers for dispersing the composition containing the compound of the present invention prepared according to the application as described above include a disper, a homomixer, a paint conditioner, a scandex, a bead mill, an attritor, a ball mill, a double roll, a triple Known dispersing machines such as rolls and pressure kneaders may be used, but are not limited to these.
  • Dispersion of the pigment composition is carried out by adding a resin and a solvent so as to obtain a viscosity that enables dispersion with these dispersers.
  • the high-concentration paint base after dispersion has a solid content of 5 to 20%, and is used as a paint by further mixing a resin and a solvent.
  • a coated article can be obtained by forming a coating film using the coating material thus prepared.
  • the compound of the present invention can be suitably used for inkjet inks, and can be suitably used for aqueous inkjet inks, particularly as an aqueous pigment dispersion liquid dispersed using a pigment dispersant or the like.
  • the water-based pigment dispersion is obtained by preparing a high-concentration water dispersion (pigment paste) of the condensed polycyclic organic pigment of the present invention, diluting it with a water-soluble solvent and/or water, and adding other additives as necessary. It can be prepared by adding agents.
  • the method of dispersing the compound of the present invention in the water-soluble solvent and/or water to obtain a pigment paste is not particularly limited, and a known dispersing method is preferably used.
  • a known pigment dispersant may be used to disperse in water, or a surfactant may be used.
  • the pigment dispersant is preferably an aqueous resin, and preferable examples thereof include polyvinyl alcohols, polyvinylpyrrolidones, urethane resins having anionic or cationic groups, and radical copolymers having anionic or cationic groups. Resin etc. are mentioned.
  • radical copolymer resins having anionic groups or cationic groups include acrylic resins such as acrylic acid-acrylic acid ester copolymers, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, Styrene-acrylic resins such as styrene-methacrylic acid-acrylic acid ester copolymer, styrene- ⁇ -methylstyrene-acrylic acid copolymer, styrene- ⁇ -methylstyrene-acrylic acid-acrylic acid ester copolymer, styrene- Examples include maleic acid copolymers, styrene-maleic anhydride copolymers, vinylnaphthalene-acrylic acid copolymers, and salts of the aqueous resins.
  • Compounds for forming salts of the copolymer include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, and diethylamine, ammonia, ethylamine, triethylamine, propylamine, isopropylamine, diethylamine, Propylamine, butylamine, isobutylamine, triethanolamine, diethanolamine, aminomethylpropanol, morpholine and the like.
  • the amount of the compound used to form these salts is preferably equal to or greater than the neutralization equivalent of the copolymer.
  • the following (1) to (3) can be shown.
  • the kneader is not particularly limited, and examples thereof include a Henschel mixer, a pressure kneader, a Banbury mixer, a planetary mixer and the like.
  • the stirring/dispersing device is not particularly limited, and examples thereof include an ultrasonic homogenizer, a high-pressure homogenizer, a paint shaker, a ball mill, a roll mill, a sand mill, a sand grinder, a dyno mill, a dispermat, an SC mill, and a nanomizer. One of these may be used alone, or two or more types of devices may be used in combination.
  • the amount of the condensed polycyclic organic pigment in the pigment paste is preferably 5 to 60% by mass, more preferably 10 to 50% by mass. If the amount of pigment is less than 5% by mass, coloring of the water-based ink prepared from the pigment paste is insufficient, and there is a tendency that sufficient image density cannot be obtained. On the other hand, if it exceeds 60% by mass, the dispersion stability of the pigment tends to be lowered in the pigment paste. Coarse particles cause nozzle clogging and deterioration of other image characteristics, so it is preferable to remove coarse particles by centrifugation, filtration, or the like before and after ink preparation.
  • the impurities may be removed by ion exchange treatment or ultrafiltration treatment, and then post-treatment may be performed.
  • Ionic substances such as cations and anions (bivalent metal ions, etc.) can be removed by ion exchange treatment, and impurities dissolved substances (residual substances during pigment synthesis, excess components in dispersion composition) can be removed by ultrafiltration treatment. , resin not adsorbed to the organic pigment, contaminants, etc.) can be removed.
  • a known ion exchange resin is used for the ion exchange treatment.
  • a known ultrafiltration membrane may be used, and either a normal type or a double capacity type may be used.
  • the pigment paste After the pigment paste is prepared, it is appropriately diluted and additives are added as necessary to obtain an aqueous pigment dispersion liquid according to the purpose.
  • a water-soluble solvent and/or water, an anionic group-containing organic polymer compound for the purpose of a binder, etc. are added, and a wetting agent is added as necessary to achieve desired physical properties. (dry inhibitor), penetrant, or other additives are added to prepare.
  • a centrifugation or filtration process may be added.
  • the viscosity is preferably 1 to 10 (mPa s)
  • the surface tension is preferably 20 to 50 (mN/m)
  • the ejection property as an inkjet ink is taken into consideration.
  • the pigment concentration is preferably 1 to 10% by mass.
  • the humectant is added for the purpose of preventing the ink from drying.
  • the content of the humectant in the ink for the purpose of preventing drying is preferably 3 to 50% by mass.
  • the wetting agent used in the present invention is not particularly limited, it is preferable to use a wetting agent that is miscible with water and has an effect of preventing clogging of the ink jet printer head.
  • glycerin ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol having a molecular weight of 2000 or less
  • propylene glycol dipropylene glycol, tripropylene glycol, 1,3-propylene glycol, isopropylene glycol, isobutylene glycol, 1,4-butane diol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, mesoerythritol, pentaerythritol, and the like.
  • the inclusion of propylene glycol and 1,3-butyl glycol is safe and has excellent effects on ink drying property and ejection performance.
  • the penetrant is added for the purpose of improving the permeability to the recording medium and adjusting the dot diameter on the recording medium.
  • Penetrants include lower alcohols such as ethanol and isopropyl alcohol, ethylene oxide adducts of alkyl alcohols such as ethylene glycol hexyl ether and diethylene glycol butyl ether, and propylene oxide adducts of alkyl alcohols such as propylene glycol propyl ether.
  • the surfactant is added to adjust ink properties such as surface tension.
  • Surfactants that can be added for this purpose are not particularly limited, and include various anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and the like. Among them, anionic surfactants and nonionic surfactants are preferred.
  • anionic surfactants include alkylbenzenesulfonates, alkylphenylsulfonates, alkylnaphthalenesulfonates, higher fatty acid salts, sulfuric acid ester salts of higher fatty acid esters, sulfonates of higher fatty acid esters, and higher alcohol ethers. Sulfuric acid ester salts and sulfonates, higher alkyl sulfosuccinates, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, etc.
  • nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, and glycerin fatty acid esters.
  • polyoxyethylene glycerin fatty acid ester polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, fatty acid alkylolamide, alkylalkanolamide, acetylene glycol, oxyethylene adduct of acetylene glycol, polyethylene glycol polypropylene glycol block copolymers, among others, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid Esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid alkylolamides, acetylene glycol, oxyethylene adducts of acetylene glycol, polyethylene glycol polypropylene glycol block copolymers are preferred.
  • surfactants include silicone-based surfactants such as polysiloxane oxyethylene adducts; fluorine-based surfactants such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and oxyethylene perfluoroalkyl ethers. spiculisporic acid, rhamnolipids, biosurfactants such as lysolecithin, and the like can also be used.
  • surfactants can be used singly or in combination of two or more.
  • the amount added is preferably in the range of 0.001 to 2% by mass, more preferably 0.001 to 1.5% by mass, and more preferably 0.001 to 1.5% by mass relative to the total mass of the ink. It is more preferably in the range of 01 to 1% by mass. If the amount of the surfactant added is less than 0.001% by mass, the effect of adding the surfactant tends not to be obtained. .
  • preservatives can be added as necessary.
  • viscosity modifiers pH modifiers
  • chelating agents plasticizers
  • antioxidants antioxidants
  • ultraviolet absorbers etc.
  • thermoplastic resins plastics for thermoforming such as injection molding and press molding, such as polyolefins such as polyethylene and polypropylene, and polyvinyl chloride resins, are used.
  • the compound can be used by kneading it into these resins by a conventionally known method.
  • thermoplastic resins such as polyester resins, polyamide resins, styrene resins and acrylic resins, which are solid at room temperature and have film-forming properties, are used as dispersing resins.
  • the toner for electrostatic image development produced using the compound of the present invention as a constituent component includes a one-component color magnetic toner containing a magnetic substance (a color toner for magnetic one-component development), a non-magnetic toner containing no magnetic substance, and a toner for developing an electrostatic charge image. It can be used as a component color toner (color toner for non-magnetic one-component development) or a color toner for a two-component color developer mixed with a carrier (color toner for two-component development).
  • the one-component color magnetic toner can be composed of, for example, colorants, binder resins, magnetic powders, charge control agents (CCA), and other additives such as release agents, in the same manner as those commonly used.
  • CCA charge control agents
  • release agents in the same manner as those commonly used.
  • the amount of the compound of the present invention used in the toner for developing an electrostatic charge image is not particularly limited, but it is preferably used in a proportion of 0.5 to 25 parts by weight with respect to 100 parts by weight of the binder resin. It is more preferable that the amount is 4 to 10 parts by mass with respect to 100 parts by mass of the binder resin in order to make the charging performance more remarkable.
  • thermoplastic resins any of the known and commonly used thermoplastic resins exemplified above can be used. Any of natural rubber, synthetic rubber, synthetic wax, etc. can be used.
  • the compound of the present invention can be used to form a pattern of green pixel portions of a color filter by a known method.
  • a coloring composition for a color filter (more specifically, a photosensitive composition for a green pixel portion of a color filter) containing the compound of the present invention and a photosensitive resin as essential components can be obtained. .
  • a photosensitive resin, a photopolymerization initiator, and an organic solvent that dissolves the resin are mixed as essential components.
  • a method of preparing a dispersion liquid using the compound of the present invention, an organic solvent and, if necessary, a dispersant, and then adding a photosensitive resin or the like thereto is generally used.
  • a yellow pigment can be used in the compound of the present invention used in the photosensitive composition for the green pixel portion of the color filter.
  • dispersants used as necessary include DISPERBYK (registered trademark) 130, 161, 162, 163, 170, LPN-6919, and LPN-21116 manufactured by BYK Chemie. Leveling agents, coupling agents, cationic surfactants, etc. can also be used together.
  • organic solvents examples include aromatic solvents such as toluene, xylene, and methoxybenzene; acetic acid ester solvents such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; and ethoxyethyl propionate.
  • alcohol solvents such as methanol and ethanol
  • ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether and diethylene glycol dimethyl ether
  • ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone
  • group hydrocarbon solvents N,N-dimethylformamide, ⁇ -butyrolactam, N-methyl-2-pyrrolidone, aniline, nitrogen compound solvents such as pyridine, lactone solvents such as ⁇ -butyrolactone, methyl carbamate and carbamic acid Carbamates such as a 48:52 mixture of ethyl, water, and the like.
  • the organic solvent propionate-based, alcohol-based, ether-based, ketone-based, nitrogen compound-based, lactone-based, and water-soluble polar solvents such as water are particularly suitable.
  • thermoplastic resins such as urethane resins, acrylic resins, polyamic acid resins, polyimide resins, styrene maleic acid resins, and styrene maleic anhydride resins.
  • Photopolymerizable monomers such as polyfunctional monomers such as triacrylate, pentaerythritol triacrylate, tris(2-hydroxyethyl)isocyanate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and the like.
  • photopolymerization initiators include acetophenone, benzophenone, benzyldimethylketal, benzoyl peroxide, 2-chlorothioxanthone, 1,3-bis(4′-azidobenzal)-2-propane, 1,3-bis(4′- azidobenzal)-2-propane-2'-sulfonic acid, 4,4'-diazidostilbene-2,2'-disulfonic acid and the like.
  • the thus-prepared photosensitive composition for a green pixel portion of a color filter is subjected to pattern exposure with ultraviolet rays through a photomask, and then the unexposed portion is washed with an organic solvent, alkaline water, or the like to form a color filter. can be done.
  • Biomass-derived maleic anhydride (24.01 g) was dissolved in diethyl ether (250 mL) in a reactor equipped with a stirrer under a nitrogen atmosphere. The reaction was carried out at 25 MPa for 18 hours. After that, the white crude substance was filtered off with a filter, washed with diethyl ether, and dried in vacuo to obtain a mixture (31.70 g) of compound (DA-1-1) and compound (DA-2-1). . The ratios of compound (DA-1-1) and compound (DA-2-1) were 97% and 0.94%.
  • Example 1 Synthesis of phthalocyanine compound (Pc-1) from mixture of compound (DA-1-1) and compound (DA-2-1) Reaction equipped with stirrer, thermometer, dropping funnel and cooling tube Acetic anhydride (21.0 g) and methanesulfonic acid (148.0 g) were added to a container and ice-cooled with stirring. A mixture (10.0 g) of the compound (DA-1-1) and the compound (DA-2-1) obtained in Synthesis Example 1 was slowly added dropwise to the reaction mixture. After stirring at room temperature for 2 hours, the temperature was raised to 80° C. and the mixture was further stirred for 4 hours. After cooling to room temperature, toluene (50 mL) was added.
  • the organic layer was separated, and the aqueous layer was re-extracted with toluene (50 mL ⁇ 2).
  • the obtained organic layers were combined, washed with water, saturated brine, and aqueous sodium hydrogencarbonate solution in that order, and after concentrating the solution, a white solid of a mixture of phthalic anhydride and 2,3-naphthalenedicarboxylic anhydride was obtained. was taken.
  • Petroleum-derived maleic anhydride 24.01 g was dissolved in diethyl ether (250 mL) in a reactor equipped with a stirrer under a nitrogen atmosphere, and biomass-derived furan (25.00 g) was added. The reaction was carried out at 25 MPa for 18 hours. After that, the white crude substance was filtered off with a filter, washed with diethyl ether, and dried in vacuo to obtain a mixture (32.54 g) of compound (DA-1-1) and compound (DA-2-1). . The ratios of compound (DA-1-1) and compound (DA-2-1) were 97% and 0.86%.
  • Example 2 Synthesis of phthalocyanine compound (Pc-2) from mixture of compound (DA-1-1) and compound (DA-2-1) Reaction equipped with stirrer, thermometer, dropping funnel and cooling tube Acetic anhydride (13.8 g) and methanesulfonic acid (73.9 g) were added to a container and cooled with ice while stirring. A mixture (5.0 g) of the compound (DA-1-1) obtained in Synthesis Example 2 and the compound (DA-2-1) was slowly added dropwise to the reaction mixture. After stirring at room temperature for 2 hours, the temperature was raised to 80° C. and the mixture was further stirred for 4 hours. After cooling to room temperature, toluene (30 mL) was added.
  • the organic layer was separated, and the aqueous layer was re-extracted with toluene (30 mL ⁇ 2).
  • the obtained organic layers were combined, washed with water, saturated brine and aqueous sodium hydrogencarbonate solution in that order, and after concentrating the solution, a white solid of a mixture of phthalic anhydride and 2,3-naphthalenedicarboxylic anhydride was obtained. was taken.
  • Pc-1 is 94.6% of the compound represented by the following formula (I-1-2) and 2.8% of the compound represented by the following formula (IA-1-2). found to contain. It was also found that Pc-2 contained 98.8% of the compound represented by the following formula (I-1-2).
  • the copper phthalocyanine compounds of the examples of the present invention can have a smaller particle size after pigmentation than the copper phthalocyanine compounds of the comparative examples. , the luminance can be improved, leading to higher performance.
  • the furan used in Synthesis Example 1 is derived from biomass, and the phthalocyanine compounds of Examples of the present invention can improve the degree of biomass.

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EP4574911A1 (en) * 2023-12-22 2025-06-25 Holland Colours N. V. Bio-sourced phthalocyanine complex, preparation and use thereof

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