WO2013069667A1 - 着色組成物及びインクジェット記録用インク - Google Patents
着色組成物及びインクジェット記録用インク Download PDFInfo
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- WO2013069667A1 WO2013069667A1 PCT/JP2012/078799 JP2012078799W WO2013069667A1 WO 2013069667 A1 WO2013069667 A1 WO 2013069667A1 JP 2012078799 W JP2012078799 W JP 2012078799W WO 2013069667 A1 WO2013069667 A1 WO 2013069667A1
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- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- LVWZTYCIRDMTEY-UHFFFAOYSA-N metamizole Chemical compound O=C1C(N(CS(O)(=O)=O)C)=C(C)N(C)N1C1=CC=CC=C1 LVWZTYCIRDMTEY-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000006626 methoxycarbonylamino group Chemical group 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000001005 nitro dye Substances 0.000 description 1
- 239000001006 nitroso dye Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000005499 phosphonyl group Chemical group 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical compound C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical class N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical group CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- MCSKRVKAXABJLX-UHFFFAOYSA-N pyrazolo[3,4-d]triazole Chemical class N1=NN=C2N=NC=C21 MCSKRVKAXABJLX-UHFFFAOYSA-N 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- QEIQICVPDMCDHG-UHFFFAOYSA-N pyrrolo[2,3-d]triazole Chemical group N1=NC2=CC=NC2=N1 QEIQICVPDMCDHG-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229940079839 sodium dehydroacetate Drugs 0.000 description 1
- 235000019259 sodium dehydroacetate Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- DSOWAKKSGYUMTF-GZOLSCHFSA-M sodium;(1e)-1-(6-methyl-2,4-dioxopyran-3-ylidene)ethanolate Chemical compound [Na+].C\C([O-])=C1/C(=O)OC(C)=CC1=O DSOWAKKSGYUMTF-GZOLSCHFSA-M 0.000 description 1
- FRTIVUOKBXDGPD-UHFFFAOYSA-M sodium;3-sulfanylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCS FRTIVUOKBXDGPD-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 125000005147 toluenesulfonyl group Chemical group C=1(C(=CC=CC1)S(=O)(=O)*)C 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000001043 yellow dye Substances 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- C09B67/006—Preparation of organic pigments
-
- 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
- C09B47/24—Obtaining compounds having —COOH or —SO3H radicals, or derivatives thereof, directly bound to the phthalocyanine radical
- C09B47/26—Amide radicals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
-
- 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
-
- 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
- C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
- C09B47/0678—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile having-COOH or -SO3H radicals or derivatives thereof directly linked to the skeleton
-
- 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
- C09B47/073—Preparation from isoindolenines, e.g. pyrrolenines
-
- 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
- C09B47/20—Obtaining compounds having sulfur atoms directly bound to the phthalocyanine skeleton
-
- 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
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
- C09B67/0034—Mixtures of two or more pigments or dyes of the same type
- C09B67/0035—Mixtures of phthalocyanines
-
- 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
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
-
- 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
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
Definitions
- the present invention relates to a coloring composition and an ink jet recording ink which have good fastness and high printing density and are excellent in storage stability over time.
- a material for forming a color image has been mainly used as an image recording material, and specifically, an ink jet recording material, a thermal transfer recording material, an electrophotographic recording material, a transfer halogen. Silver halide photosensitive materials, printing inks, recording pens and the like are actively used. Further, a color filter is used for recording and reproducing a color image in an imaging device such as a CCD in a photographing apparatus and in an LCD or PDP in a display.
- the ink jet recording method is rapidly spreading and further developing because of its low material cost, high speed recording, low noise during recording, and easy color recording.
- Inkjet recording methods include a continuous method in which droplets are continuously ejected and an on-demand method in which droplets are ejected in accordance with image information signals.
- ink for ink jet recording water-based ink, oil-based ink, or solid (melting type) ink is used.
- the solvent has good solubility or dispersibility, high-density recording is possible, hue is good, light, heat, in the environment Fast against active gases (NOx, ozone and other oxidizing gases, SOx, etc.), excellent fastness to water and chemicals, good fixability to image-receiving materials, and low bleeding. It is required that the ink has excellent storability, has no toxicity, has high purity, and can be obtained at low cost.
- Cyan dye skeletons used in such inks for ink jet recording include phthalocyanine, anthraquinone, and triphenylmethane, and phthalocyanine compounds with excellent hue and light fastness are used. In particular, since it does not have sufficient fastness to ozone and ink stability cannot be satisfied, improvement is desired.
- Phthalocyanine dyes represented by Direct Blue 87 or Direct Blue 199 which are currently widely used, and also described in the above publications, etc., are characterized by their excellent light resistance compared to magenta and yellow, but are soluble in dyes. In many cases, for example, a dissolution failure occurs at the time of manufacturing, resulting in a manufacturing trouble, or an insoluble material precipitates during product storage or use. In particular, the above-described ink jet recording has problems such as clogging of the print head and ejection failure due to poor ink storage stability such as precipitation of dye, leading to significant deterioration of the printed image.
- Patent Document 1 discloses a phthalocyanine dye having a specific sulfonyl group or sulfinyl group as a phthalocyanine dye that achieves both hue, light and ozone fastness. Further, in the phthalocyanine dye described in this document, the substitution position of the substituent is a ⁇ -position substitution type (the following general formula) rather than the ⁇ , ⁇ -position mixed type (the substitution position of the substitution group is not regular).
- R 1 to R 16 in (IV) are respectively in the 1st to 16th positions, specific sulfonyl groups at the 2nd and / or 3rd position, 6th or 7th position, 10th and / or 11th position, 14th and 15th position Or those having a sulfinyl group) are excellent in hue, light and ozone fastness.
- Patent Document 2 discloses an azaphthalocyanine dye having a sulfo group and a substituted sulfamoyl group as a phthalocyanine dye that achieves both hue, light and ozone fastness.
- the ozone fastness and the print density are not sufficiently compatible.
- the substitution position ratio ⁇ position positions 1, 4, 5, 8, 9, 12, 13 and 16
- ⁇ position (2, 3, 6, 7, (10th, 11th, 14th and 15th positions) ⁇ are adjusted in the molecule to control the association, thereby balancing the print density and the robustness. That is, both are in a trade-off relationship, and the other performance was not sufficient to satisfy one performance. Further, it was found that the ink fastness and the print density are not sufficiently compatible with each other even in the ink jet recording ink comprising only the ⁇ -substituted phthalocyanine dye, and there is room for further improvement in the print density.
- the aspect I of the present invention has been made in view of such circumstances, and an object thereof is to provide a coloring composition having good ozone gas fastness and a high printing density, and an ink jet recording ink.
- the aspect II of the present invention has been made in view of such circumstances, and an object thereof is to provide a coloring composition and ink jet recording ink that suppresses bronze gloss and has good ozone gas fastness and high printing density.
- the aspect III of the present invention has been made in view of such circumstances, and an object thereof is to provide a coloring composition and ink jet recording ink that suppresses bronze gloss and has good ozone gas fastness and high printing density. To do.
- the present inventors have found that the above trade-off relationship can be overcome by using a mixture of ⁇ -substituted phthalocyanine and ⁇ -substituted phthalocyanine, and have completed the present invention. Moreover, it turned out that the coloring composition of this invention is excellent in storage stability with time unexpectedly.
- the present inventors have found that by using a mixture of phthalocyanine having a specific structure and azaphthalocyanine having a specific substituent, the association can be suppressed and the trade-off relationship can be avoided, and the present invention is It came to be completed.
- the gray and black images prepared by combining the commercially available magenta ink and yellow ink using the coloring composition of the present invention as cyan ink are unexpectedly different from each other in light sources (for example, under fluorescent light and under sunlight). It turned out that it is excellent in light source dependency that it looks the same color visually.
- the present inventors have found that by using a mixture of a phthalocyanine having a specific structure and a phthalocyanine having a specific substituent, the association can be suppressed and the above trade-off relationship can be avoided, and the present invention has been completed. It came to do.
- the coloring composition of this invention is excellent in the storage stability with time of being hard to precipitate also in high concentration aqueous solution unexpectedly.
- Excellent storage stability over time is advantageous in terms of storage and transportation because the aqueous dye solution used as an ink-jet ink raw material can be adjusted at a high concentration, and when preparing ink-jet ink using a high-concentration dye aqueous solution.
- it is difficult to cause a density shift which is useful.
- the object of the present invention has been achieved by the following method.
- a phthalocyanine dye represented by the following general formula (1) and a phthalocyanine dye represented by the following general formula (I-2), the following general formula (II-2), or the following general formula (III-2) A coloring composition characterized by the above.
- R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group , Heterocyclic group, cyano group, hydroxyl group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, Alkoxycarbonylamino group, sulfonamido group, carbamoyl
- Z 1 , Z 2 , Z 3 and Z 4 are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group. Represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. However, at least one of Z 1 , Z 2 , Z 3 , and Z 4 has an ionic hydrophilic group as a substituent.
- M 1 represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.
- R 1 , R 4 , R 5 , R 8 , R 9 , R 12 , R 13 and R 16 are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group , Heterocyclic group, cyano group, hydroxyl group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, Alkoxycarbonylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, ary
- Z 5 , Z 6 , Z 7 and Z 8 are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group. Represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. However, at least one of Z 5 , Z 6 , Z 7 , and Z 8 has an ionic hydrophilic group as a substituent.
- M 2 represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.
- R 21 and R 22 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.
- R 23 represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.
- R 24 represents a substituted or unsubstituted hydrocarbon group.
- R 23 and R 24 may be bonded together with a nitrogen atom to form a substituted or unsubstituted heterocycle.
- x, y, and z each independently represent 0 or more and 4 or less.
- x + y + z is 1 or more and 4 or less.
- R 17 and R 18 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, substituted or unsubstituted An unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, A represents a divalent linking group, and adjacent R 17 , R 18 , and A are linked to each other.
- Y and Z may be independently a halogen atom, a hydroxyl group, a sulfonic acid group, a carboxyl group, an amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyloxy group.
- Z 5 , Z 6 , Z 7 and Z 8 in the phthalocyanine dye represented by the general formula (I-2) are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted group. Or the coloring composition as described in [1] characterized by representing an unsubstituted heterocyclic group.
- R 1 , R 4 , R 5 , R 8 , R 9 , R 12 , R 13 and R 16 in the phthalocyanine dye represented by the general formula (I-2) are hydrogen atoms [1 ] Or the coloring composition as described in [2].
- Z 5 , Z 6 , Z 7 , and Z 8 represent a substituted alkyl group, and at least one of the substituents of the alkyl group is a —SONHR group (provided that R Represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted phenyl group), [1] to [3].
- R Represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted phenyl group [1] to [3].
- the azaphthalocyanine dye represented by the general formula (II-2) is an azaphthalocyanine dye represented by the following general formula (II-3-1) or the general formula (II-3-2). Coloring composition.
- Each P independently represents a nitrogen atom or CH, and at least one P represents a nitrogen atom.
- R 21 and R 22 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.
- R 23 and R 24 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.
- x, y, and z each independently represent 0 or more and 4 or less.
- x + y + z is 1 or more and 4 or less.
- R 23 represents a hydrogen atom
- R 24 is represented by the following general formula (T1).
- L represents a single bond or a substituted or unsubstituted alkylene group.
- X represents independently a substituent selected from —OR 25 , —SR 25 , and —NR 25 R 26 , and R 25 and R 26 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted group Alternatively, it represents an unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, and at least one of R 25 and R 26 has an ionic hydrophilic group as a substituent.
- R 27 represents a hydrogen atom or a substituted or unsubstituted alkyl group.
- L represents a single bond or a substituted or unsubstituted alkylene group.
- R 29 , R 210 , and R 211 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group
- R 212 represents a substituted alkyl group, a substituted aryl group, or a substituted heterocyclic group, and is ionic It has at least one hydrophilic group as a substituent.
- R 27 represents a hydrogen atom or a substituted or unsubstituted alkyl group.
- each of R 27 and R 28 independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, A substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, A represents a divalent linking group, and adjacent R 27 , R 28 , and A are They may be linked to form a ring.
- R 29 , R 210 , and R 211 each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group
- R 212 represents a sulfonic acid group, a carboxyl group, a substituted alkyl group, a substituted aryl group, or a substituted hetero group.
- m and n are 1 to 3, and the sum of m and n is 2 to 4.
- R 1 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 in the phthalocyanine dye represented by the general formula (1) are hydrogen atoms [1] to [10]
- Z 1 , Z 2 , Z 3 and Z 4 in the phthalocyanine dye represented by the general formula (1) are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted group.
- a coloring composition and an ink jet recording ink having good ozone fastness, high printing density, and excellent storage stability with time.
- a coloring composition having good ozone fastness, high printing density, suppressing bronze gloss, realizing excellent hue, and excellent in light source dependency, and inkjet Recording ink is provided.
- a coloring composition and an ink jet having good ozone fastness, high printing density, suppressing bronze gloss, realizing excellent hue, and excellent storage stability over time. Recording ink is provided.
- Halogen atom for example, chlorine atom, bromine atom
- Specific examples of the above group include, for example, methyl, ethyl, propyl, isopropyl, t-butyl, 2-methanesulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl
- aryl group for example, phenyl, 4-t- Butylphenyl, 2,4-di-t-amylphenyl
- heteroatom for example, phenyl
- the coloring composition of the present invention is represented by a phthalocyanine dye represented by the following general formula (1) and the following general formula (I-2), the following general formula (II-2), or the following general formula (III-2). Phthalocyanine dyes.
- R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group , Heterocyclic group, cyano group, hydroxyl group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, Alkoxycarbonylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryl
- Z 1 , Z 2 , Z 3 and Z 4 are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group. Represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. However, at least one of Z 1 , Z 2 , Z 3 , and Z 4 has an ionic hydrophilic group as a substituent.
- M 1 represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.
- R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, or an alkenyl.
- Examples of the halogen atom represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 include a fluorine atom, a chlorine atom and a bromine atom.
- the alkyl group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an alkyl group having a substituent and an unsubstituted alkyl group.
- an alkyl group having 1 to 12 carbon atoms when a substituent is removed is preferable.
- the substituent include a hydroxyl group, an alkoxy group, a cyano group, and a halogen atom and an ionic hydrophilic group.
- alkyl group examples include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl and 4-sulfobutyl.
- the cycloalkyl group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes a cycloalkyl group having a substituent and an unsubstituted cycloalkyl group.
- the cycloalkyl group is preferably a cycloalkyl group having 5 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the cycloalkyl group include a cyclohexyl group.
- the alkenyl group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an alkenyl group having a substituent and an unsubstituted alkenyl group.
- an alkenyl group having 2 to 12 carbon atoms when a substituent is removed is preferable.
- the substituent include an ionic hydrophilic group.
- Examples of the alkenyl group include a vinyl group and an allyl group.
- the aralkyl group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an aralkyl group having a substituent and an unsubstituted aralkyl group.
- an aralkyl group having 7 to 12 carbon atoms when a substituent is removed is preferable.
- the substituent include an ionic hydrophilic group.
- the aralkyl group include a benzyl group and a 2-phenethyl group.
- the aryl group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an aryl group having a substituent and an unsubstituted aryl group.
- the aryl group is preferably an aryl group having 6 to 12 carbon atoms when the substituent is removed.
- the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkylamino group, and an ionic hydrophilic group.
- Examples of the aryl group include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl.
- the heterocyclic group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group.
- the heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group.
- the substituent include an ionic hydrophilic group.
- Examples of the heterocyclic group include a 2-pyridyl group, a 2-thienyl group and a 2-furyl group.
- the alkylamino group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an alkylamino group having a substituent and an unsubstituted alkylamino group.
- the alkylamino group is preferably an alkylamino group having 1 to 6 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylamino group include a methylamino group and a diethylamino group.
- the alkoxy group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an alkoxy group having a substituent and an unsubstituted alkoxy group.
- the alkoxy group excluding the substituent is preferably an alkoxy group having 1 to 12 carbon atoms.
- Examples of the substituent include an alkoxy group, a hydroxyl group, and an ionic hydrophilic group.
- Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a methoxyethoxy group, a hydroxyethoxy group, and a 3-carboxypropoxy group.
- the aryloxy group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an aryloxy group having a substituent and an unsubstituted aryloxy group.
- the aryloxy group is preferably an aryloxy group having 6 to 12 carbon atoms when a substituent is removed.
- the substituent include an alkoxy group and an ionic hydrophilic group.
- Examples of the aryloxy group include a phenoxy group, a p-methoxyphenoxy group, and an o-methoxyphenoxy group.
- the amide group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an amide group having a substituent and an unsubstituted amide group.
- the amide group is preferably an amide group having 2 to 12 carbon atoms when a substituent is removed.
- the substituent include an ionic hydrophilic group.
- Examples of the amide group include an acetamide group, a propionamide group, a benzamide group, and a 3,5-disulfobenzamide group.
- the arylamino group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an arylamino group having a substituent and an unsubstituted arylamino group.
- the arylamino group is preferably an arylamino group having 6 to 12 carbon atoms when a substituent is removed. Examples of the substituent include a halogen atom and an ionic hydrophilic group. Examples of the arylamino group include an anilino group and a 2-chloroanilino group.
- the ureido group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes a ureido group having a substituent and an unsubstituted ureido group.
- the ureido group is preferably a ureido group having 1 to 12 carbon atoms when a substituent is removed.
- the substituent include an alkyl group and an aryl group.
- Examples of the ureido group include a 3-methylureido group, a 3,3-dimethylureido group, and a 3-phenylureido group.
- the sulfamoylamino group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes a sulfamoylamino group having a substituent and an unsubstituted sulfamoylamino group.
- a group is included.
- the substituent include an alkyl group.
- Examples of the sulfamoylamino group include N, N-dipropylsulfamoylamino group.
- the alkylthio group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an alkylthio group having a substituent and an unsubstituted alkylthio group.
- the alkylthio group is preferably an alkylthio group having 1 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylthio group include a methylthio group and an ethylthio group.
- the arylthio group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an arylthio group having a substituent and an unsubstituted arylthio group.
- the arylthio group is preferably an arylthio group having 6 to 12 carbon atoms when a substituent is removed.
- the substituent include an alkyl group and an ionic hydrophilic group.
- Examples of the arylthio group include a phenylthio group and a p-tolylthio group.
- the alkoxycarbonylamino group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an alkoxycarbonylamino group having a substituent and an unsubstituted alkoxycarbonylamino group. It is.
- the alkoxycarbonylamino group is preferably an alkoxycarbonylamino group having 2 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonylamino group include an ethoxycarbonylamino group.
- the sulfonamide group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes a sulfonamide group having a substituent and an unsubstituted sulfonamide group.
- the sulfonamide group is preferably a sulfonamide group having 1 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the sulfonamide group include methanesulfonamide, benzenesulfonamide, and 3-carboxybenzenesulfonamide.
- the carbamoyl group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes a carbamoyl group having a substituent and an unsubstituted carbamoyl group.
- the substituent include an alkyl group.
- the carbamoyl group include a methylcarbamoyl group and a dimethylcarbamoyl group.
- the sulfamoyl group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes a sulfamoyl group having a substituent and an unsubstituted sulfamoyl group.
- the substituent include an alkyl group and an aryl group.
- the sulfamoyl group include a dimethylsulfamoyl group, a di- (2-hydroxyethyl) sulfamoyl group, and a phenylsulfamoyl group.
- the alkoxycarbonyl group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an alkoxycarbonyl group having a substituent and an unsubstituted alkoxycarbonyl group.
- the alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.
- the heterocyclic oxy group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes a heterocyclic oxy group having a substituent and an unsubstituted heterocyclic oxy group. It is.
- the heterocyclic oxy group is preferably a heterocyclic oxy group having a 5-membered or 6-membered heterocyclic ring.
- the substituent include a hydroxyl group and an ionic hydrophilic group.
- Examples of the heterocyclic oxy group include a 2-tetrahydropyranyloxy group.
- the azo group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an azo group having a substituent and an unsubstituted azo group.
- Examples of the azo group include a p-nitrophenylazo group.
- the acyloxy group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an acyloxy group having a substituent and an unsubstituted acyloxy group.
- the acyloxy group is preferably an acyloxy group having 1 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.
- the carbamoyloxy group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes a carbamoyloxy group having a substituent and an unsubstituted carbamoyloxy group.
- the substituent include an alkyl group.
- the carbamoyloxy group include an N-methylcarbamoyloxy group.
- the silyloxy group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes a silyloxy group having a substituent and an unsubstituted silyloxy group.
- the substituent include an alkyl group.
- the silyloxy group include a trimethylsilyloxy group.
- the aryloxycarbonyl group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an aryloxycarbonyl group having a substituent and an unsubstituted aryloxycarbonyl group. It is.
- the aryloxycarbonyl group is preferably an aryloxycarbonyl group having 7 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.
- the aryloxycarbonylamino group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an aryloxycarbonylamino group having a substituent and an unsubstituted aryloxycarbonylamino A group is included.
- the aryloxycarbonylamino group is preferably an aryloxycarbonylamino group having 7 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group.
- the imide group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an imide group having a substituent and an unsubstituted imide group.
- Examples of the imide group include an N-phthalimide group and an N-succinimide group.
- the heterocyclic thio group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes a heterocyclic thio group having a substituent and an unsubstituted heterocyclic thio group. It is.
- the heterocyclic thio group preferably has a 5-membered or 6-membered heterocyclic ring. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic thio group include a 2-pyridylthio group.
- the phosphoryl group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes a phosphoryl group having a substituent and an unsubstituted phosphoryl group.
- Examples of the phosphoryl group include a phenoxyphosphoryl group and a phenylphosphoryl group.
- the acyl group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes an acyl group having a substituent and an unsubstituted acyl group.
- the acyl group is preferably an acyl group having 1 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the acyl group include an acetyl group and a benzoyl group.
- the ionic hydrophilic group represented by R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 includes a sulfo group, a carboxyl group, a quaternary ammonium group, and the like.
- a carboxyl group and a sulfo group are preferable, and a sulfo group is particularly preferable.
- the carboxyl group and the sulfo group may be in a salt state, and examples of the counter ion forming the salt include alkali metal ions (eg, sodium ion, potassium ion) and organic cations (eg, tetramethylguanidinium ion). ) Is included.
- R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 are hydrogen atom, halogen atom, alkyl group, aryl group, cyano group, alkoxy group, amide group, ureido, among others Group, sulfonamido group, carbamoyl group, sulfamoyl group and alkoxycarbonyl group are preferable, hydrogen atom, halogen atom and cyano group are particularly preferable, and hydrogen atom is most preferable.
- Z 1 , Z 2 , Z 3 , and Z 4 are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, It represents a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
- at least one of Z 1 , Z 2 , Z 3 , and Z 4 has an ionic hydrophilic group as a substituent. Examples of the substituent include the substituents described in the above substituent group A.
- the alkyl group represented by Z 1 , Z 2 , Z 3 , and Z 4 includes an alkyl group having a substituent and an unsubstituted alkyl group.
- the alkyl group is preferably an alkyl group having 1 to 12 carbon atoms when a substituent is removed.
- substituent group a hydroxyl group, an alkoxy group, a cyano group, an alkylamino group (RNH-, RR'N-), a carbamoyl group (-CONHR), a sulfamoyl group (-SO 2 NHR, -SO 2 NRR ') Sulfonylamino group (—NHSO 2 R), —SONHR group, —SONRR ′ group, halogen atom and ionic hydrophilic group.
- R and R ′ represent an alkyl group and a phenyl group, and these may further have a substituent.
- Examples of the substituent include an alkylamino group, a hydroxyl group, and an ionic hydrophilic group. R and R ′ may form a ring by a chemical bond.
- Examples of the alkyl group include methyl, ethyl, butyl, n-propyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trimethyl. Included are fluoromethyl, 3-sulfopropyl and 4-sulfobutyl.
- the cycloalkyl group represented by Z 1 , Z 2 , Z 3 , and Z 4 includes a cycloalkyl group having a substituent and an unsubstituted cycloalkyl group.
- the cycloalkyl group is preferably a cycloalkyl group having 5 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the cycloalkyl group include a cyclohexyl group.
- the alkenyl group represented by Z 1 , Z 2 , Z 3 , and Z 4 includes an alkenyl group having a substituent and an unsubstituted alkenyl group.
- an alkenyl group having 2 to 12 carbon atoms when a substituent is removed is preferable.
- the substituent include an ionic hydrophilic group.
- Examples of the alkenyl group include a vinyl group and an allyl group.
- the aralkyl group represented by Z 1 , Z 2 , Z 3 and Z 4 includes an aralkyl group having a substituent and an unsubstituted aralkyl group.
- an aralkyl group having 7 to 12 carbon atoms when a substituent is removed is preferable.
- the substituent include an ionic hydrophilic group.
- the aralkyl group include a benzyl group and a 2-phenethyl group.
- the aryl group represented by Z 1 , Z 2 , Z 3 , and Z 4 includes an aryl group having a substituent and an unsubstituted aryl group.
- the aryl group is preferably an aryl group having 6 to 12 carbon atoms when the substituent is removed. Examples of the aryl group include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl, m-sulfophenyl.
- substituents examples include an alkyl group (R—), an alkoxy group (RO—), an alkylamino group (RNH—, RR′N—), a carbamoyl group (—CONHR), a sulfamoyl group (—SO 2 NHR), A sulfonylamino group (—NHSO 2 R), a halogen atom, and an ionic hydrophilic group are included (wherein R and R ′ represent an alkyl group and a phenyl group, and these may have an ionic hydrophilic group). Good).
- the heterocyclic group represented by Z 1 , Z 2 , Z 3 , and Z 4 includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group, and may form a condensed ring with another ring.
- the heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group.
- the heterocyclic group may form a condensed ring with another ring. Examples of the heterocyclic group include, but are not limited to, the substitution position of the heterocyclic ring.
- substituents examples include an alkyl group (R—), an aryl group (R—), an alkoxy group (RO—), an alkylamino group (RNH—, RR′N—), a carbamoyl group (—CONHR), and a sulfamoyl group.
- R— alkyl group
- R— aryl group
- R— an alkoxy group
- RNH—, RR′N— an alkylamino group
- CONHR —CONHR
- sulfamoyl group —SO 2 NHR
- sulfonylamino group —NHSO 2 R
- sulfonyl group —SO 2 R
- acylamino group —NHCOR
- halogen atom, ionic hydrophilic group are included (note that R, R 'Represents an alkyl group or an aryl group, and these may have an ionic hydrophilic group or a substituent having an ionic hydrophil
- Z 1 , Z 2 , Z 3 and Z 4 are preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted alkyl group or a substituted aryl group.
- a substituted heterocyclic group is more preferred, and a substituted alkyl group is still more preferred.
- At least one of Z 1 , Z 2 , Z 3 , and Z 4 has an ionic hydrophilic group as a substituent.
- the ionic hydrophilic group as a substituent include a sulfo group, a carboxyl group, and a quaternary ammonium group.
- a carboxyl group and a sulfo group are preferable, and a sulfo group is particularly preferable.
- the carboxyl group and the sulfo group may be in a salt state, and examples of the counter ion forming the salt include alkali metal ions (eg, sodium ion, potassium ion) and organic cations (eg, tetramethylguanidinium ion). ) Is included.
- alkali metal ions eg, sodium ion, potassium ion
- organic cations eg, tetramethylguanidinium ion.
- q 1 , q 2 , q 3 and q 4 each independently represent 1 or 2.
- M 1 represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.
- M 1 is a metal element other than a hydrogen atom, such as Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru. Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, and the like. Of these, Cu, Ni, Zn, Al and the like are particularly preferable, and Cu is most preferable.
- Preferred examples of the metal oxide include VO and GeO.
- Si (OH) 2 , Cr (OH) 2 , Sn (OH) 2, etc. are mentioned preferably.
- the metal halide AlCl, SiCl 2, VCl, VCl 2, VOCl, FeCl, GaCl, ZrCl , and the like.
- R 1 , R 4 , R 5 , R 8 , R 9 , R 12 , R 13 and R 16 are each independently R 2 , R 3 , R 6 , R 7 , R in the general formula (1).
- 10 , R 11 , R 14 and R 15 are synonymous with each other.
- Z 5 , Z 6 , Z 7 , and Z 8 are each independently synonymous with Z 1 , Z 2 , Z 3 , and Z 4 in the general formula (1).
- t, u, v, w, q 5 , q 6 , q 7 and q 8 each independently represent 1 or 2.
- M 2 has the same meaning as M 1 in the general formula (1).
- R 1 , R 4 , R 5 , R 8 , R 9 , R 12 , R 13 and R 16 are each independently R 2 , R 3 , R 6 , R 7 , R in the general formula (1).
- 10 , R 11 , R 14, and R 15 each having the same meaning, a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amide group, a ureido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, and An alkoxycarbonyl group is preferred, a hydrogen atom, a halogen atom and a cyano group are particularly preferred, and a hydrogen atom is most preferred.
- These groups may further have a substituent. Examples of the substituent include the substituents described in the above substituent group A.
- Z 5 , Z 6 , Z 7 , and Z 8 are each independently synonymous with Z 1 , Z 2 , Z 3 , and Z 4 in the general formula (1).
- Z 5 , Z 6 , Z 7 and Z 8 are preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted alkyl group or a substituted aryl group.
- a substituted heterocyclic group is more preferred, and a substituted alkyl group is still more preferred.
- at least one of the substituents of the substituted alkyl group is most preferably a —SONHR group from the viewpoint of ozone fastness.
- the ionic hydrophilic group which at least one of Z 5 , Z 6 , Z 7 and Z 8 has as a substituent is substituted by Z 1 , Z 2 , Z 3 and Z 4 in the general formula (1). It is synonymous with the ionic hydrophilic group which has as a group, and its preferable example is also the same.
- q 5 , q 6 , q 7 and q 8 each independently represent 1 or 2.
- M 2 has the same meaning as M 1 in the general formula (1), and preferred examples thereof are also the same.
- phthalocyanine dyes examples include “Phthalocyanine—Chemistry and Function” (P. 1 to 62) published by K. Shirai and Kobayashi, Inc. C. Leznoff-A. B. P. Lever co-authored, published by VCH, “Phthalogicanes-Properties and Applications” (P. 1 to 54), etc., can be synthesized by combining quoted or similar methods.
- R 1 , R 4 , R 5 , R 8 , R 9 , R 12 , R 13 and R 16 are hydrogen, q 5 , q 6 .
- the compound in which q 7 and q 8 are 2 includes, for example, a phthalonitrile derivative represented by the following general formula (V) and / or a diiminoisoindoline derivative represented by the following general formula (VI) and the following M- (Y ) It is synthesized by reacting a metal derivative represented by d.
- R 1 , R 4 , R 5 , R 8 , R 9 , R 12 , R 13 and R 16 are each independently R 2 , R 3 , R 6 , R 7 , R in the general formula (1).
- 10 , R 11 , R 14 and R 15 have the same meanings.
- Z 5 , Z 6 , Z 7 , and Z 8 are each independently synonymous with Z 1 , Z 2 , Z 3 , and Z 4 in the general formula (1).
- t, u, v, w, q 5 , q 6 , q 7 and q 8 each independently represent 1 or 2.
- x has the same meaning as t, u, v and w in general formula (I-2).
- Z represents a substituent corresponding to Z 5 , Z 6 , Z 7 , and Z 8 .
- Y represents a monovalent or divalent ligand such as a halogen atom, acetate anion, acetylacetonate or oxygen, and d is an integer of 1 to 4.
- Examples of the metal derivative represented by M- (Y) d include Al, Si, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ge, Ru, Rh, Pd, In, Sn, Pt, and Pb. Halides, carboxylic acid derivatives, sulfates, nitrates, carbonyl compounds, oxides, complexes, and the like. Specific examples include copper chloride, copper bromide, copper iodide, nickel chloride, nickel bromide, nickel acetate, cobalt chloride, cobalt bromide, cobalt acetate, iron chloride, zinc chloride, zinc bromide, zinc iodide, acetic acid.
- Examples include zinc, vanadium chloride, vanadium oxytrichloride, palladium chloride, palladium acetate, aluminum chloride, manganese chloride, manganese acetate, acetylacetone manganese, manganese chloride, lead chloride, lead acetate, indium chloride, titanium chloride, tin chloride and the like.
- the amount of the metal derivative and the phthalonitrile compound represented by the general formula (V) is preferably 1: 3 to 1: 6 in terms of molar ratio.
- the amount of the metal derivative and the diiminoisoindoline derivative represented by the general formula (VI) is preferably 1: 3 to 1: 6 in terms of molar ratio.
- the reaction is usually performed in the presence of a solvent.
- a solvent an organic solvent having a boiling point of 80 ° C. or higher, preferably 130 ° C. or higher is used.
- the amount of the solvent used is 1 to 100 times, preferably 5 to 20 times, that of the phthalonitrile compound.
- 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) or ammonium molybdate may be added as a catalyst.
- the addition amount is 0.1 to 10 times mol, preferably 0.5 to 2 times mol, per mol of the phthalonitrile compound and / or diiminoisoindoline derivative.
- the reaction temperature is preferably 80 to 300 ° C., preferably 100 to 250 ° C., and particularly preferably 130 to 230 ° C. Below 80 ° C, the reaction rate is extremely slow. If it exceeds 300 ° C, the phthalocyanine compound may be decomposed.
- the reaction time is 2 to 20 hours, preferably 5 to 15 hours, more preferably 5 to 10 hours. If it is less than 2 hours, there are many unreacted raw materials, and if it exceeds 20 hours, decomposition of the phthalocyanine compound may occur.
- the product obtained by these reactions is treated as a product after being treated according to a post-treatment method of a normal organic synthesis reaction and then purified or not purified. That is, for example, those which are liberated from the reaction system are not purified, or operations for purification by recrystallization or column chromatography (for example, gel permeation chromatography (SEPHADEX TM LH-20: manufactured by Pharmacia) etc. are used alone or in combination.
- the reaction solvent is distilled off or is poured into water or ice without being distilled off, and is neutralized or liberated without being neutralized.
- the product can be provided as a product after it has been purified by recrystallization, column chromatography, etc. alone or in combination.
- the product can be provided as a product after it has been purified alone or in combination without being purified, or purified by crystallization or column chromatography.
- R 1 , R 4 , R 5 , R 8 , R 9 , R 12 , R 13 and R 16 are hydrogen
- phthalocyanine compounds in which q 7 and q 8 are represented by 2 are usually Ra (SO 2 -Z 5 ), Rb (SO 2 -Z 6 ), Rc (SO 2 -Z 7 ), Rd (SO 2 -Z 8 ), and a mixture of compounds represented by the following general formulas (a) -1 to (a) -4 It has become.
- the compounds represented by the above general formulas (a) -1 to (a) -4 have ⁇ -position substitution type (R 1 to R 16 in the following general formula (IV) are respectively in the 1st to 16th positions.
- a phthalocyanine compound having a specific substituent at the 2 and / or 3 position, 6 and / or 7 position, 10 and / or 11 position, 14 and / or 15 position In the case, a phthalocyanine compound having a specific substituent at the 2 and / or 3 position, 6 and / or 7 position, 10 and / or 11 position, 14 and / or 15 position).
- the phthalocyanine dye represented by the general formula (1) of the present invention is an ⁇ -position-substituted type (1 and / or 4 position, 5 and / or 8 position, 9 and / or 12 position, 13 and / or 16 position).
- the phthalocyanine dye represented by the general formula (I-2) is a ⁇ -position substituted type (2 and / or 3 position, 6 and / or 7 position, 10 and or 11 position, 14 and or 15 position)
- a phthalocyanine compound having a specific substituent in the present invention, in any substitution type, having a specific substituent represented by —SO—Z and / or —SO 2 —Z is important for good robustness.
- phthalocyanine dye represented by the general formula (1) or the general formula (I-2) are shown below using the following general formula (IV), but the phthalocyanine dye used in the present invention is the following example. It is not limited to.
- Each P independently represents a nitrogen atom or CH, and at least one P represents a nitrogen atom. However, in each of the four rings containing P, P representing a nitrogen atom is 2 or less.
- R 21 and R 22 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.
- R 23 represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.
- R 24 represents a substituted or unsubstituted hydrocarbon group.
- R 23 and R 24 may be bonded together with a nitrogen atom to form a substituted or unsubstituted heterocycle.
- x, y, and z each independently represent 0 or more and 4 or less.
- x + y + z is 1 or more and 4 or less.
- the azaphthalocyanine dye represented by the general formula (II-2) is preferably an azaphthalocyanine dye represented by the following general formula (II-3-1) or general formula (II-3-2).
- Each P independently represents a nitrogen atom or CH, and at least one P represents a nitrogen atom.
- R 21 and R 22 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.
- R 23 represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.
- R 24 represents a substituted or unsubstituted hydrocarbon group.
- R 23 and R 24 may be bonded together with a nitrogen atom to form a substituted or unsubstituted heterocycle.
- x, y, and z each independently represent 0 or more and 4 or less.
- x + y + z is 1 or more and 4 or less.
- the substituted or unsubstituted alkyl group represented by R 21 and R 22 is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and 1 to More preferred is an alkyl group of 4.
- Substituent group A is mentioned as a substituent, A hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group are preferable, and a hydroxyl group or an ionic hydrophilic group is more preferable.
- the alkyl group is preferably methyl, ethyl, butyl, isopropyl, n-propyl, or t-butyl, more preferably methyl or n-propyl, and still more preferably n-propyl.
- R 21 preferably represents a methyl group or a hydrogen atom, and more preferably represents a hydrogen atom.
- R 22 preferably represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and when it has a substituent, the substituent is preferably a hydroxyl group, n-propyl or a hydrogen atom Is more preferable, and a hydrogen atom is more preferable.
- the substituted or unsubstituted hydrocarbon group represented by R 23 and R 24 is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted aryl group.
- the substituted or unsubstituted alkyl group represented by R 23 and R 24 is preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms when the substituent is removed. Further, an alkyl group having 1 to 4 carbon atoms is more preferable.
- Substituent group A is mentioned as a substituent.
- the alkyl group methyl, ethyl, butyl, isopropyl and t-butyl are preferable.
- the substituted or unsubstituted heterocyclic group represented by R 23 and R 24 is preferably a 5-membered or 6-membered heterocyclic group.
- Substituent group A is mentioned as a substituent, and an ionic hydrophilic group is contained.
- the heterocyclic group a 2-pyridyl group, a 2-thienyl group and a 2-furyl group are preferable.
- the substituted or unsubstituted aryl group represented by R 23 and R 24 is preferably an aryl group having 6 to 12 carbon atoms when the substituent is removed.
- substituent group A examples include substituent group A, and an alkyl group, an alkoxy group, a halogen atom, an alkylamino group, and an ionic hydrophilic group are preferable.
- aryl group phenyl or naphthyl is preferable.
- R 23 preferably represents a methyl group or a hydrogen atom, and more preferably represents a hydrogen atom.
- R 24 is preferably a substituent represented by the following general formula (T1).
- R 23 represents a hydrogen atom
- R 24 is represented by the following general formula (T1). A substituent is preferred.
- L represents a single bond or a substituted or unsubstituted alkylene group.
- X represents independently a substituent selected from —OR 25 , —SR 25 , and —NR 25 R 26 , and R 25 and R 26 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted group Alternatively, it represents an unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, and at least one of R 25 and R 26 has an ionic hydrophilic group as a substituent.
- R 27 represents a hydrogen atom or a substituted or unsubstituted alkyl group.
- the substituted or unsubstituted alkylene group represented by L is preferably an alkylene group having 1 to 12 carbon atoms when the substituent is removed, more preferably an alkylene group having 1 to 8 carbon atoms, Is more preferably an alkylene group of 1 to 4.
- Substituent group A is mentioned as a substituent.
- the alkylene group methylene, ethylene, butylene, isopropylene and t-butylene are preferable.
- X is preferably —NR 25 R 26 .
- R 27 is preferably an alkyl group having 1 to 12 carbon atoms when the substituent is removed, more preferably an alkyl group having 1 to 8 carbon atoms, More preferred are alkyl groups having 1 to 4 numbers.
- R 27 preferably represents a methyl group or a hydrogen atom, and more preferably represents a hydrogen atom.
- the substituent represented by the general formula (T1) is a substituent represented by the following general formula (T2).
- L represents a single bond or a substituted or unsubstituted alkylene group.
- R 29 , R 210 , and R 211 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group
- R 212 represents a substituted alkyl group, a substituted aryl group, or a substituted heterocyclic group, and is ionic It has at least one hydrophilic group as a substituent.
- R 27 represents a hydrogen atom or a substituted or unsubstituted alkyl group.
- L and R 27 are synonymous with L and R 27 in formula (T1), and preferred ones are also the same.
- the substituted or unsubstituted alkyl group represented by R 29 , R 210 , and R 211 has the same meaning as that described for R 27 in General Formula (T1), and preferred examples thereof are also the same.
- R 27 , R 29 , R 210 , and R 211 preferably represent a methyl group or a hydrogen atom, and more preferably represent a hydrogen atom.
- R 212 preferably represents a substituted aryl group, and examples of the substituent include Substituent Group A, which has at least one ionic hydrophilic group as a substituent.
- the substituent is preferably an ionic hydrophilic group, preferably a sulfo group, a carboxyl group, a thiocarboxyl group, a sulfino group, a phosphono group, a dihydroxyphosphino group, and a quaternary ammonium group, more preferably a carboxyl group and a sulfo group.
- a sulfo group is more preferable.
- the carboxyl group and the sulfo group may be in a salt state, and examples of the counter ion forming the salt include alkali metal ions (eg, sodium ion, potassium ion) and organic cations (eg, tetramethylguanidinium ion). ) Is included.
- R 212 is preferably an aryl group substituted with 1 to 3 ionic hydrophilic groups, preferably an aryl group substituted with 2 ionic hydrophilic groups (preferably a carboxyl group or a sulfo group). It is more preferable.
- the azaphthalocyanine compound represented by the general formula (II-2) according to the present invention can be synthesized by the method described in International Publication No. 2010/020802.
- R 17 and R 18 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, substituted or unsubstituted An unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, A represents a divalent linking group, and adjacent R 17 , R 18 , and A are linked to each other.
- Y and Z may be independently a halogen atom, a hydroxyl group, a sulfonic acid group, a carboxyl group, an amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyloxy group.
- the substituted or unsubstituted alkyl group represented by R 17 and R 18 is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and 1 to More preferred is an alkyl group of 4.
- Substituent group A is mentioned as a substituent, A hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group are preferable, and a hydroxyl group or an ionic hydrophilic group is more preferable.
- the alkyl group is preferably methyl, ethyl, butyl, isopropyl, n-propyl, or t-butyl, more preferably methyl or n-propyl, and still more preferably n-propyl.
- R 27 and R 28 preferably represent a methyl group or a hydrogen atom, and more preferably represent a hydrogen atom.
- the cycloalkyl group represented by R 17 and R 18 includes a cycloalkyl group having a substituent and an unsubstituted cycloalkyl group.
- the cycloalkyl group is preferably a cycloalkyl group having 5 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group.
- a cyclohexyl group is preferred as an example of a cycloalkyl group.
- Examples of the aralkyl group represented by R 17 and R 18 include a substituted aralkyl group and an unsubstituted aralkyl group.
- an aralkyl group having 7 to 12 carbon atoms when a substituent is removed is preferable.
- the substituent include an ionic hydrophilic group.
- Examples of the aralkyl group are preferably a benzyl group and a 2-phenethyl group.
- the substituted or unsubstituted aryl group represented by R 17 and R 18 is preferably an aryl group having 6 to 12 carbon atoms when the substituent is removed.
- substituent group A examples include substituent group A, and an alkyl group, an alkoxy group, a halogen atom, an alkylamino group, and an ionic hydrophilic group are preferable.
- aryl group phenyl or naphthyl is preferable.
- the substituted or unsubstituted heterocyclic group represented by R 17 and R 18 is preferably a 5-membered or 6-membered heterocyclic group.
- Substituent group A is mentioned as a substituent, and an ionic hydrophilic group is contained.
- the heterocyclic group a 2-pyridyl group, a 2-thienyl group and a 2-furyl group are preferable.
- the alkenyl group represented by R 17 and R 18 includes an alkenyl group having a substituent and an unsubstituted alkenyl group.
- an alkenyl group having 2 to 12 carbon atoms when a substituent is removed is preferable.
- the substituent include an ionic hydrophilic group.
- Preferred examples of the alkenyl group include a vinyl group and an allyl group.
- the aryloxy group represented by R 17 and R 18 includes an aryloxy group having a substituent and an unsubstituted aryloxy group.
- the aryloxy group is preferably an aryloxy group having 6 to 12 carbon atoms when a substituent is removed.
- Examples of the substituent include an alkoxy group and an ionic hydrophilic group.
- Examples of the aryloxy group are preferably a phenoxy group, a p-methoxyphenoxy group, and an o-methoxyphenoxy group.
- a halogen atom represented by Y and Z a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted Aralkyloxy group, substituted or unsubstituted alkenyloxy group, substituted or unsubstituted alkylamino group, substituted or unsubstituted cycloalkylamino group, substituted or unsubstituted arylamino group, substituted or unsubstituted heterocyclic amino group Substituted or unsubstituted aralkylamino group, substituted or unsubstituted alkenylamino group, substituted or unsubstituted dialkylamino group, substituted or unsubstituted alkylthio group, substituted
- the divalent linking group represented by A includes an alkylene group, an arylene group, a heterocyclic residue, -CO-, -SOn- (n is 0, 1, 2), -NR- (R is a hydrogen atom, an alkyl group, Represents an aryl group), -O-, and a divalent group obtained by combining these linking groups, and further include an alkyl group, an aryl group, an alkoxy group, an amino group, an acyl group, an acylamino group, a halogen atom, You may have substituents, such as a hydroxyl group, a carboxyl group, a sulfamoyl group, a carbamoyl group, and a sulfonamide group.
- An alkylene group is preferred, and an ethylene group and an n-propylene group are preferred.
- the phthalocyanine dye represented by the general formula (III-2) is preferably a phthalocyanine dye represented by the following general formula (III-2-1).
- each of R 27 and R 28 independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, A substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, A represents a divalent linking group, and adjacent R 27 , R 28 , and A are They may be linked to form a ring.
- R 29 , R 210 , and R 211 each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group
- R 212 represents a sulfonic acid group, a carboxyl group, a substituted alkyl group, a substituted aryl group, or a substituted hetero group.
- m and n are 1 to 3, and the sum of m and n is 2 to 4.
- R 27 and R 28 have the same meanings as A, R 17 and R 18 in formula (1), and preferred ones are also the same.
- the substituted or unsubstituted alkyl group represented by R 29 , R 210 and R 211 is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, More preferred are alkyl groups having 1 to 4 numbers.
- Substituent group A is mentioned as a substituent, A hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group are preferable, and a hydroxyl group or an ionic hydrophilic group is more preferable.
- the alkyl group is preferably methyl, ethyl, butyl, isopropyl, n-propyl, or t-butyl, more preferably methyl or n-propyl, and still more preferably n-propyl.
- R 27 and R 28 preferably represent a methyl group or a hydrogen atom, and more preferably represent a hydrogen atom.
- R 212 preferably represents a substituted aryl group, and examples of the substituent include Substituent Group A, which has at least one ionic hydrophilic group as a substituent.
- the substituent is preferably an ionic hydrophilic group, preferably a sulfo group, a carboxyl group, a thiocarboxyl group, a sulfino group, a phosphono group, a dihydroxyphosphino group, and a quaternary ammonium group, more preferably a carboxyl group and a sulfo group.
- a sulfo group is more preferable.
- the carboxyl group and the sulfo group may be in a salt state, and examples of the counter ion forming the salt include alkali metal ions (eg, sodium ion, potassium ion) and organic cations (eg, tetramethylguanidinium ion). ) Is included.
- alkali metal ions eg, sodium ion, potassium ion
- organic cations eg, tetramethylguanidinium ion.
- R 212 represents a sulfonic acid group, a carboxyl group, a substituted alkyl group, a substituted aryl group, or a substituted heterocyclic group, and more preferably a substituted alkyl group or a substituted aryl group.
- R 212 is preferably an aryl group substituted with 1 to 3 ionic hydrophilic groups, preferably an aryl group substituted with 2 ionic hydrophilic groups (preferably a carboxyl group or a sulfo group). It is more preferable.
- phthalocyanine dye represented by formula (III-2) Specific examples of the phthalocyanine dye represented by formula (III-2) are shown below, but the phthalocyanine dye used in the present invention is not limited to the following examples.
- the coloring composition of the present invention may further contain a compound (Acid Blue 9) represented by the following formula (AB9).
- Me represents a methyl group
- M represents a hydrogen atom, lithium, sodium, potassium, or ammonium.
- M is preferably sodium, potassium or ammonium, more preferably sodium or ammonium, and most preferably sodium, from the viewpoint of solubility and availability.
- the colored composition of the present invention comprises a phthalocyanine dye represented by the above general formula (1) and the above general formula (I-2), the above general formula (II-2), or the above general formula (III-2).
- one containing Acid Blue 9 is also one preferred form.
- Acid Blue 9 having a high printing density, it is possible to achieve a higher printing density and to achieve both good fastness and higher printing density.
- Acid Blue 9 that can be preferably used in the present invention can be easily obtained as a commercial product (for example, catalog number B0790 manufactured by Tokyo Chemical Industry Co., Ltd.).
- the colored composition according to the aspect I of the present invention contains a phthalocyanine dye represented by the above general formula (1) and a phthalocyanine dye represented by the above general formula (I-2).
- a phthalocyanine dye represented by the above general formula (1) By using the ⁇ -position-substituted dye of the general formula (1) and the ⁇ -position-substituted dye of the general formula (I-2), the ratio between the ⁇ -position and the ⁇ -position between molecules rather than within the molecule As a result, it is possible to achieve both good fastness and high print density.
- the colored composition according to the embodiment II of the present invention contains a phthalocyanine dye represented by the above general formula (1) and an azaphthalocyanine dye represented by the above general formula (II-2).
- the colored composition according to the aspect III of the present invention contains a phthalocyanine dye represented by the above general formula (1) and a phthalocyanine dye represented by the above general formula (III-2).
- a phthalocyanine dye represented by the above general formula (1) and a phthalocyanine dye represented by the above general formula (III-2).
- the colored composition of the present invention can be preferably used as a colored composition for image formation.
- Applications of the colored composition of the present invention include image recording materials for forming images, particularly color images, and specifically, thermal transfer type images including ink jet recording materials described in detail below. Recording materials, pressure-sensitive recording materials, recording materials using electrophotographic methods, transfer-type silver halide photosensitive materials, printing inks, recording pens, etc., preferably ink-jet recording materials, thermal transfer type image recording materials, electrophotographic methods In particular, an ink jet recording material is preferable. It can also be applied to dyeing solutions for dyeing various fibers of color filters used in solid-state imaging devices such as LCDs and CCDs described in US Pat.
- the phthalocyanine dye used in the present invention is used by adjusting physical properties such as solubility and heat transfer properties suitable for the intended use with a substituent.
- the phthalocyanine dye used in the present invention can be used in a uniform dissolved state or a dispersed dissolved state such as an emulsified dispersion depending on the system used.
- Mass of the phthalocyanine dye represented by the general formula (1) and the phthalocyanine dye represented by the general formula (I-2), the general formula (II-2), or the general formula (III-2) in the coloring composition The ratio is preferably 50/50 to 10/90, more preferably 40/60 to 20/80.
- the colored composition is excellent in stability over time (viscosity change, precipitation, etc.) at a high concentration, and is excellent in ozone fastness of a print sample using the colored composition. Further, it is possible to obtain a feature that the print density is excellent.
- the content of the phthalocyanine dye represented by the general formula (1) is preferably 0.1 to 10% by mass.
- the amount is less than 0.1% by mass, the color composition has a high stability over time and the printing density is poor, and when it exceeds 10% by mass, the ozone fastness of the printing sample is lowered.
- the dye content in the coloring composition that is, the phthalocyanine dye represented by the general formula (1), the general formula (I-2), the general formula (II-2), or the general formula (III-2) It was found that the precipitation of the dye over time can be suppressed even in the case of a concentrated dye solution having a total amount of 15 to 20% by mass with the phthalocyanine dye represented by For this reason, the colored composition of the present invention is also useful as a dense inkjet ink.
- the total and acid of the phthalocyanine dyes represented by general formula (1) and general formula (I-2), general formula (II-2) or general formula (III-2) is preferably 90/10 to 99/1, more preferably 95/5 to 97.5 / 2.5.
- the ink for inkjet recording of the present invention contains the above colored composition.
- the ink for inkjet recording can be produced by dissolving and / or dispersing the phthalocyanine compound in an oleophilic medium or an aqueous medium.
- the ink uses an aqueous medium. If necessary, other additives are contained within a range that does not impair the effects of the present invention.
- additives include, for example, anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, anti-fungal agents, pH adjusters, surface tension adjusters, Well-known additives, such as a foaming agent, a viscosity modifier, a dispersing agent, a dispersion stabilizer, a rust preventive agent, a chelating agent, are mentioned. These various additives are directly added to the ink liquid in the case of water-soluble ink. When an oil-soluble dye is used in the form of a dispersion, it is generally added to the dispersion after the preparation of the dye dispersion, but it may be added to the oil phase or the aqueous phase at the time of preparation.
- the anti-drying agent is preferably used for the purpose of preventing clogging due to drying of the ink-jet ink at the ink jet port of the nozzle used in the ink-jet recording method.
- a water-soluble organic solvent having a vapor pressure lower than that of water is preferable.
- Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin.
- Polyhydric alcohols typified by trimethylolpropane, etc., lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, heterocyclic rings such as N-ethylmorpholine, sulfolane, dimethyl sulfoxide, 3 Sulfur-containing compounds such as sulfolane, diacetone alcohol, polyfunctional compounds such as diethanolamine, and urea derivatives.
- lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl)
- polyhydric alcohols such as glycerin and diethylene glycol are more preferred.
- said anti-drying agent may be used independently and may be used together 2 or more types. These drying inhibitors are preferably contained in the ink in an amount of 10 to 50% by mass.
- the penetration accelerator is preferably used for the purpose of allowing the ink for inkjet to penetrate better into the paper.
- penetration enhancers alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, nonionic surfactants, etc. can be used. . If these are contained in the ink in an amount of 5 to 30% by mass, they usually have a sufficient effect, and it is preferable to use them in an additive amount range that does not cause printing bleeding or paper loss (print-through).
- UV absorbers are used for the purpose of improving image storage stability.
- examples of the ultraviolet absorber include benzotriazoles described in JP-A Nos. 58-185677, 61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like.
- the anti-fading agent is used for the purpose of improving image storage stability.
- various organic and metal complex anti-fading agents can be used.
- Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Complex, zinc complex and the like. More specifically, Research Disclosure No. No. 17643, Nos. VII to I, J; 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid.
- the compounds described in the patent cited in Japanese Patent No. 15162 and the compounds represented by the general formulas and compound examples of the representative compounds described on pages 127 to 137 of JP-A-62-215272 can be used.
- antifungal agent examples include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one and salts thereof. These are preferably used in an amount of 0.02 to 1.00% by mass in the ink.
- the neutralizing agent organic base, inorganic alkali
- the pH adjuster is preferably added so that the ink for ink jet recording has a pH of 6 to 10, and more preferably added to have a pH of 7 to 10. preferable.
- the surface tension adjusting agent includes nonionic, cationic or anionic surfactants.
- the surface tension of the inkjet ink of the present invention is preferably 25 to 70 mN / m. Further, 25 to 60 mN / m is preferable. Further, the viscosity of the ink for ink jet recording of the present invention is preferably 30 mPa ⁇ s or less. Furthermore, it is more preferable to adjust to 20 mPa ⁇ s or less.
- surfactants include fatty acid salts, alkyl sulfate esters, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate ester salts, naphthalene sulfonate formalin condensates, polyoxyethylene alkyl sulfates.
- Anionic surfactants such as ester salts, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester
- Nonionic surfactants such as oxyethyleneoxypropylene block copolymers are preferred.
- SURFYNOLS Air Products & Chemicals
- An amine oxide type amphoteric surfactant such as N, N-dimethyl-N-alkylamine oxide is also preferred.
- pages (37) to (38) of JP-A-59-157,636, Research, Disclosure No. The surfactants described in 308119 (1989) can also be used.
- fluorine-based, silicone-based compounds, chelating agents represented by EDTA, and the like can be used as necessary.
- phthalocyanine compound of the present invention is dispersed in an aqueous medium, as described in JP-A-11-286637, Japanese Patent Application Nos. 2000-78491, 2000-80259, 2000-62370, etc.
- colored fine particles containing a dye and an oil-soluble polymer are dispersed in an aqueous medium, or each of the specifications of Japanese Patent Application Nos. 2000-78454, 2000-78491, 2000-203856, and 2000-203857.
- the specific method for dispersing the compound of the present invention in an aqueous medium, the oil-soluble polymer to be used, the high-boiling organic solvent, the additive, and the amount used thereof are preferably those described in the above-mentioned patent publications. be able to.
- the phthalocyanine compound may be dispersed in a fine particle state as a solid. At the time of dispersion, a dispersant or a surfactant can be used.
- Dispersing devices include simple stirrer, impeller stirring method, in-line stirring method, mill method (for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.), ultrasonic method, high pressure emulsification dispersion method (high pressure homogenizer)
- mill method for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.
- ultrasonic method for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.
- ultrasonic method for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.
- ultrasonic method for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.
- high pressure homogenizer high pressure homogenizer
- Specific examples of commercially available devices include gorin homogenizers, microfluid
- the ink jet recording ink preparation method described above is disclosed in JP-A-5-148436, JP-A-5-295212, JP-A-7-97541, JP-A-7-82515, JP-A-7-118584, Details are described in Japanese Laid-Open Patent Publication No. 11-286637 and Japanese Patent Application No. 2000-87539, and can also be used to prepare the ink for inkjet recording of the present invention.
- a mixture containing water as a main component and optionally adding a water-miscible organic solvent can be used.
- the water-miscible organic solvent include alcohol (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyvalent Alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), glycol derivatives (eg , Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene
- the phthalocyanine compound is preferably contained in an amount of 0.2 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 10 parts by mass or less. More preferred are those containing from 5 to 5 parts by weight, and most preferred are those containing from 4 to 5 parts by weight.
- other pigments may be used in combination with the phthalocyanine compound. When two or more kinds of dyes are used in combination, the total content of the dyes is preferably within the above range.
- the ink for ink jet recording of the present invention preferably has a viscosity of 40 cp or less.
- the surface tension is preferably 20 mN / m or more and 70 mN / m or less.
- Viscosity and surface tension are various additives such as viscosity modifiers, surface tension modifiers, specific resistance modifiers, film modifiers, UV absorbers, antioxidants, antifading agents, antifungal agents, and rust inhibitors. It can be adjusted by adding a dispersant and a surfactant.
- the ink for inkjet recording of the present invention can be used not only for forming a single color image but also for forming a full color image.
- a magenta color ink, a cyan color ink, and a yellow color ink can be used, and a black color ink may be further used to adjust the color tone.
- Any applicable yellow dye can be used.
- coupler components as coupling components (hereinafter referred to as coupler components); for example, coupler components Azomethine dyes having open-chain active methylene compounds as examples; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes, and other dyes Examples of the species include quinophthalone dyes, nitro and nitroso dyes, acridine dyes, and acridinone dyes.
- magenta dye Any applicable magenta dye can be used.
- aryl or heteryl azo dyes having phenols, naphthols, anilines, etc. as coupler components for example, azomethine dyes having pyrazolones, pyrazolotriazoles, etc.
- coupler components for example arylidene dyes, styryl dyes, merocyanine dyes, cyanine dyes, Methine dyes such as oxonol dyes; Carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, etc., quinone dyes such as naphthoquinone, anthraquinone, anthrapyridone, etc., condensed polycycles such as dioxazine dyes, etc. And dyes.
- arylidene dyes for example arylidene dyes, styryl dyes, merocyanine dyes, cyanine dyes, Methine dyes such as oxonol dyes; Carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, etc., quinone dyes such as naphthoquinone, an
- cyan dye can be used.
- aryl or heteryl azo dyes having phenols, naphthols, anilines and the like as coupler components for example, azomethine dyes having phenols, naphthols, heterocyclic rings such as pyrrolotriazole as coupler components; cyanine dyes, oxonol dyes, Polymethine dyes such as merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes; phthalocyanine dyes; anthraquinone dyes; indigo and thioindigo dyes.
- each of the above dyes may exhibit yellow, magenta, and cyan colors only after a part of the chromophore is dissociated.
- the counter cation is an alkali metal or an inorganic cation such as ammonium.
- it may be an organic cation such as pyridinium or a quaternary ammonium salt, and may further be a polymer cation having these in a partial structure.
- Applicable black materials include disazo, trisazo, tetraazo dyes, and carbon black dispersions.
- Inkjet recording method energy is supplied to the ink for ink jet recording, and a known image receiving material, that is, plain paper, resin-coated paper, such as JP-A-8-169172, JP-A-8-27693, JP-A-2-276670, JP-A-7-276789, JP-A-9-323475, JP-A-62-238783, JP-A-10-153789, JP-A-10-217473, JP-A-10-235995 10-337947, 10-217597, 10-337947, etc.
- a known image receiving material that is, plain paper, resin-coated paper, such as JP-A-8-169172, JP-A-8-27693, JP-A-2-276670, JP-A-7-276789, JP-A-9-323475, JP-A-62-238783, JP-A-10-153789, JP-A-10-217473, JP-A-10-235995 10-337947, 10-21
- a polymer fine particle dispersion (also referred to as polymer latex) may be used in combination for the purpose of imparting glossiness or water resistance or improving weather resistance.
- the timing of applying the polymer latex to the image receiving material may be before, after, or simultaneously with the application of the colorant, and therefore the addition place may be in the image receiving paper. It may be in ink or may be used as a liquid material of polymer latex alone.
- the method described in the specification can be preferably used.
- the support in recording paper and recording film is made of chemical pulp such as LBKP and NBKP, mechanical pulp such as GP, PGW, RMP, TMP, CTMP, CMPMP, CGP, and waste paper pulp such as DIP.
- Additives such as known pigments, binders, sizing agents, fixing agents, cationic agents, paper strength enhancers, etc. can be mixed and manufactured using various devices such as long net paper machines and circular net paper machines. is there.
- either synthetic paper or plastic film sheets may be used.
- the thickness of the support is preferably 10 to 250 ⁇ m and the basis weight is preferably 10 to 250 g / m 2.
- the support may be provided with an ink receiving layer and a backcoat layer as they are, or after a size press or anchor coat layer is provided with starch, polyvinyl alcohol or the like, an ink receiving layer and a backcoat layer may be provided.
- the support may be flattened by a calendar device such as a machine calendar, a TG calendar, or a soft calendar.
- paper and plastic films laminated on both sides with polyolefin for example, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof
- a white pigment for example, titanium oxide or zinc oxide
- a tinting dye for example, cobalt blue, ultramarine blue, or neodymium oxide
- the ink receiving layer provided on the support contains a pigment and an aqueous binder.
- a white pigment is preferable, and as the white pigment, calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopone, zeolite, Examples thereof include white inorganic pigments such as barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide and zinc carbonate, and organic pigments such as styrene pigments, acrylic pigments, urea resins and melamine resins.
- porous inorganic pigments are preferable, and synthetic amorphous silica having a large pore area is particularly preferable.
- synthetic amorphous silica either anhydrous silicic acid obtained by a dry production method or hydrous silicic acid obtained by a wet production method can be used, but it is particularly desirable to use hydrous silicic acid.
- aqueous binder contained in the ink receiving layer examples include water-soluble polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, polyalkylene oxide derivatives, and the like.
- Water-dispersible polymers such as water-soluble polymers, styrene butadiene latexes, and acrylic emulsions. These aqueous binders can be used alone or in combination of two or more.
- polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferable in terms of adhesion to the pigment and resistance to peeling of the ink receiving layer.
- the ink receiving layer can contain a mordant, a water resistance agent, a light resistance improver, a surfactant, and other additives in addition to the pigment and the aqueous binder.
- the mordant added to the ink receiving layer is preferably immobilized.
- a polymer mordant is preferably used.
- the polymer mordant JP-A-48-28325, JP-A-54-74430, JP-A-54-124726, JP-A-55-22766, JP-A-55-142339, JP-A-60-23850, JP-A-60-23851, 60-23852, 60-23835, 60-57836, 60-60643, 60-118834, 60-122940, 60-122941, 60-122942, 60- No. 235134, JP-A-1-161236, U.S. Pat.Nos.
- the water-proofing agent is effective for making the image water-resistant.
- cationic resins are particularly desirable.
- examples of such cationic resins include polyamide polyamine epichlorohydrin, polyethyleneimine, polyamine sulfone, dimethyl diallyl ammonium chloride polymer, cationic polyacrylamide, colloidal silica, etc.
- polyamide polyamine epichlorohydrin is particularly preferable. is there.
- the content of these cationic resins is preferably 1 to 15% by mass, particularly 3 to 10% by mass, based on the total solid content of the ink receiving layer.
- the light resistance improver examples include zinc sulfate, zinc oxide, hindered amine antioxidants, benzotriazole ultraviolet absorbers such as benzophenone, and the like. Of these, zinc sulfate is particularly preferred.
- the surfactant functions as a coating aid, a peelability improver, a slippage improver or an antistatic agent.
- Surfactants are described in JP-A Nos. 62-173463 and 62-183457.
- An organic fluoro compound may be used in place of the surfactant.
- the organic fluoro compound is preferably hydrophobic.
- Examples of the organic fluoro compound include a fluorine-based surfactant, an oily fluorine-based compound (for example, fluorine oil), and a solid fluorine compound resin (for example, tetrafluoroethylene resin).
- the organic fluoro compounds are described in JP-B-57-9053 (columns 8 to 17), JP-A-61-2994 and JP-A-62-135826.
- the ink receiving layer may be one layer or two layers.
- Recording paper and recording film can be provided with a backcoat layer, and examples of components that can be added to this layer include white pigments, aqueous binders, and other components.
- white pigments contained in the backcoat layer include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, and aluminum silicate.
- White inorganic pigments such as diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudoboehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrous halloysite, magnesium carbonate, magnesium hydroxide
- organic pigments such as styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsule, urea resin and melamine resin.
- aqueous binder contained in the backcoat layer As the aqueous binder contained in the backcoat layer, styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose Water-soluble polymers such as hydroxyethyl cellulose and polyvinyl pyrrolidone, and water-dispersible polymers such as styrene butadiene latex and acrylic emulsion. Examples of other components contained in the backcoat layer include an antifoaming agent, an antifoaming agent, a dye, a fluorescent brightening agent, a preservative, and a water-proofing agent.
- Polymer latex may be added to the constituent layers (including the backcoat layer) of the inkjet recording paper and recording film.
- the polymer latex is used for the purpose of improving film physical properties such as dimensional stabilization, curling prevention, adhesion prevention, and film cracking prevention.
- the polymer latex is described in JP-A Nos. 62-245258, 62-1316648, and 62-110066.
- a polymer latex having a low glass transition temperature 40 ° C. or lower
- cracking and curling of the layer can be prevented.
- curling can be prevented by adding a polymer latex having a high glass transition temperature to the backcoat layer.
- the ink of the present invention is not limited to an ink jet recording system, and is a known system, for example, a charge control system that discharges ink using electrostatic attraction, a drop-on-demand system (pressure) that uses the vibration pressure of a piezo element.
- Pulse method acoustic ink jet method that converts electrical signal into acoustic beam and irradiates ink and uses ink to discharge ink
- thermal ink jet that heats ink to form bubbles and uses generated pressure Used for systems.
- Inkjet recording methods use a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent inks. The method is included.
- Acid Blue 9 used in the present specification was obtained by desalting and purifying a commercially available product (catalog number B0790, manufactured by Tokyo Chemical Industry Co., Ltd.) using a dialysis tube.
- the phthalocyanine compound of the present invention can be derived from, for example, the following synthetic route.
- ⁇ max is the absorption maximum wavelength
- ⁇ max is the molar extinction coefficient at the absorption maximum wavelength.
- Synthesis Example 1 Synthesis of Compound (A)
- 26.0 g of 4-nitrophthalonitrile (Tokyo Kasei) was dissolved in 200 mL of DMSO (dimethyl sulfoxide) and stirred at an internal temperature of 20 ° C.
- 30.3 g of sodium 3-mercapto-propane-sulfonate (Aldrich) was added.
- 24.4 g of anhydrous sodium carbonate was gradually added to the mixture being stirred at an internal temperature of 20 ° C. While stirring the reaction solution, it was heated to 30 ° C. and stirred at the same temperature for 1 hour.
- the reaction solution is filtered with Nutsche, the filtrate is poured into 15000 mL of ethyl acetate for crystallization, and subsequently stirred at room temperature for 30 minutes, and the precipitated crude crystals are filtered with Nutsche, and ethyl acetate is filtered. Washed with and dried. The obtained crude crystals were recrystallized from methanol / ethyl acetate to obtain 42.5 g of Compound A.
- Synthesis Example 2 Synthesis of Compound (B) 42.0 g of Compound (A) was dissolved in 300 mL of acetic acid, and 2.5 g Na 2 WO 4 , 2H 2 O was added to the stirring at an internal temperature of 20 ° C. Then, it was cooled to an internal temperature of 10 ° C. in an ice bath. Subsequently, 32 mL of hydrogen peroxide (30%) was gradually added dropwise while paying attention to heat generation. After stirring at an internal temperature of 15 to 20 ° C. for 30 minutes, the reaction solution was heated to an internal temperature of 60 ° C. and stirred at the same temperature for 1 hour.
- Synthesis Example 3 Synthesis of Exemplified Compound 102 ⁇ (Dye 1A of General Formula (1)) To a three-necked flask equipped with a cooling tube, 70 mL of n-amyl alcohol was added, and 6.7 g of compound B, copper (II) chloride 1 was added thereto. 0.0 g was added, and 7.0 mL of 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) was added dropwise at room temperature with stirring. Subsequently, the reaction solution was heated to an internal temperature of 100 ° C. and stirred at the same temperature for 10 hours. After cooling to 40 ° C., 250 mL of heated methanol at 50 ° C.
- DBU 1,8-diazabicyclo [5.4.0] -7-undecene
- the phthalocyanine copper (II) -substitution position defined in this specification is ⁇ -position substituted type ⁇ in each (2 or 3 position), (6 or 7 position), (10 or 11 position), (14 or 15 position) of each benzene nucleus- ⁇ SO 2- (CH 2 ) 3 one of -SO 3 Na ⁇ group, copper phthalocyanine per molecule - a (CH 2) 3 -SO 3 Na ⁇ group confirmed that the a total of four to chromatic ⁇ - ⁇ SO 2.
- Example I-1 Deionized water was added to the following ingredients to make 100 g, followed by stirring for 1 hour while heating at 30 to 40 ° C. Thereafter, the pH was adjusted to 9 with NaOH 10 mol / L, and filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m to prepare an ink solution for cyan.
- Phthalocyanine dye (compound 1A) 0.3 g 2.7 g of phthalocyanine dye (Compound I-2B) Diethylene glycol 2g Glycerin 12g 23 g of diethylene glycol monobutyl ether 2-pyrrolidone 8g 1.79 g of triethanolamine Benzotriazole 0.006g Surfynol TG 0.85g PROXEL XL2 0.18g
- Example I-2 to I-74 Comparative Examples I-1 to I-20
- Examples I-2 to I-74 were prepared in the same manner as in the preparation of the ink liquid of Example I-1, except that the types and addition amounts of the dyes were changed as shown in Tables I-17 to I-19 below.
- Ink solutions of Comparative Examples I-1 to I-20 were prepared.
- the photo glossy paper on which the image has been formed is left in a box set at an ozone gas concentration of 0.5 ⁇ 0.1 ppm, room temperature and dark place for 7 days, and the image density before and after being left under ozone gas is measured by a reflection densitometer (X -Rite310TR) and evaluated as the residual ratio of the dye.
- the reflection density was measured at three points of 1, 1.5 and 2.0.
- the ozone gas concentration in the box was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS.
- the evaluation was made in three stages, with A being a dye residual ratio of 70% or more at any concentration, A being 1 or 2 points being less than 70% B, and C being less than 70% at all concentrations.
- Print density When the reflection density of plain paper at 100% print density is measured using a reflection densitometer (X-Rite 310TR), the print density is 1.10 or more when A is 1.00 or more and less than 1.10. Was B, and the case of less than 1.00 was C, and was evaluated in three stages.
- Example I-101 Deionized water was added to the following components to make 33.3 g, and the mixture was stirred for 1 hour while heating at 50 ° C. Thereafter, the pH was adjusted to 9 with NaOH 10 mol / L to prepare a concentrated aqueous solution.
- Phthalocyanine dye (Compound 1A) 0.5g Phthalocyanine dye (compound I-2B) 4.5g
- Examples I-102 to I-132 Comparative Examples I-101 to I-108
- Examples I-102 to I-132 were prepared in the same manner as in the preparation of the concentrated aqueous solution of Example I-101, except that the phthalocyanine dye and the dye addition amount were changed as shown in Tables I-20 to I-21 below.
- Ink solutions of Comparative Examples I-101 to I-108 were prepared.
- the ink for inkjet recording of the present invention achieved a high printing density while maintaining the same image fastness as compared with the ink of the comparative example. It was also found that the ink storage stability over time was excellent.
- Example II-1 Deionized water was added to the following ingredients to make 100 g, followed by stirring for 1 hour while heating at 30 to 40 ° C. Thereafter, the pH was adjusted to 9 with NaOH 10 mol / L, and filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m to prepare an ink solution for cyan.
- Phthalocyanine dye Compound II-3A
- Diethylene glycol 2g Glycerin 12g 23 g of diethylene glycol monobutyl ether 2-pyrrolidone 8g 1.79 g of triethanolamine Benzotriazole 0.006g Surfynol 465 (trade name, manufactured by Air Products) 0.85 g PROXEL XL2 (trade name, manufactured by FUJIFILM Imaging Colorants) 0.18 g
- Example II-2 to II-10 Comparative Examples II-1 to II-6
- Example II-2 to II-10 Comparative Example II were the same as the preparation of the ink liquid of Example II-1, except that the phthalocyanine dye and the dye addition amount were changed as shown in Table II-23 below.
- Ink liquids of -1 to II-6 were prepared.
- the photo glossy paper on which the image has been formed is left in a box set at an ozone gas concentration of 0.5 ⁇ 0.1 ppm, room temperature and dark place for 7 days, and the image density before and after being left under ozone gas is measured by a reflection densitometer (X -Rite310TR) and evaluated as the residual ratio of the dye.
- the reflection density was measured at three points of 1, 1.5 and 2.0.
- the ozone gas concentration in the box was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS.
- the evaluation was made in three stages, with A being a dye residual ratio of 70% or more at any concentration, A being 1 or 2 points being less than 70% B, and C being less than 70% at all concentrations.
- Print density The reflection density at a printing density of 100% on plain paper is measured by using a reflection densitometer (X-Rite 310TR) as the image density (printing density), and when the printing density is 1.10 or more, A, 1.05 or more. A case of less than 10 was evaluated as B, and a case of less than 1.05 was evaluated as C.
- X-Rite 310TR reflection densitometer
- the ink for inkjet recording of the present invention was found to exhibit a high print density, suppress bronze gloss, and achieve an excellent hue while maintaining equivalent ozone resistance as compared with the comparative ink. . Moreover, it turned out that the light source dependence that there are few color differences by the difference in a light source can be suppressed.
- Example II The structure of the compound used in Example II (other than 1A and 1B) is shown below.
- Example III-1 Deionized water was added to the following ingredients to make 100 g, followed by stirring for 1 hour while heating at 30 to 40 ° C. Thereafter, the pH was adjusted to 9 with NaOH 10 mol / L, and filtered under reduced pressure with a microfilter having an average pore size of 0.25 ⁇ m to prepare an ink solution for cyan.
- Phthalocyanine dye Compound III-4A
- 2-pyrrolidone 8g 1.79 g of triethanolamine Benzotriazole 0.006g Surfynol 465 (trade name, manufactured by Air Products) 0.85 g
- PROXEL XL2 manufactured by FUJIFILM Imaging Colorant 0.18g
- Example III-2 to III-6 Comparative Examples III-1 to III-5)
- Example III-2 to III-6 and Comparative Example III were the same as the preparation of the ink liquid of Example III-1, except that the phthalocyanine dye and the dye addition amount were changed as shown in Table III-9 below.
- Ink liquids of -1 to III-5 were prepared.
- the photo-glossy paper on which the image has been formed is left in a box set at an ozone gas concentration of 5 ⁇ 0.1 ppm, room temperature, in a dark place for one day, and the image density before and after being left under ozone gas is measured by a reflection densitometer ) And evaluated as a dye residual ratio.
- the reflection density was measured at three points of 1, 1.5 and 2.0.
- the ozone gas concentration in the box was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS.
- the evaluation was made in three stages, with A being a dye residual ratio of 70% or more at any concentration, A being 1 or 2 points being less than 70% B, and C being less than 70% at all concentrations.
- Print density When the reflection density of plain paper at 100% print density is measured using a reflection densitometer (X-Rite310TR), the print density is 1.10 or more when A is 1.05 or more and less than 1.10. Was evaluated in three stages, with B being less than 1.05 and C being less than 1.05.
- Example III-101 Deionized water was added to the following components to make 33.3 g, and the mixture was stirred for 1 hour while heating at 50 ° C. Thereafter, the pH was adjusted to 9 with NaOH 10 mol / L to prepare a concentrated aqueous solution.
- Phthalocyanine dye Compound III-4A
- 2-pyrrolidone 8g 1.79 g of triethanolamine Benzotriazole 0.006g Surfynol 465 (trade name, manufactured by Air Products) 0.85 g
- PROXEL XL2 manufactured by FUJIFILM Imaging Colorant 0.18g
- Example III-102 to III-106 Comparative Examples III-101 to III-105
- Example III-102 to III-106 and Comparative Example III-101 were the same as the preparation of the concentrated aqueous solution of Example 101 except that the phthalocyanine dye and the dye addition amount were changed as shown in Table III-10 below.
- Ink liquids of III to 105 were prepared.
- the ink for inkjet recording of the present invention was found to exhibit a high print density, suppress bronze gloss, and achieve an excellent hue while maintaining equivalent ozone resistance as compared with the comparative ink. . Moreover, it turned out that it is excellent also in storage stability with time.
- Example III The structure of the compound used in Example III (other than 1A and 1B) is shown below.
- a coloring composition and an ink jet recording ink having good ozone fastness, high printing density, and excellent storage stability with time.
- a coloring composition having good ozone fastness, high printing density, suppressing bronze gloss, realizing excellent hue, and excellent in light source dependency, and inkjet Recording ink is provided.
- a coloring composition and an ink jet having good ozone fastness, high printing density, suppressing bronze gloss, realizing excellent hue, and excellent storage stability over time. Recording ink is provided.
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Abstract
Description
また、β位置換型のフタロシアニン色素のみからなるインクジェット記録用インクにおいても、オゾン堅牢性と印画濃度は十分には両立しておらず、印画濃度についてはさらなる改良の余地があることがわかった。
本発明のIIの態様はこのような事情に鑑みなされたもので、ブロンズ光沢を抑制し、良好なオゾンガス堅牢性と高い印画濃度を有する着色組成物及びインクジェット用記録インクを提供することを目的とする。
本発明のIIIの態様はこのような事情に鑑みなされたもので、ブロンズ光沢を抑制し、良好なオゾンガス堅牢性と高い印画濃度を有する着色組成物及びインクジェット用記録インクを提供することを目的とする。
IIの態様において本発明者らは、特定構造のフタロシアニンと特定の置換基を有するアザフタロシアニンとを混合して用いることで会合を抑制し、上記トレードオフの関係を脱却できることを見出し、本発明を完成するに至った。また、本発明の着色組成物をシアンインクとして用い、市販のマゼンタインク及びイエローインクを組み合わせて作成したグレイ及び黒色画像は、予想外にも異なる光源(例えば蛍光灯下と太陽光下など)のもとでも視覚的に同じ色に見えるという光源依存性に優れている事がわかった。
IIIの態様において本発明者らは、特定構造のフタロシアニンと特定の置換基を有するフタロシアニンとを混合して用いることで会合を抑制し、上記トレードオフの関係を脱却できることを見出し、本発明を完成するに至った。また、本発明の着色組成物は、予想外にも高濃度水溶液においても析出にしくいという経時貯蔵安定性に優れている事がわかった。優れた経時貯蔵安定性は、インクジェット用インクの原料となる染料水溶液を高濃度で調整できることから保管・輸送の点で有利であり、また高濃度染料水溶液を用いてインクジェット用インクを調液する際に、染料の析出などがないため濃度のずれが起きにくく有用である。
下記一般式(1)で表されるフタロシアニン染料と、下記一般式(I-2)、下記一般式(II-2)又は下記一般式(III-2)で表されるフタロシアニン染料とを含むことを特徴とする着色組成物。
一般式(1)中、
R2、R3、R6、R7、R10、R11、R14及びR15は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、シクロアルキル基、アルケニル基、アラルキル基、アリール基、ヘテロ環基、シアノ基、ヒドロキシル基、ニトロ基、アミノ基、アルキルアミノ基、アルコキシ基、アリールオキシ基、アミド基、アリールアミノ基、ウレイド基、スルファモイルアミノ基、アルキルチオ基、アリールチオ基、アルコキシカルボニルアミノ基、スルホンアミド基、カルバモイル基、スルファモイル基、アルコキシカルボニル基、ヘテロ環オキシ基、アゾ基、アシルオキシ基、カルバモイルオキシ基、シリルオキシ基、アリールオキシカルボニル基、アリールオキシカルボニルアミノ基、イミド基、ヘテロ環チオ基、ホスホリル基、アシル基又はイオン性親水性基を表す。これらの基は、更に置換基を有していてもよい。
Z1、Z2、Z3、及びZ4は、それぞれ独立に、置換若しくは無置換のアルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアラルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のヘテロ環基を表す。但し、Z1、Z2、Z3、及びZ4のうち少なくとも1つは、イオン性親水性基を置換基として有する。
l、m、n、p、q1、q2、q3及びq4は、それぞれ独立に、1又は2を表す。
M1は、水素原子、金属元素、金属酸化物、金属水酸化物又は金属ハロゲン化物を表す。
一般式(I-2):
(一般式(I-2)中、
R1、R4、R5、R8、R9、R12、R13及びR16は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、シクロアルキル基、アルケニル基、アラルキル基、アリール基、ヘテロ環基、シアノ基、ヒドロキシル基、ニトロ基、アミノ基、アルキルアミノ基、アルコキシ基、アリールオキシ基、アミド基、アリールアミノ基、ウレイド基、スルファモイルアミノ基、アルキルチオ基、アリールチオ基、アルコキシカルボニルアミノ基、スルホンアミド基、カルバモイル基、スルファモイル基、アルコキシカルボニル基、ヘテロ環オキシ基、アゾ基、アシルオキシ基、カルバモイルオキシ基、シリルオキシ基、アリールオキシカルボニル基、アリールオキシカルボニルアミノ基、イミド基、ヘテロ環チオ基、ホスホリル基、アシル基又はイオン性親水性基を表す。これらの基は、更に置換基を有していてもよい。
Z5、Z6、Z7、及びZ8は、それぞれ独立に、置換若しくは無置換のアルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアラルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のヘテロ環基を表す。但し、Z5、Z6、Z7、及びZ8のうち少なくとも1つは、イオン性親水性基を置換基として有する。
t、u、v、w、q5、q6、q7及びq8は、それぞれ独立に、1又は2を表す。
M2は、水素原子、金属元素、金属酸化物、金属水酸化物又は金属ハロゲン化物を表す。)
一般式(II-2):
(一般式(II-2)中、
Pはそれぞれ独立に窒素原子又はCHを表し、少なくとも1つのPは窒素原子を表す。ただし、Pを含む4つの環において、それぞれ、窒素原子を表すPは2以下である。
R21及びR22はそれぞれ独立に、水素原子又は置換若しくは無置換のアルキル基を表す。
R23は水素原子又は置換若しくは無置換の炭化水素基を表す。
R24は置換若しくは無置換の炭化水素基を表す。
R23及びR24は窒素原子と共に互いに結合して置換若しくは無置換のヘテロ環を形成してもよい。
x、y、及びzはそれぞれ独立に0以上4以下を表す。
x+y+zは1以上4以下である。)
一般式(III-2):
(一般式(III-2)中、R17及びR18はそれぞれ独立して水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアラルキル基、置換若しくは無置換のアリール基、置換若しくは無置換のヘテロ環基、置換若しくは無置換のアルケニル基を表す。Aは二価の連結基をそれぞれ表し、隣接するR17、R18、及びAは互いに連結して環を形成しても良い。Y及びZは、それぞれ独立してハロゲン原子、水酸基、スルホン酸基、カルボキシル基、アミノ基、置換若しくは無置換のアルコキシ基、置換若しくは無置換のシクロアルキルオキシ基、置換若しくは無置換のアリロキシ基、置換若しくは無置換のヘテロ環オキシ基、置換若しくは無置換のアラルキルオキシ基、置換若しくは無置換のアルケニルオキシ基、置換若しくは無置換のアルキルアミノ基、置換若しくは無置換のシクロアルキルアミノ基、置換若しくは無置換のアリールアミノ基、置換若しくは無置換のヘテロ環アミノ基、置換若しくは無置換のアラルキルアミノ基、置換若しくは無置換のアルケニルアミノ基、置換若しくは無置換のジアルキルアミノ基、置換若しくは無置換のアルキルチオ基、置換若しくは無置換のアリールチオ基、置換若しくは無置換のヘテロ環チオ基、置換若しくは無置換のアラルキルチオ基、置換若しくは無置換のアルケニルチオ基を表す。但し、Y、Zのうち少なくとも1つは、スルホン酸基、カルボキシル基、又はイオン性親水性基を置換基として有する基である。m、及びnは1から3であり、かつmとnの和は2から4である。)
〔2〕
一般式(I-2)で表されるフタロシアニン染料におけるZ5、Z6、Z7、及びZ8が、それぞれ独立に、置換若しくは無置換のアルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のヘテロ環基を表すことを特徴とする〔1〕に記載の着色組成物。
〔3〕
一般式(I-2)で表されるフタロシアニン染料におけるR1、R4、R5、R8、R9、R12、R13及びR16が、水素原子であることを特徴とする〔1〕又は〔2〕に記載の着色組成物。
〔4〕
一般式(I-2)で表されるフタロシアニン染料におけるZ5、Z6、Z7、及びZ8が、置換アルキル基を表し、アルキル基が有する置換基の少なくとも一つが-SONHR基(但しRは置換若しくは無置換のアルキル基、又は置換若しくは無置換のフェニル基を表す)である〔1〕~〔3〕のいずれか1項に記載の着色組成物。
〔5〕
一般式(I-2)で表されるフタロシアニン染料におけるt、u、v及びwが1である〔1〕~〔4〕のいずれか1項に記載の着色組成物。
〔6〕
一般式(I-2)で表されるフタロシアニン染料におけるq5、q6、q7及びq8が2である〔1〕~〔5〕のいずれか1項に記載の着色組成物。
〔7〕
一般式(II-2)で表されるアザフタロシアニン染料が、下記一般式(II-3-1)又は一般式(II-3-2)で表されるアザフタロシアニン染料である〔1〕に記載の着色組成物。
(一般式(II-3-1)及び一般式(II-3-2)中、
Pはそれぞれ独立に窒素原子又はCHを表し、少なくとも1つのPは窒素原子を表す。
R21及びR22はそれぞれ独立に、水素原子又は置換若しくは無置換のアルキル基を表す。
R23及びR24はそれぞれ独立に、水素原子又は置換若しくは無置換のアルキル基又は置換若しくは無置換のアリール基を表す。
x、y、及びzはそれぞれ独立に0以上4以下を表す。
x+y+zは1以上4以下である。)
〔8〕
前記一般式(II-2)、一般式(II-3-1)又は一般式(II-3-2)における、R23が水素原子を表し、R24が下記一般式(T1)で表される置換基で置換された置換アルキル基である〔1〕又は〔7〕に記載の着色組成物。
(一般式(T1)中、
Lは単結合又は置換若しくは無置換のアルキレン基を表す。
Xはそれぞれ独立に-OR25、-SR25、及び-NR25R26より選択される置換基を表し、R25及びR26はそれぞれ独立に、水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のヘテロ環基を表し、R25及びR26の少なくとも一つはイオン性親水性基を置換基として有する。R27は水素原子又は置換若しくは無置換のアルキル基を表す。)
〔9〕
前記一般式(T1)で表される置換基が、下記一般式(T2)で表される置換基である〔8〕に記載の着色組成物。
(一般式(T2)中、
Lは単結合又は置換若しくは無置換のアルキレン基を表す。
R29、R210、及びR211はそれぞれ独立に、水素原子、又は置換若しくは無置換のアルキル基を表し、R212は、置換アルキル基、置換アリール基、又は置換ヘテロ環基を表し、イオン性親水性基を少なくとも一つ置換基として有する。R27は水素原子又は置換若しくは無置換のアルキル基を表す。)
〔10〕
前記一般式(III-2)で表されるフタロシアニン染料が、一般式(III-2-1)で表されるフタロシアニン染料である〔1〕に記載の着色組成物。
(一般式(III-2-1)中、R27及びR28はそれぞれ独立して水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアラルキル基、置換若しくは無置換のアリール基、置換若しくは無置換のヘテロ環基、置換若しくは無置換のアルケニル基を表す。Aは二価の連結基をそれぞれ表し、隣接するR27、R28、及びAは互いに連結して環を形成しても良い。
R29、R210、及びR211はそれぞれ独立に、水素原子、又は置換若しくは無置換のアルキル基を表し、R212は、スルホン酸基、カルボキシル基、置換アルキル基、置換アリール基、又は置換ヘテロ環基を表し、イオン性親水性基を少なくとも一つ置換基として有する。m、及びnは1から3であり、かつmとnの和は2から4である。)
〔11〕
一般式(1)で表されるフタロシアニン染料におけるR2、R3、R6、R7、R10、R11、R14及びR15が、水素原子であることを特徴とする〔1〕~〔10〕のいずれか1項に記載の着色組成物。
〔12〕
一般式(1)で表されるフタロシアニン染料におけるZ1、Z2、Z3、及びZ4が、それぞれ独立に、置換若しくは無置換のアルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のヘテロ環基を表すことを特徴とする〔1〕~〔11〕のいずれか1項に記載の着色組成物。
〔13〕
一般式(1)で表されるフタロシアニン染料におけるl、m、n及びpが1である〔1~〔12〕のいずれか1項に記載の着色組成物。
〔14〕
一般式(1)で表されるフタロシアニン染料におけるq1、q2、q3及びq4が2である〔1〕~〔13〕のいずれか1項に記載の着色組成物。
〔15〕
更に下記式(AB9)で表される化合物を含む〔1〕~〔14〕のいずれか1項に記載の着色組成物。
(式(AB9)中Meはメチル基を表し、Mは水素原子、リチウム、ナトリウム、カリウム又はアンモニウムを表す。)
〔16〕
一般式(1)で表されるフタロシアニン染料と、一般式(I-2)、一般式(II-2)又は一般式(III-2)で表されるフタロシアニン染料との質量比が50/50~10/90である〔1〕~〔15〕のいずれか1項に記載の着色組成物。
〔17〕
一般式(1)で表されるフタロシアニン染料の含有量が1~20質量%である〔1〕~〔16〕のいずれか1項に記載の着色組成物。
〔18〕
一般式(1)、及び、一般式(I-2)、一般式(II-2)又は一般式(III-2)で表されるフタロシアニン染料の総量と、式(AB9)で表される化合物との質量比が90/10~99/1である〔15〕~〔17〕のいずれか1項に記載の着色組成物。
〔19〕
〔1〕~〔18〕のいずれか1項に記載の着色組成物を含むインクジェット記録用インク。
本発明のIIの態様によれば、良好なオゾン堅牢性、高い印画濃度を有し、ブロンズ光沢を抑制し、優れた色相を実現し、更には光源依存性に優れた着色組成物及びインクジェット用記録インクが提供される。
本発明のIIIの態様によれば、良好なオゾン堅牢性、高い印画濃度を有し、ブロンズ光沢を抑制し、優れた色相を実現し、更には経時貯蔵安定性に優れた着色組成物及びインクジェット用記録インクが提供される。
ハロゲン原子(例えば、塩素原子、臭素原子);炭素数1~12の直鎖状又は分岐状鎖アルキル基、炭素数7~18のアラルキル基、炭素数2~12のアルケニル基、炭素数2~12の直鎖状又は分岐鎖状アルキニル基、側鎖を有していてもよい炭素数3~12のシクロアルキル基、側鎖を有していてもよい炭素数3~12のシクロアルケニル基(上記基の具体的例として、例えばメチル、エチル、プロピル、イソプロピル、t-ブチル、2-メタンスルホニルエチル、3-フェノキシプロピル、トリフルオロメチル、シクロペンチル):アリール基(例えば、フェニル、4-t-ブチルフェニル、2,4-ジ-t-アミルフェニル);ヘテロ環基(例えば、イミダゾリル、ピラゾリル、トリアゾリル、2-フリル、2-チエニル、2-ピリミジニル、2-ベンゾチアゾリル);アルキルオキシ基(例えば、メトキシ、エトキシ、2-メトキシエトキシ、2-メタンスルホニルエトキシ);アリールオキシ基(例えば、フェノキシ、2-メチルフェノキシ、4-t-ブチルフェノキシ、3-ニトロフェノキシ、3-t-ブチルオキシカルバモイルフェノキシ、3-メトキシカルバモイル);アシルアミノ基(例えば、アセトアミド、ベンズアミド、4-(3-t-ブチル-4-ヒドロキシフェノキシ)ブタンアミド);アルキルアミノ基(例えば、メチルアミノ、ブチルアミノ、ジエチルアミノ、メチルブチルアミノ);アニリノ基(例えば、フェニルアミノ、2-クロロアニリノ;ウレイド基(例えば、フェニルウレイド、メチルウレイド、N,N-ジブチルウレイド);スルファモイルアミノ基(例えば、N,N-ジプロピルスルファモイルアミノ);アルキルチオ基(例えば、メチルチオ、オクチルチオ、2-フェノキシエチルチオ);アリールチオ基(例えば、フェニルチオ、2-ブトキシ-5-t-オクチルフェニルチオ、2-カルボキシフェニルチオ);アルキルオキシカルボニルアミノ基(例えば、メトキシカルボニルアミノ);スルホンアミド基(例えば、メタンスルホンアミド、ベンゼンスルホンアミド、p-トルエンスルホンアミド、オクタデカン);カルバモイル基(例えば、N-エチルカルバモイル、N,N-ジブチルカルバモイル);スルファモイル基(例えば、N-エチルスルファモイル、N,N-ジプロピルスルファモイル、N,N-ジエチルスルファモイル);スルホニル基(例えば、メタンスルホニル、オクタンスルホニル、ベンゼンスルホニル、トルエンスルホニル);アルキルオキシカルボニル基(例えば、メトキシカルボニル、ブチルオキシカルボニル);ヘテロ環オキシ基(例えば、1-フェニルテトラゾール-5-オキシ、2-テトラヒドロピラニルオキシ);アゾ基(例えば、フェニルアゾ、4-メトキシフェニルアゾ、4-ピバロイルアミノフェニルアゾ、2-ヒドロキシ-4-プロパノイルフェニルアゾ);アシルオキシ基(例えば、アセトキシ);カルバモイルオキシ基(例えば、N-メチルカルバモイルオキシ、N-フェニルカルバモイルオキシ);シリルオキシ基(例えば、トリメチルシリルオキシ、ジブチルメチルシリルオキシ);アリールオキシカルボニルアミノ基(例えば、フェノキシカルボニルアミノ);イミド基(例えば、N-スクシンイミド、N-フタルイミ);ヘテロ環チオ基(例えば、2-ベンゾチアゾリルチオ、2,4-ジ-フェノキシ-1,3,5-トリアゾール-6-チオ、2-ピリジルチオ);スルフィニル基(例えば、3-フェノキシプロピルスルフィニル);ホスホニル基(例えば、フェノキシホスホニル、オクチルオキシホスホニル、フェニルホスホニル);アリールオキシカルボニル基(例えば、フェノキシカルボニル);アシル基(例えば、アセチル、3-フェニルプロパノイル、ベンゾイル);イオン性親水性基(例えば、カルボキシル基、スルホ基、及び4級アンモニウム基);その他シアノ基、ヒドロキシル基、ニトロ基、アミノ基。
まず、一般式(1)で表されるフタロシアニン染料について詳細に説明する。
R2、R3、R6、R7、R10、R11、R14及びR15は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、シクロアルキル基、アルケニル基、アラルキル基、アリール基、ヘテロ環基、シアノ基、ヒドロキシル基、ニトロ基、アミノ基、アルキルアミノ基、アルコキシ基、アリールオキシ基、アミド基、アリールアミノ基、ウレイド基、スルファモイルアミノ基、アルキルチオ基、アリールチオ基、アルコキシカルボニルアミノ基、スルホンアミド基、カルバモイル基、スルファモイル基、アルコキシカルボニル基、ヘテロ環オキシ基、アゾ基、アシルオキシ基、カルバモイルオキシ基、シリルオキシ基、アリールオキシカルボニル基、アリールオキシカルボニルアミノ基、イミド基、ヘテロ環チオ基、ホスホリル基、アシル基又はイオン性親水性基を表す。これらの基は、更に置換基を有していてもよい。
Z1、Z2、Z3、及びZ4は、それぞれ独立に、置換若しくは無置換のアルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアラルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のヘテロ環基を表す。但し、Z1、Z2、Z3、及びZ4のうち少なくとも1つは、イオン性親水性基を置換基として有する。
l、m、n、p、q1、q2、q3及びq4は、それぞれ独立に、1又は2を表す。
M1は、水素原子、金属元素、金属酸化物、金属水酸化物又は金属ハロゲン化物を表す。
次に、一般式(I-2)で表されるフタロシアニン染料について詳細に説明する。
R1、R4、R5、R8、R9、R12、R13及びR16は、それぞれ独立に、前記一般式(1)中のR2、R3、R6、R7、R10、R11、R14及びR15と各々同義である。
Z5、Z6、Z7、及びZ8は、それぞれ独立に、前記一般式(1)中のZ1、Z2、Z3、及びZ4と各々同義である。
t、u、v、w、q5、q6、q7及びq8は、それぞれ独立に、1又は2を表す。
M2は、前記一般式(1)中のM1と同義である。
これらの基は、更に置換基を有していてもよい。置換基としては、上記置換基群Aに記載の置換基が挙げられる。
Z5、Z6、Z7、及びZ8は、置換若しくは無置換のアルキル基、置換若しくは無置換のアリール基、置換若しくは無置換のヘテロ環基が好ましく、置換のアルキル基、置換のアリール基、置換のヘテロ環基がより好ましく、置換のアルキル基であることが更に好ましい。また、置換のアルキル基が有する置換基の少なくとも一つが、-SONHR基であることがオゾン堅牢性の観点から最も好ましい。
Z5、Z6、Z7、及びZ8のうち少なくとも1つが置換基として有するイオン性親水性基は、前記一般式(1)中のZ1、Z2、Z3、及びZ4が置換基として有するイオン性親水性基と同義であり、好ましい例も同様である。
本発明に用いられるフタロシアニン誘導体は、例えば白井-小林共著、(株)アイピーシー発行「フタロシアニン-化学と機能-」(P.1~62)、C.C.Leznoff-A.B.P.Lever共著、VCH発行‘Phthalocyanines-Properties and Applications’(P.1~54)等に記載、引用若しくはこれらに類似の方法を組み合わせて合成することができる。
本発明の一般式(I-2)で表されるフタロシアニン染料のうちR1、R4、R5、R8、R9、R12、R13及びR16が水素、q5、q6、q7及びq8が2である化合物は、例えば下記一般式(V)で表されるフタロニトリル誘導体及び/又は下記一般式(VI)で表されるジイミノイソインドリン誘導体と下記M-(Y)dで表される金属誘導体を反応させることにより合成される。
R1、R4、R5、R8、R9、R12、R13及びR16は、それぞれ独立に、前記一般式(1)中のR2、R3、R6、R7、R10、R11、R14及びR15と各々同義である。
Z5、Z6、Z7、及びZ8は、それぞれ独立に、前記一般式(1)中のZ1、Z2、Z3、及びZ4と各々同義である。
t、u、v、w、q5、q6、q7及びq8は、それぞれ独立に、1又は2を表す。
M及びM2は、前記一般式(1)中のM1と同義であり、M=M2である。
Yはハロゲン原子、酢酸陰イオン、アセチルアセトネート、酸素などの1価又は2価の配位子を示し、dは1~4の整数である。
Pはそれぞれ独立に窒素原子又はCHを表し、少なくとも1つのPは窒素原子を表す。ただし、Pを含む4つの環において、それぞれ、窒素原子を表すPは2以下である。
R21及びR22はそれぞれ独立に、水素原子又は置換若しくは無置換のアルキル基を表す。
R23は水素原子又は置換若しくは無置換の炭化水素基を表す。
R24は置換若しくは無置換の炭化水素基を表す。
R23及びR24は窒素原子と共に互いに結合して置換若しくは無置換のヘテロ環を形成してもよい。
x、y、及びzはそれぞれ独立に0以上4以下を表す。
x+y+zは1以上4以下である。)
Pはそれぞれ独立に窒素原子又はCHを表し、少なくとも1つのPは窒素原子を表す。
R21及びR22はそれぞれ独立に、水素原子又は置換若しくは無置換のアルキル基を表す。
R23は水素原子又は置換若しくは無置換の炭化水素基を表す。
R24は置換若しくは無置換の炭化水素基を表す。
R23及びR24は窒素原子と共に互いに結合して置換若しくは無置換のヘテロ環を形成してもよい。
x、y、及びzはそれぞれ独立に0以上4以下を表す。
x+y+zは1以上4以下である。)
R21はメチル基又は水素原子を表すことが好ましく、水素原子を表すことがより好ましい。
R22は水素原子又は置換若しくは無置換の炭素原子数が1~4のアルキル基を表すことが好ましく、置換基を有する場合の置換基はヒドロキシル基であることが好ましく、n-プロピル又は水素原子を表すことが好ましく、水素原子を表すことがより好ましい。
R24は下記一般式(T1)で表される置換基であることが好ましい。
Lは単結合又は置換若しくは無置換のアルキレン基を表す。
Xはそれぞれ独立に-OR25、-SR25、及び-NR25R26より選択される置換基を表し、R25及びR26はそれぞれ独立に、水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のヘテロ環基を表し、R25及びR26の少なくとも一つはイオン性親水性基を置換基として有する。R27は水素原子又は置換若しくは無置換のアルキル基を表す。)
R25及びR26が表す置換若しくは無置換のアルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のヘテロ環基としては、R23及びR24が表すものと同様の基が挙げられる。
R27が表す置換若しくは無置換のアルキル基としては、置換基を除いたときの炭素原子数が1~12のアルキル基が好ましく、炭素原子数が1~8のアルキル基がより好ましく、炭素原子数が1~4のアルキル基が更に好ましい。アルキル基としては、メチル、エチル、ブチル、イソプロピル、t-ブチルが好ましい。置換基としては、置換基群Aが挙げられる。
R27はメチル基又は水素原子を表すことが好ましく、水素原子を表すことがより好ましい。
Lは単結合又は置換若しくは無置換のアルキレン基を表す。
R29、R210、及びR211はそれぞれ独立に、水素原子、又は置換若しくは無置換のアルキル基を表し、R212は、置換アルキル基、置換アリール基、又は置換ヘテロ環基を表し、イオン性親水性基を少なくとも一つ置換基として有する。R27は水素原子又は置換若しくは無置換のアルキル基を表す。)
R29、R210、及びR211が表す置換若しくは無置換のアルキル基としては、一般式(T1)におけるR27で挙げたものと同義であり好ましいものも同様である。
R27、R29、R210、及びR211はメチル基又は水素原子を表すことが好ましく、水素原子を表すことがより好ましい。
R212は1~3個のイオン性親水性基で置換されたアリール基であることが好ましく、2個のイオン性親水性基(好ましくはカルボキシル基又はスルホ基)で置換されたアリール基であることがより好ましい。
R27及びR28はメチル基又は水素原子を表すことが好ましく、水素原子を表すことがより好ましい。
R17及びR18が表すアラルキル基としては、置換基を有するアラルキル基及び無置換のアラルキル基が挙げられる。アラルキル基としては、置換基を除いたときの炭素原子数が7~12のアラルキル基が好ましい。置換基の例には、イオン性親水性基が挙げられる。アラルキル基の例には、ベンジル基、及び2-フェネチル基が好ましい。
R29、R210、及びR211はそれぞれ独立に、水素原子、又は置換若しくは無置換のアルキル基を表し、R212は、スルホン酸基、カルボキシル基、置換アルキル基、置換アリール基、又は置換ヘテロ環基を表し、イオン性親水性基を少なくとも一つ置換基として有する。スルホン酸基、カルボキシル基、又はイオン性親水性基を置換基として有する基である。m、及びnは1から3であり、かつmとnの和は2から4である。)
R29、R210、及びR211が表す置換若しくは無置換のアルキル基としては、炭素原子数が1~12のアルキル基が好ましく、炭素原子数が1~8のアルキル基がより好ましく、炭素原子数が1~4のアルキル基が更に好ましい。置換基としては、置換基群Aが挙げられ、ヒドロキシル基、アルコキシ基、シアノ基、ハロゲン原子及びイオン性親水性基が好ましく、ヒドロキシル基又はイオン性親水性基がより好ましい。アルキル基としては、メチル、エチル、ブチル、イソプロピル、n-プロピル、又はt-ブチルが好ましく、メチル、又はn-プロピルがより好ましく、n-プロピルが更に好ましい。
R27及びR28メチル基又は水素原子を表すことが好ましく、水素原子を表すことがより好ましい。
R212は1~3個のイオン性親水性基で置換されたアリール基であることが好ましく、2個のイオン性親水性基(好ましくはカルボキシル基又はスルホ基)で置換されたアリール基であることがより好ましい。
一般式(III-2)で表されるフタロシアニン誘導体は、例えば特開2004-329677号公報に記載の方法により合成することができる。
本発明の着色組成物は、更に下記式(AB9)で表される化合物(アシッドブルー9)を含有してもよい。
本発明のIの態様の着色組成物は、上記一般式(1)で表されるフタロシアニン染料と、上記一般式(I-2)で表されるフタロシアニン染料とを含有する。α-位置換型の一般式(1)の染料とβ-位置換型の一般式(I-2)の染料とを用いることにより、分子内ではなく分子間でのα位とβ位の比率調整が可能となり、結果、良好な堅牢性と高い印画濃度とを両立することが可能となる。
本発明のIIの態様の着色組成物は、上記一般式(1)で表されるフタロシアニン染料と、上記一般式(II-2)で表されるアザフタロシアニン染料とを含有する。α-位置換型の一般式(1)の染料とフタロシアニン骨格の一部に窒素原子を有する一般式(II-2)のアザフタロシアニン染料とを用いることにより、会合の制御が可能となり、結果、良好な堅牢性と高い印画濃度とを両立することが可能となる。
本発明のIIIの態様の着色組成物は、上記一般式(1)で表されるフタロシアニン染料と、上記一般式(III-2)で表されるフタロシアニン染料とを含有する。α-位置換型の一般式(1)の染料と特定の置換基を有する一般式(III-2)のフタロシアニン染料とを用いることにより、分子内ではなく分子間でのα位とβ位の比率調整が可能となり、結果、良好な堅牢性と高い印画濃度とを両立することが可能となる。
本発明の着色組成物は、好ましくは画像形成用着色組成物として用いることができる。本発明の着色組成物の用途としては、画像、特にカラー画像を形成するための画像記録材料が挙げられ、具体的には、以下に詳述するインクジェット方式記録材料を始めとして、感熱転写型画像記録材料、感圧記録材料、電子写真方式を用いる記録材料、転写式ハロゲン化銀感光材料、印刷インク、記録ペン等であり、好ましくはインクジェット方式記録材料、感熱転写型画像記録材料、電子写真方式を用いる記録材料であり、更に好ましくはインクジェット方式記録材料である。また、米国特許4808501号明細書、特開平6-35182号公報などに記載されているLCDやCCDなどの固体撮像素子で用いられているカラーフィルター各種繊維の染色のための染色液にも適用できる。本発明に用いるフタロシアニン染料は、その用途に適した溶解性、熱移動性などの物性を、置換基により調整して使用する。また、本発明に用いるフタロシアニン染料は、用いられる系に応じて均一な溶解状態、乳化分散のような分散された溶解状態で使用する事が出来る。
次に本発明のインクジェット記録用インクについて説明する。本発明のインクジェット記録用インクは、上記着色組成物を含む。インクジェット記録用インクは、親油性媒体や水性媒体中に前記フタロシアニン化合物を溶解及び/又は分散させることによって作製することができる。好ましくは、水性媒体を用いたインクである。必要に応じてその他の添加剤を、本発明の効果を害しない範囲内において含有される。その他の添加剤としては、例えば、乾燥防止剤(湿潤剤)、褪色防止剤、乳化安定剤、浸透促進剤、紫外線吸収剤、防腐剤、防黴剤、pH調整剤、表面張力調整剤、消泡剤、粘度調整剤、分散剤、分散安定剤、防錆剤、キレート剤等の公知の添加剤が挙げられる。これらの各種添加剤は、水溶性インクの場合にはインク液に直接添加する。油溶性染料を分散物の形で用いる場合には、染料分散物の調製後分散物に添加するのが一般的であるが、調製時に油相又は水相に添加してもよい。
本発明のインクジェット記録方法は、前記インクジェット記録用インクにエネルギーを供与して、公知の受像材料、即ち普通紙、樹脂コート紙、例えば特開平8-169172号公報、同8-27693号公報、同2-276670号公報、同7-276789号公報、同9-323475号公報、特開昭62-238783号公報、特開平10-153989号公報、同10-217473号公報、同10-235995号公報、同10-337947号公報、同10-217597号公報、同10-337947号公報等に記載されているインクジェット専用紙、フィルム、電子写真共用紙、布帛、ガラス、金属、陶磁器等に画像を形成する。
本明細書中で用いているアシッドブルー9は、市販品(東京化成製カタログ番号B0790)を透析チューブを用いて脱塩精製したものを用いた。
以下、実施例に本発明のフタロシアニン系色素誘導体の合成法を詳しく説明するが、出発物質、色素中間体及び合成ル-トについて限定されるものでない。
窒素気流下、4-ニトロフタロニトリル(東京化成)26.0gを200mLのDMSO(ジメチルスルホキシド)に溶解し、内温20℃で攪拌しているところへ、30.3gの3-メルカプト-プロパン-スルホン酸ナトリウム(アルドリッチ)を添加した。続いて、内温20℃で攪拌しているところへ、24.4gの無水炭酸ナトリウムを徐々に加えた。反応液を攪拌しながら、30℃まで加温し、同温度で1時間撹拌した。20℃まで冷却した後、反応液をヌッチェでろ過し、ろ液を15000mLの酢酸エチルにあけて晶析し、引き続き室温で30分間撹拌して、析出した粗結晶をヌッチェでろ過し、酢酸エチルで洗浄し、乾燥した。得られた粗結晶を、メタノール/酢酸エチルから再結晶して、42.5gの化合物Aを得た。1H-NMR(DMSO-d6),δ値TMS基準:1.9~2.0(2H,t);2.5~2.6(2H,m);3.2~3.3(2H,t);7.75~7.85(1H,d);7.93~8.03(1H,d);8.05~8.13(1H,s)
42.0gの化合物(A)を300mLの酢酸に溶解し、内温20℃で攪拌しているところへ、2.5gNa2WO4,2H2Oを添加した後、氷浴中、内温10℃まで冷却した。引き続き、32mLの過酸化水素水(30%)を発熱に注意しながら徐々に滴下した。内温15~20℃で30分間撹拌した後に、反応液を内温60℃まで加温して、同温度で1時間撹拌した。20℃まで冷却した後、反応液に1500mLの酢酸エチルを注入し、引き続き同温度にて30分間撹拌した後に、析出した粗結晶をヌッチェでろ過し、200mLの酢酸エチルで洗浄し、乾燥した。得られた粗結晶を、メタノール/酢酸エチルを用いて加熱洗浄して精製して、40.0gの化合物Bを得た。1H-NMR(DMSO-d6),δ値TMS基準:1.8~1.9(2H,t);2.4~2.5(2H,m);3.6~3.7(2H,t);8.3~8.4(1H,d);8.4~8.5(1H,d);8.6~8.7(1H,s)
冷却管の付いた三つ口フラスコに、n-アミルアルコール70mL加え、そこに化合物B6.7g、塩化銅(II)1.0gを加え、攪拌しながら室温で7.0mLの1,8-ジアザビシクロ[5.4.0]-7-ウンデセン(DBU)を滴下した。引き続き、反応液を内温100℃まで加温して、同温度で10時間撹拌した。40℃まで冷却した後、50℃の加温したメタノ-ル250mLを注入して、還流下で1時間攪拌した。次に、反応液を室温まで冷却した後、得られた固体をヌッチェでろ過し、200mLのメタノールで洗浄した。続いて得られた固体を塩化ナトリウムで飽和した100mLの1M塩酸水溶液に加え、未反応の銅塩を溶かし出した。不溶物をろ過した後、ろ液に300mLのメタノールを滴下して晶析した後、得られた粗結晶をヌッチェでろ過し、200mLのメタノールで洗浄した。粗結晶を、50mLの水に溶解させた後、水溶液を攪拌しながら酢酸ナトリウムの飽和メタノール溶液100mLを徐々に添加して造塩した。更に、攪拌しながら還流温度まで加温し、同温度で1時間撹拌した。室温まで冷却した後、析出した結晶をろ過し、メタノールで洗浄した。引き続き、80%メタノール100mLに得られた結晶を加え、1時間還流下撹拌し、室温まで冷却した後、析出した結晶をろ過し、更に、70%メタノール水溶液100mLに得られた結晶を加え、1時間還流撹拌し、室温まで冷却した後、析出した結晶をろ過し、メタノ-ル100mLで洗浄後乾燥して、3.8gの例示化合物102βを青色結晶として得た。
λmax(吸収極大波長):629.1nm;εmax(吸収極大波長におけるモル吸光係数)=6.19×104(水溶液中)。得られた化合物を分析(質量分析法:ESI-MS、元素分析、中和滴定等種々の機器解析方法により測定)した結果、本明細書中で定義したフタロシアニン銅(II)-置換位置が、β-位置換型{それぞれの各ベンゼン核の(2又は3位)、(6又は7位)、(10又は11位)、(14又は15位)に-{SO2-(CH2)3-SO3Na}基を1個、銅フタロシアニン一分子中-{SO2-(CH2)3-SO3Na}基を合計4個有する}であることが確認できた。
(実施例I-1)
下記の成分に脱イオン水を加え100gとした後、30~40℃で加熱しながら1時間撹拌した。その後NaOH10mol/LにてpH=9に調製し、平均孔径0.25μmのミクロフィルターで減圧濾過しシアン用インク液を調製した。
フタロシアニン染料(化合物I-2B)2.7g
ジエチレングリコール2g
グリセリン12g
ジエチレングリコールモノブチルエーテル23g
2-ピロリドン8g
トリエタノールアミン 1.79g
ベンゾトリアゾール 0.006g
サーフィノールTG 0.85g
PROXEL XL2 0.18g
染料の種類と添加量を、下記表I-17~I-19に示すように変更した以外は、実施例I-1のインク液の調製と同様にして、実施例I-2~I-74及び比較例I-1~I-20のインク液を調製した。
以上の各実施例(実施例I-1~I-74)及び比較例(比較例I-1~I-20)のインクジェット用インクについて、下記評価を行った。その結果を表I-17~I-19に示した。なお、画像記録は、各インクジェット用インクを、インクジェットプリンター(EPSON(株)社製;PM-700C)でフォト光沢紙(PT-101、Canon)、及び普通紙(GF500、Canon)に画像を記録した。
前記画像を形成したフォト光沢紙を、オゾンガス濃度が0.5±0.1ppm、室温、暗所に設定されたボックス内に7日間放置し、オゾンガス下放置前後の画像濃度を反射濃度計(X-Rite310TR)を用いて測定し、色素残存率として評価した。なお、前記反射濃度は、1、1.5及び2.0の3点で測定した。ボックス内のオゾンガス濃度は、APPLICS製オゾンガスモニター(モデル:OZG-EM-01)を用いて設定した。何れの濃度でも色素残存率が70%以上の場合をA、1又は2点が70%未満をB、全ての濃度で70%未満の場合をCとして、三段階で評価した。
普通紙における印画濃度100%における反射濃度を画像濃度を反射濃度計(X-Rite310TR)を用いて測定し、印画濃度が1.10以上の場合をA、1.00以上1.10未満の場合をB、1.00未満の場合をCとして、三段階で評価した。
印画したサンプルの最高濃度部分を白色蛍光灯下で目視で観測し、赤銅がかった光沢が観測されない場合をA、うっすらと観測される場合をB、明らかに観測される場合をCの三段階で評価した。
印画したサンプルを目視で観測し、純色のシアンである場合をA、やや赤みがかった青色に近いシアンをB、明らかに青色の場合をCの三段階で評価した。
下記の成分に脱イオン水を加え33.3gとした後、50℃で加熱しながら1時間撹拌した。その後NaOH10mol/LにてpH=9に調製し、濃厚水溶液を調製した。
フタロシアニン染料(化合物I-2B)4.5g
フタロシアニン染料及び染料添加量を、下記表I-20~I-21に示すように変更した以外は、実施例I-101の濃厚水溶液の調製と同様にして、実施例I-102~I-132及び比較例I-101~I-108のインク液を調製した。
以上の各実施例(実施例I-101~I-132)及び比較例(比較例I-101~I-108)の濃厚水溶液に関して、密封かつ静置状態で室温2週間経時貯蔵し、目視にて溶解状態を保っているものをA、染料の析出や分離が起きたものをBの2段階で評価した。その結果を表I-20~I-21に示した。
(実施例II-1)
下記の成分に脱イオン水を加え100gとした後、30~40℃で加熱しながら1時間撹拌した。その後NaOH10mol/LにてpH=9に調製し、平均孔径0.25μmのミクロフィルターで減圧濾過しシアン用インク液を調製した。
フタロシアニン染料(化合物II-3A)3.5g
ジエチレングリコール2g
グリセリン12g
ジエチレングリコールモノブチルエーテル23g
2-ピロリドン8g
トリエタノールアミン 1.79g
ベンゾトリアゾール 0.006g
サーフィノール465(商品名、エアープロダクツ社製)0.85g
PROXEL XL2 (商品名、富士フイルムイメージングカラランツ社製)0.18g
フタロシアニン染料及び染料添加量を、下記表II-23に示すように変更した以外は、実施例II-1のインク液の調製と同様にして、実施例II-2~II-10及び比較例II-1~II-6のインク液を調製した。
以上の各実施例(実施例II-1~II-10)及び比較例(比較例II-1~II-6)のインクジェット用インクについて、下記評価を行った。その結果を表II-23に示した。なお、画像記録は、各インクジェット用インクを、インクジェットプリンター(キヤノン社製;PIXUS Pro9000MkII)でフォト光沢紙(PT-101、Canon)、及び普通紙(GF500、Canon)に画像を記録した。
前記画像を形成したフォト光沢紙を、オゾンガス濃度が0.5±0.1ppm、室温、暗所に設定されたボックス内に7日間放置し、オゾンガス下放置前後の画像濃度を反射濃度計(X-Rite310TR)を用いて測定し、色素残存率として評価した。なお、前記反射濃度は、1、1.5及び2.0の3点で測定した。ボックス内のオゾンガス濃度は、APPLICS製オゾンガスモニター(モデル:OZG-EM-01)を用いて設定した。何れの濃度でも色素残存率が70%以上の場合をA、1又は2点が70%未満をB、全ての濃度で70%未満の場合をCとして、三段階で評価した。
普通紙における印画濃度100%における反射濃度を画像濃度(印画濃度)を反射濃度計(X-Rite310TR)を用いて測定し、印画濃度が1.10以上の場合をA、1.05以上1.10未満の場合をB、1.05未満の場合をCとして、三段階で評価した。
印画したサンプルの最高濃度部分を白色蛍光灯下で目視で観測し、赤銅がかった光沢が観測されない場合をA、うっすらと観測される場合をB、明らかに観測される場合をCの三段階で評価した。
印画したサンプルを目視で観測し、純色のシアンである場合をA、やや赤みがかった青色に近いシアンをB、明らかに青色の場合をCの三段階で評価した。
印画したサンプルに対して、標準光D50の下で観察したときの色と、標準光Aの下で観察したときの色の間の色差ΔEを算出し、ΔEが3未満をA、3以上をBで評価した。
(実施例III-1)
下記の成分に脱イオン水を加え100gとした後、30~40℃で加熱しながら1時間撹拌した。その後NaOH10mol/LにてpH=9に調製し、平均孔径0.25μmのミクロフィルターで減圧濾過しシアン用インク液を調製した。
フタロシアニン染料(化合物III-4A)3.5g
ジエチレングリコール2g
グリセリン12g
ジエチレングリコールモノブチルエーテル 23g
2-ピロリドン8g
トリエタノールアミン 1.79g
ベンゾトリアゾール 0.006g
サーフィノール465(商品名、エアープロダクツ社製)0.85g
PROXEL XL2(富士フイルムイメージングカララント社製)0.18g
フタロシアニン染料及び染料添加量を、下記表III-9に示すように変更した以外は、実施例III-1のインク液の調製と同様にして、実施例III-2~III-6及び比較例III-1~III-5のインク液を調製した。
以上の各実施例(実施例III-1~III-6)及び比較例(比較例III-1~III-5)のインクジェット用インクについて、下記評価を行った。その結果を表III-9に示した。なお、画像記録は、各インクジェット用インクを、インクジェットプリンター(EPSON(株)社製;PM-700C)でフォト光沢紙(PT-101、Canon)、及び普通紙(GF500、Canon)に画像を記録した。
前記画像を形成したフォト光沢紙を、オゾンガス濃度が5±0.1ppm、室温、暗所に設定されたボックス内に1日間放置し、オゾンガス下放置前後の画像濃度を反射濃度計(X-Rite310TR)を用いて測定し、色素残存率として評価した。なお、前記反射濃度は、1、1.5及び2.0の3点で測定した。ボックス内のオゾンガス濃度は、APPLICS製オゾンガスモニター(モデル:OZG-EM-01)を用いて設定した。何れの濃度でも色素残存率が70%以上の場合をA、1又は2点が70%未満をB、全ての濃度で70%未満の場合をCとして、三段階で評価した。
普通紙における印画濃度100%における反射濃度を画像濃度を反射濃度計(X-Rite310TR)を用いて測定し、印画濃度が1.10以上の場合をA、1.05以上1.10未満の場合をB、1.05未満の場合をCとして、三段階で評価した。
印画したサンプルの最高濃度部分を白色蛍光灯下で目視で観測し、赤銅がかった光沢が観測されない場合をA、うっすらと観測される場合をB、明らかに観測される場合をCの三段階で評価した。
印画したサンプルを目視で観測し、純色のシアンである場合をA、やや赤みがかった青色に近いシアンをB、明らかに青色の場合をCの三段階で評価した。
下記の成分に脱イオン水を加え33.3gとした後、50℃で加熱しながら1時間撹拌した。その後NaOH10mol/LにてpH=9に調製し、濃厚水溶液を調製した。
フタロシアニン染料(化合物III-4A)3.5g
ジエチレングリコール 2g
グリセリン 12g
ジエチレングリコールモノブチルエーテル 23g
2-ピロリドン 8g
トリエタノールアミン 1.79g
ベンゾトリアゾール 0.006g
サーフィノール465(商品名、エアープロダクツ社製)0.85g
PROXEL XL2(富士フイルムイメージングカララント社製)0.18g
フタロシアニン染料及び染料添加量を、下記表III-10に示すように変更した以外は、実施例101の濃厚水溶液の調製と同様にして、実施例III-102~III-106及び比較例III-101~III-105のインク液を調製した。
以上の各実施例(実施例III-101~III-106)及び比較例(比較例III-101~III-105)の濃厚水溶液に関して、密封かつ静置状態で室温2週間経時貯蔵し、目視にて溶解状態を保っているものをA、染料の析出や分離が起きたものをBの2段階で評価した。
本発明のIIの態様によれば、良好なオゾン堅牢性、高い印画濃度を有し、ブロンズ光沢を抑制し、優れた色相を実現し、更には光源依存性に優れた着色組成物及びインクジェット用記録インクが提供される。
本発明のIIIの態様によれば、良好なオゾン堅牢性、高い印画濃度を有し、ブロンズ光沢を抑制し、優れた色相を実現し、更には経時貯蔵安定性に優れた着色組成物及びインクジェット用記録インクが提供される。
本出願は、2012年8月21日出願の日本特許出願(特願2012-182688)、2011年11月30日出願の日本特許出願(特願2011-262830)、2011年11月30日出願の日本特許出願(特願2011-262829)、及び2011年11月8日出願の日本特許出願(特願2011-244971)に基づくものであり、その内容はここに参照として取り込まれる。
Claims (19)
- 下記一般式(1)で表されるフタロシアニン染料と、下記一般式(I-2)、下記一般式(II-2)又は下記一般式(III-2)で表されるフタロシアニン染料とを含むことを特徴とする着色組成物。
一般式(1)中、
R2、R3、R6、R7、R10、R11、R14及びR15は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、シクロアルキル基、アルケニル基、アラルキル基、アリール基、ヘテロ環基、シアノ基、ヒドロキシル基、ニトロ基、アミノ基、アルキルアミノ基、アルコキシ基、アリールオキシ基、アミド基、アリールアミノ基、ウレイド基、スルファモイルアミノ基、アルキルチオ基、アリールチオ基、アルコキシカルボニルアミノ基、スルホンアミド基、カルバモイル基、スルファモイル基、アルコキシカルボニル基、ヘテロ環オキシ基、アゾ基、アシルオキシ基、カルバモイルオキシ基、シリルオキシ基、アリールオキシカルボニル基、アリールオキシカルボニルアミノ基、イミド基、ヘテロ環チオ基、ホスホリル基、アシル基又はイオン性親水性基を表す。これらの基は、更に置換基を有していてもよい。
Z1、Z2、Z3、及びZ4は、それぞれ独立に、置換若しくは無置換のアルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアラルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のヘテロ環基を表す。但し、Z1、Z2、Z3、及びZ4のうち少なくとも1つは、イオン性親水性基を置換基として有する。
l、m、n、p、q1、q2、q3及びq4は、それぞれ独立に、1又は2を表す。
M1は、水素原子、金属元素、金属酸化物、金属水酸化物又は金属ハロゲン化物を表す。
一般式(I-2):
(一般式(I-2)中、
R1、R4、R5、R8、R9、R12、R13及びR16は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、シクロアルキル基、アルケニル基、アラルキル基、アリール基、ヘテロ環基、シアノ基、ヒドロキシル基、ニトロ基、アミノ基、アルキルアミノ基、アルコキシ基、アリールオキシ基、アミド基、アリールアミノ基、ウレイド基、スルファモイルアミノ基、アルキルチオ基、アリールチオ基、アルコキシカルボニルアミノ基、スルホンアミド基、カルバモイル基、スルファモイル基、アルコキシカルボニル基、ヘテロ環オキシ基、アゾ基、アシルオキシ基、カルバモイルオキシ基、シリルオキシ基、アリールオキシカルボニル基、アリールオキシカルボニルアミノ基、イミド基、ヘテロ環チオ基、ホスホリル基、アシル基又はイオン性親水性基を表す。これらの基は、更に置換基を有していてもよい。
Z5、Z6、Z7、及びZ8は、それぞれ独立に、置換若しくは無置換のアルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアラルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のヘテロ環基を表す。但し、Z5、Z6、Z7、及びZ8のうち少なくとも1つは、イオン性親水性基を置換基として有する。
t、u、v、w、q5、q6、q7及びq8は、それぞれ独立に、1又は2を表す。
M2は、水素原子、金属元素、金属酸化物、金属水酸化物又は金属ハロゲン化物を表す。)
一般式(II-2):
(一般式(II-2)中、
Pはそれぞれ独立に窒素原子又はCHを表し、少なくとも1つのPは窒素原子を表す。ただし、Pを含む4つの環において、それぞれ、窒素原子を表すPは2以下である。
R21及びR22はそれぞれ独立に、水素原子又は置換若しくは無置換のアルキル基を表す。
R23は水素原子又は置換若しくは無置換の炭化水素基を表す。
R24は置換若しくは無置換の炭化水素基を表す。
R23及びR24は窒素原子と共に互いに結合して置換若しくは無置換のヘテロ環を形成してもよい。
x、y、及びzはそれぞれ独立に0以上4以下を表す。
x+y+zは1以上4以下である。)
一般式(III-2):
(一般式(III-2)中、R17及びR18はそれぞれ独立して水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアラルキル基、置換若しくは無置換のアリール基、置換若しくは無置換のヘテロ環基、置換若しくは無置換のアルケニル基を表す。Aは二価の連結基をそれぞれ表し、隣接するR17、R18、及びAは互いに連結して環を形成しても良い。Y及びZは、それぞれ独立してハロゲン原子、水酸基、スルホン酸基、カルボキシル基、アミノ基、置換若しくは無置換のアルコキシ基、置換若しくは無置換のシクロアルキルオキシ基、置換若しくは無置換のアリロキシ基、置換若しくは無置換のヘテロ環オキシ基、置換若しくは無置換のアラルキルオキシ基、置換若しくは無置換のアルケニルオキシ基、置換若しくは無置換のアルキルアミノ基、置換若しくは無置換のシクロアルキルアミノ基、置換若しくは無置換のアリールアミノ基、置換若しくは無置換のヘテロ環アミノ基、置換若しくは無置換のアラルキルアミノ基、置換若しくは無置換のアルケニルアミノ基、置換若しくは無置換のジアルキルアミノ基、置換若しくは無置換のアルキルチオ基、置換若しくは無置換のアリールチオ基、置換若しくは無置換のヘテロ環チオ基、置換若しくは無置換のアラルキルチオ基、置換若しくは無置換のアルケニルチオ基を表す。但し、Y、Zのうち少なくとも1つは、スルホン酸基、カルボキシル基、又はイオン性親水性基を置換基として有する基である。m、及びnは1から3であり、かつmとnの和は2から4である。) - 一般式(I-2)で表されるフタロシアニン染料におけるZ5、Z6、Z7、及びZ8が、それぞれ独立に、置換若しくは無置換のアルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のヘテロ環基を表すことを特徴とする請求項1に記載の着色組成物。
- 一般式(I-2)で表されるフタロシアニン染料におけるR1、R4、R5、R8、R9、R12、R13及びR16が、水素原子であることを特徴とする請求項1又は2に記載の着色組成物。
- 一般式(I-2)で表されるフタロシアニン染料におけるZ5、Z6、Z7、及びZ8が、置換アルキル基を表し、アルキル基が有する置換基の少なくとも一つが-SONHR基(但しRは置換若しくは無置換のアルキル基、又は置換若しくは無置換のフェニル基を表す)である請求項1~3のいずれか1項に記載の着色組成物。
- 一般式(I-2)で表されるフタロシアニン染料におけるt、u、v及びwが1である請求項1~4のいずれか1項に記載の着色組成物。
- 一般式(I-2)で表されるフタロシアニン染料におけるq5、q6、q7及びq8が2である請求項1~5のいずれか1項に記載の着色組成物。
- 一般式(II-2)で表されるアザフタロシアニン染料が、下記一般式(II-3-1)又は一般式(II-3-2)で表されるアザフタロシアニン染料である請求項1に記載の着色組成物。
(一般式(II-3-1)及び一般式(II-3-2)中、
Pはそれぞれ独立に窒素原子又はCHを表し、少なくとも1つのPは窒素原子を表す。
R21及びR22はそれぞれ独立に、水素原子又は置換若しくは無置換のアルキル基を表す。
R23及びR24はそれぞれ独立に、水素原子又は置換若しくは無置換のアルキル基又は置換若しくは無置換のアリール基を表す。
x、y、及びzはそれぞれ独立に0以上4以下を表す。
x+y+zは1以上4以下である。) - 前記一般式(II-2)、一般式(II-3-1)又は一般式(II-3-2)における、R23が水素原子を表し、R24が下記一般式(T1)で表される置換基で置換された置換アルキル基である請求項1又は7に記載の着色組成物。
(一般式(T1)中、
Lは単結合又は置換若しくは無置換のアルキレン基を表す。
Xはそれぞれ独立に-OR25、-SR25、及び-NR25R26より選択される置換基を表し、R25及びR26はそれぞれ独立に、水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のヘテロ環基を表し、R25及びR26の少なくとも一つはイオン性親水性基を置換基として有する。R27は水素原子又は置換若しくは無置換のアルキル基を表す。) - 前記一般式(III-2)で表されるフタロシアニン染料が、一般式(III-2-1)で表されるフタロシアニン染料である請求項1に記載の着色組成物。
(一般式(III-2-1)中、R27及びR28はそれぞれ独立して水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアラルキル基、置換若しくは無置換のアリール基、置換若しくは無置換のヘテロ環基、置換若しくは無置換のアルケニル基を表す。Aは二価の連結基をそれぞれ表し、隣接するR27、R28、及びAは互いに連結して環を形成しても良い。
R29、R210、及びR211はそれぞれ独立に、水素原子、又は置換若しくは無置換のアルキル基を表し、R212は、スルホン酸基、カルボキシル基、置換アルキル基、置換アリール基、又は置換ヘテロ環基を表し、イオン性親水性基を少なくとも一つ置換基として有する。m、及びnは1から3であり、かつmとnの和は2から4である。) - 一般式(1)で表されるフタロシアニン染料におけるR2、R3、R6、R7、R10、R11、R14及びR15が、水素原子であることを特徴とする請求項1~10のいずれか1項に記載の着色組成物。
- 一般式(1)で表されるフタロシアニン染料におけるZ1、Z2、Z3、及びZ4が、それぞれ独立に、置換若しくは無置換のアルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のヘテロ環基を表すことを特徴とする請求項1~11のいずれか1項に記載の着色組成物。
- 一般式(1)で表されるフタロシアニン染料におけるl、m、n及びpが1である請求項1~12のいずれか1項に記載の着色組成物。
- 一般式(1)で表されるフタロシアニン染料におけるq1、q2、q3及びq4が2である請求項1~13のいずれか1項に記載の着色組成物。
- 一般式(1)で表されるフタロシアニン染料と、一般式(I-2)、一般式(II-2)又は一般式(III-2)で表されるフタロシアニン染料との質量比が50/50~10/90である請求項1~15のいずれか1項に記載の着色組成物。
- 一般式(1)で表されるフタロシアニン染料の含有量が1~20質量%である請求項1~16のいずれか1項に記載の着色組成物。
- 一般式(1)、及び、一般式(I-2)、一般式(II-2)又は一般式(III-2)で表されるフタロシアニン染料の総量と、式(AB9)で表される化合物との質量比が90/10~99/1である請求項15~17のいずれか1項に記載の着色組成物。
- 請求項1~18のいずれか1項に記載の着色組成物を含むインクジェット記録用インク。
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WO2014077223A1 (ja) * | 2012-11-15 | 2014-05-22 | 富士フイルム株式会社 | 着色組成物、該着色組成物を用いたインクジェット記録用インク、該インクジェット記録用インクを用いたインクジェット記録方法、インクカートリッジ、及び、インクジェット記録物 |
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- 2012-11-07 KR KR1020147012264A patent/KR101717829B1/ko active IP Right Grant
- 2012-11-07 CA CA2854674A patent/CA2854674C/en not_active Expired - Fee Related
- 2012-11-07 EP EP12847099.4A patent/EP2778201B1/en not_active Not-in-force
- 2012-11-07 AU AU2012336801A patent/AU2012336801B2/en not_active Ceased
- 2012-11-07 WO PCT/JP2012/078799 patent/WO2013069667A1/ja active Application Filing
- 2012-11-07 CN CN201280054831.6A patent/CN103917607B/zh not_active Expired - Fee Related
- 2012-11-08 TW TW101141669A patent/TWI546346B/zh not_active IP Right Cessation
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C.C. LEZNOFF-A.B.; P. LEVER: "Phthalocyanines Properties and Applications", VCH, pages: 1 - 54 |
See also references of EP2778201A4 |
SHIRAI KOBAYASHI: "Phthalocyanine - Chemistry and Function", IPC CO., LTD., pages: 1 - 62 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2014077291A1 (ja) * | 2012-11-15 | 2014-05-22 | 富士フイルム株式会社 | 着色組成物、インクジェット記録用インク、インクジェット記録方法、インクジェットプリンタカートリッジ、及びインクジェット記録物 |
WO2014077223A1 (ja) * | 2012-11-15 | 2014-05-22 | 富士フイルム株式会社 | 着色組成物、該着色組成物を用いたインクジェット記録用インク、該インクジェット記録用インクを用いたインクジェット記録方法、インクカートリッジ、及び、インクジェット記録物 |
EP2921530A4 (en) * | 2012-11-15 | 2016-08-03 | Fujifilm Corp | COLORING COMPOSITION, INK-INK PRINTING INK USING THE COLORING COMPOSITION, INK-JET PRINTING METHOD USING THIS INK FOR INK-JET PRINTING, INK CARTRIDGE, AND JET-PRINTED MATERIAL INK |
US9528014B2 (en) | 2012-11-15 | 2016-12-27 | Fujifilm Corporation | Coloring composition, ink for inkjet recording using the coloring composition, method for inkjet recording using the ink for inkjet recording, ink cartridge, and inkjet recording material |
Also Published As
Publication number | Publication date |
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TW201323532A (zh) | 2013-06-16 |
CN103917607A (zh) | 2014-07-09 |
KR101717829B1 (ko) | 2017-03-17 |
EP2778201A4 (en) | 2015-06-24 |
EP2778201A1 (en) | 2014-09-17 |
AU2012336801A2 (en) | 2014-11-06 |
US20140238264A1 (en) | 2014-08-28 |
TWI546346B (zh) | 2016-08-21 |
AU2012336801B2 (en) | 2016-11-03 |
EP2778201B1 (en) | 2016-04-06 |
KR20140091546A (ko) | 2014-07-21 |
CN103917607B (zh) | 2016-01-20 |
US8876915B2 (en) | 2014-11-04 |
CA2854674A1 (en) | 2013-05-16 |
AU2012336801A1 (en) | 2014-05-29 |
CA2854674C (en) | 2016-09-27 |
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