WO2010140519A1 - 緑色顔料、その製造方法、それを含んでなる着色剤およびそれを用いた着色方法 - Google Patents
緑色顔料、その製造方法、それを含んでなる着色剤およびそれを用いた着色方法 Download PDFInfo
- Publication number
- WO2010140519A1 WO2010140519A1 PCT/JP2010/058908 JP2010058908W WO2010140519A1 WO 2010140519 A1 WO2010140519 A1 WO 2010140519A1 JP 2010058908 W JP2010058908 W JP 2010058908W WO 2010140519 A1 WO2010140519 A1 WO 2010140519A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pigment
- polyhalogeno
- phthalocyanine
- green
- green pigment
- Prior art date
Links
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- 238000000034 method Methods 0.000 title claims description 55
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- 230000008569 process Effects 0.000 title claims description 13
- 239000000049 pigment Substances 0.000 claims abstract description 223
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 93
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 62
- 239000011701 zinc Substances 0.000 claims abstract description 62
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- 239000000203 mixture Substances 0.000 claims description 40
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- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims description 12
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- SVYSBVAQQFUQPV-UHFFFAOYSA-L bromo(chloro)zinc Chemical group Cl[Zn]Br SVYSBVAQQFUQPV-UHFFFAOYSA-L 0.000 claims 1
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- 239000003085 diluting agent Substances 0.000 description 1
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical class C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 125000005543 phthalimide group Chemical class 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 239000001039 zinc pigment Substances 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
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
- C09B47/10—Obtaining compounds having halogen 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
-
- 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
- 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
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0017—Influencing the physical properties by treatment with an acid, H2SO4
- C09B67/0019—Influencing the physical properties by treatment with an acid, H2SO4 of phthalocyanines
-
- 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
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- C—CHEMISTRY; METALLURGY
- 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
- C09D11/322—Pigment inks
Definitions
- the present invention relates to a green pigment, a method for producing the same, a colorant comprising the same, and a method for coloring an article using the same. More specifically, a green pigment in which a polyhalogeno zinc phthalocyanine molecule and a polyhalogeno non-zinc metal phthalocyanine molecule are compositely stacked, a green pigment composition containing the same, a method for producing the same, a colorant containing the same, and coloring of an article using the same It relates to a method and a colored article.
- LCD color displays are used as information display members for personal computers, mobile information devices, televisions, projectors, monitors, car navigation systems, mobile phones, electronic calculators and electronic dictionaries. It is used in a wide variety of information display related equipment such as information bulletin boards, information bulletin boards, function display boards, sign boards, and other digital display screens.
- color filters hereinafter sometimes abbreviated as “CF”) mounted on liquid crystal color displays also have images such as high image quality, wide color gamut, high definition, color density, light transmission, and contrast.
- CF color filters
- Pigment Green 36 (hereinafter sometimes referred to as “PG36”) has been used, but when a high image quality and a wide color gamut are desired, C.I. I. Pigment Green 58 (hereinafter sometimes referred to as “PG58”) has been evaluated for its color tone and sharpness of absorption wavelength.
- PG36 C.I. I. Pigment Green 58
- PG58 C.I. I. Pigment Green 58
- Polybromo / polychlorozinc phthalocyanine pigments such as PG58 are used as specific colors to complement the four primary color expressions of yellow, red, blue and black, which are usually used in the coloring field such as paints and printing inks.
- PG58 Polybromo / polychlorozinc phthalocyanine pigments
- CF green pigment As described above, recently, it has been used as a CF green pigment.
- organic solvent-based colorants such as paints and printing inks
- It is easy to cause problems such as changes in color tone, deterioration of sharpness, and deterioration of stability due to problems of fastness such as solvent resistance and heat resistance.
- the present inventors have stacked PG58 molecules with strong non-zinc metal pigment molecules having a similar molecular structure. It was found that by building a new composite pigment structure obtained, it was possible to impart fastness to organic solvents and heating while maintaining excellent color characteristics, and to solve the above-mentioned problems. It came to complete.
- a green pigment which comprises a polyhalogenozinc phthalocyanine having an average halogen group substitution number of 12 to 16 and an average halogen group substitution number of 12 to 16. It is characterized by being a composite stack with a certain polyhalogeno non-zinc metal phthalocyanine.
- a method for producing the above green pigment which comprises dissolving the polyhalogeno zinc phthalocyanine and the polyhalogeno non-zinc metal phthalocyanine in a medium, The two molecules are co-deposited as a composite stack.
- a green pigment dispersion composition comprising an organic solvent-based, aqueous or water-hydrophilic organic solvent mixed solvent-based liquid medium, and a polymerizable oligomer.
- a polymerizable liquid medium composed of a polymerizable monomer and a resin medium composed of a plasticizer, an oligomer, or a synthetic resin, and if necessary, a polymer system dispersant or a low molecular weight dispersion aid as a dispersion aid.
- it is characterized by comprising.
- a colorant is provided.
- the colorant further comprises a diluent medium, a thermoplastic polymer as a film-forming material, a reactive weight, and the green pigment dispersion composition.
- a diluent medium e.g., ethylene glycol dimethacrylate copolymer
- a thermoplastic polymer e.g., polyethylene glycol dimethacrylate copolymer
- a reactive weight e.g., a reactive weight
- the green pigment dispersion composition e.g., a thermoplastic polymer as a film-forming material
- the green pigment dispersion composition e.g., a reactive weight, and the green pigment dispersion composition.
- a coloring method for an article characterized by coloring the article using the above-described pigment dispersion composition or colorant, and a colored article formed thereby.
- This green pigment is excellent in physical properties, particularly fastness such as heat resistance and solvent resistance, while maintaining a clear and yellowish green color tone, and can be used particularly advantageously as a green pixel pigment for a color filter.
- Such an effect of the green pigment according to the present invention is not achieved by using a mixture of two pigments.
- the excellent effect of the green pigment according to the present invention is that a new composite pigment structure reinforced by intermolecular interaction is obtained by firmly stacking (stacking) the two pigment molecules constituting the pigment. It is assumed that it is provided by. In particular, two molecules are stacked with each other by ⁇ - ⁇ interaction, and both molecules are combined to form a crystal. Unlike the original pigment crystals, a new pigment is formed. It is done.
- the above theory is only an assumption, and the present invention is not limited to such a theory.
- polyhalogeno zinc phthalocyanine having an average halogen group substitution number of 12 to 16 poly (12 to 16) halogeno zinc phthalocyanine
- polyhalogeno non-zinc metal phthalocyanine having an average halogen group substitution number of 12 to 16 Is sometimes referred to as poly (12-16) halogeno non-zinc metal phthalocyanine. That is, “(12 to 16)” in these notations indicates the average number of halogen groups substituted in each pigment molecule.
- poly (12-16) halogeno zinc phthalocyanine and poly (12-16) halogeno non-zinc metal phthalocyanine are described with the intention of pigments that are aggregates of molecules
- 12-16) Halogeno zinc phthalocyanine pigments and poly (12-16) halogeno non-zinc metal phthalocyanine pigments may be abbreviated as A pigments and B pigments, and the molecules constituting these pigments will be described intentionally.
- poly (12 to 16) halogenozinc phthalocyanine and poly (12 to 16) halogeno non-zinc metal phthalocyanine may be referred to as compound names, or may be abbreviated to A and B molecules, respectively.
- a composite stack of a polyhalogenozinc phthalocyanine having an average halogen group substitution number of 12 to 16 and a polyhalogeno non-zinc metal phthalocyanine having an average halogen group substitution number of 12 to 16 is a molecular level.
- the green pigment according to the present invention is prepared, for example, by the following method. That is, a poly (12-16) halogenozinc phthalocyanine pigment (A pigment) and a poly (12-16) halogeno non-zinc metal phthalocyanine pigment (B pigment) are dissolved in a medium in which both pigments are dissolved, and the A pigment The green pigment is obtained by eutecting so that both the A molecule of B and the B molecule of the B pigment are compositely stacked.
- an acid preferably sulfuric acid, more preferably fuming sulfuric acid or 100% sulfuric acid is used.
- the A molecule and the B molecule are simultaneously dissolved so that the A molecules are deposited (stacked) by the B molecules.
- a condition where only A molecules are precipitated and B molecules are not precipitated must be avoided.
- eutectoid methods include: (1) A method in which a hydrous acid is added to an acid solution (preferably a high concentration acid solution) in which the A pigment and the B pigment are dissolved to decrease the acid concentration and precipitate both molecules. (2) A method of precipitating both molecules by absorbing moisture in a high-concentration acid solution in which the A pigment and B pigment are dissolved to lower the acid concentration to lower the solubility. (3) A method in which a high-concentration acid solution in which A pigment and B pigment are dissolved is injected into a large amount of vigorously stirred or jetted water or ice water, and both molecules are instantaneously precipitated and stacked. Etc.
- the water for precipitation or ice water may contain an organic solvent.
- the method (3) is preferred.
- a preferred embodiment also includes a method in which an acid solution of a pigment is dropped, dropped or injected (hereinafter, “injection” is used to include dropping and flowing), and the pigment particles are diffused into water to precipitate the pigment particles. .
- the process of removing impurities from the crude pigment to increase the purity of the pigment it is preferable to carry out the step of preparing and / or the step of preparing crystals as a pigment.
- the pigmentation process in the eutectoid process is carried out by injecting or forcing contact with water or ice water containing a hydrophobic organic solvent and / or hydrophilic organic solvent to cause eutectoid and refinement and crystal adjustment pigmentation.
- a method of adding the organic solvent to the treated water containing the eutectoid and bringing them into contact with each other is carried out.
- a known pigmentation treatment such as a solvent finish method such as a heat treatment in an organic solvent such as xylol or a crystallization treatment such as a heat treatment with xylol emulsion is carried out.
- a solvent finish method such as a heat treatment in an organic solvent such as xylol or a crystallization treatment such as a heat treatment with xylol emulsion
- agents, rosins, various resins, polymer dispersants, and pigment derivatives can be used in combination.
- Pigment refinement can be performed in the eutectoid process, and when it is performed subsequent to the eutectoid process, water-soluble salts can be added in a kneader such as a kneader by a dry grinding method or a salt milling method. Then, it may be carried out by a known pigment refining method such as kneading, grinding and refining with a water-soluble organic solvent.
- the average particle diameter of the primary particles of the finely divided pigment is 5 to 130 nm, preferably 10 to 110 nm.
- the halogen group as a substituent means a chlorine group, a bromine group or both groups.
- a phthalocyanine green pigment mainly composed of bromine groups is preferred, and bromine groups and chlorine groups are introduced (12 to less than 16, preferably Preferred are 12 to 15.9) bromo- (0 to less than 4 and preferably 0.1 to 4) chlorozinc phthalocyanine pigments and (12 to 16) bromozinc phthalocyanine pigments containing only bromine groups.
- a more specific preferred pigment is PG58.
- the non-zinc metal of the poly (12-16) halogeno non-zinc metal phthalocyanine pigment constituting the green pigment according to the present invention includes a group I metal such as copper, a group II metal such as aluminum, magnesium, and the like. Examples include one or more metals selected from the group consisting of Group III metals, Group IV metals such as titanium and tin, and Group VIII metals such as iron, cobalt and nickel.
- the halogen group means a chlorine group, a bromine group or both.
- Preferable poly (12 to 16) halogeno non-zinc metal phthalocyanine for realizing the green pigment according to the present invention having high fastness is a poly (12 to 16 and preferably 12 to 15.9) having a bromine group and a chlorine group introduced. ) Bromo (exceeding 0 to 4 or less, preferably 0.1 to 4) Chloro non-zinc metal phthalocyanine, bromine-only poly (12 to 16) Bromo non-zinc metal phthalocyanine, and chlorine-only poly (12 to 16) Examples include chloro non-zinc metal phthalocyanine, and (14-16) bromo non-zinc metal phthalocyanine is particularly preferably used.
- Polybromochlorozinc phthalocyanine and polybromochloro non-zinc metal phthalocyanine can be obtained by a “post-bromination method” in which a phthalocyanine pigment is brominated.
- a phthalocyanine pigment is brominated.
- chlorination occurs along with bromination, and it is difficult to completely control the type of halogen and the number of substitutions, so the pigment of the desired color is selected from the obtained one. , Preferably used.
- polybromozinc phthalocyanine pigments or polybromo non-zinc metal phthalocyanine pigments having only a bromine group are tri- or tetrabromophthalic anhydride, tri- or tetrabromophthalimide, tri- or tetrabromophthalodinitriles, or tri- or tetrabromo. It is preferably obtained by a method for synthesizing a pigment by a condensation reaction using aminoiminoisoindolenine as a raw material together with zinc salt or non-zinc metal salt.
- the green pigment according to the present invention is excellent in fastness such as solvent resistance and heat resistance.
- the green pigment according to the present invention is such that the particle diameter of the pigment particles does not greatly expand before and after heating and boiling in an organic solvent, and the diffraction angle and diffraction intensity of X-ray diffraction do not substantially change. .
- a heat treatment method in an organic solvent can be mentioned.
- the green pigment according to the present invention is heat-treated under a treatment condition in which crystal grains grow and become coarse. Changes in the obtained treated pigment particles can be confirmed and evaluated by the degree to which the pigment particles grow more coarsely like needles from an electron micrograph.
- the X-ray diffraction chart of the treated pigment or the coarse pigment portion separated therefrom does not substantially show diffraction at an angle characteristic only to the polyhalogeno zinc phthalocyanine pigment, or the mixture of pigment particles depending on the degree The degree of can be confirmed.
- PG36 pigment, PG58 pigment, and green pigment according to the present invention were prepared.
- a simple pigment mixture prepared by kneading PG36 pigment and PG58 pigment in methanol paste was also prepared.
- Each pigment was added in a xylene solvent, heated and boiled to treat the pigment with a solvent, and changes in the particle diameter and crystal state of the treated pigment were examined.
- Electron micrographs were taken at 60,000 times the PG36 pigment before solvent treatment, PG58 pigment, the green pigment according to the present invention, and a simple pigment mixture. The photographs showed that the pigments were fine or spherical, each having a size of approximately 30-50 nm (0.03-0.05 ⁇ m).
- the treated pigment of PG58 was coarsened with crystal grains growing very much.
- the electron micrograph was taken at a magnification of 10,000 times, the magnification being lower than that of other pigments. Electron micrographs showed no fine particles, but only needle-like or thicker glass fiber crystals on the entire surface.
- the crystal was expressed by “length ⁇ width”, it was a large needle crystal having a size of about 1 ⁇ m ⁇ 0.05 ⁇ m to 7 ⁇ m ⁇ 0.2 ⁇ m, and further, it was observed to grow into the combined coarse crystal particles.
- PG58 pigment was shown to be very solvent labile.
- PG36 pigments, simple pigment mixtures and green pigment xylene boiling treated pigments according to the present invention were taken at 60,000 times as electron micrographs.
- the shape of the pigment particles of the treated pigment of PG36 was in the form of fine particles or spheres of about 30 to 70 nm as before the treatment, indicating that it was stable to the solvent.
- the mixture of PG36 pigment and PG58 pigment showed fine particles and needle-like or glass fiber-like crystal particles, showing a photograph in which both pigments were mixed.
- the green pigment according to the present invention showed fine particles or spheres of about 30 to 70 nm as before the treatment. However, in some cases, thin acicular crystals with a width of about 30 nm and a length of about 1 ⁇ m can be seen, and there is a mixture of non-stacked PG58 that may be caused by fluctuation of the stacking conditions. was assumed. However, when used as a colorant, it has little effect on fastness and in many cases is used substantially equally.
- Tables 1 and 2 show the main diffraction peaks and relative intensities when the diffraction angles are substantially matched.
- “2 ⁇ ” indicates the diffraction angle (°)
- the “%” column indicates the relative intensity of diffraction in%
- the “shape” column indicates the pattern of the diffraction peak
- “s” is sharp.
- “B” represents a broad pattern.
- the PG36 pigment had almost the same diffraction angle and relative intensity before and after the treatment, except that the crystal pattern became slightly sharper.
- PG58 pigment showed a sharp and large diffraction pattern at many diffraction angles from X-ray diffraction, and it was shown that the crystal of the pigment grew greatly and the interplanar spacing was adjusted.
- the diffraction of the mixture of PG36 pigment and PG58 pigment is naturally shown as a combined pattern of the diffraction of both pigments.
- the green pigment according to the present invention exhibits diffraction that is completely different from the diffraction of the above mixture, indicating that the mixture is a crystal of a completely different dimension.
- the charts before and after the solvent treatment both show diffraction patterns similar to the diffraction chart of PG36 pigment, including diffraction angle and relative intensity. It is inferred that the diffraction pattern of the green pigment according to the present invention is slightly broad and shows a difference in sharpness, indicating an accumulation of non-zinc pigment molecules.
- the overlap of the A pigment and the B pigment is considered as follows. That is, the green pigment according to the present invention has a difference in sharpness of diffraction compared to the PG36 pigment and PG58 pigment, and although there are some broad points, the overall diffraction pattern of these three types of pigments is different. Similar to each other, diffraction appears where diffraction angles almost coincide with each other, and their relative intensities are also similar. From this, it is inferred that the PG36 molecule and the PG58 molecule are molecules that tend to overlap each other in terms of molecular structure.
- the green pigment according to the present invention is expected to show a clear yellowish green color particularly as a green pigment for forming a green pixel for CF.
- the green pigment according to the present invention can be used in the case where a slight mixture of non-stacked polyhalogenozinc phthalocyanine pigments does not substantially affect the colorant formulation, processing conditions, or application used. Mixing is allowed.
- the molar ratio of polyhalogeno zinc phthalocyanine to polyhalogeno non-zinc metal phthalocyanine it is possible to retain the yellowish green color tone, which is an excellent property of polyhalogeno zinc phthalocyanine, or to be a range that does not hinder, and is a disadvantage of polyhalogeno zinc phthalocyanine.
- the molar ratio be such that a structure that brings about the above performance and physical properties can be formed.
- the ratio of heat resistance, solvent resistance, etc. may be appropriately determined depending on the type of solvent used when forming the colorant, and heat resistance is determined depending on the heating conditions in the post-treatment when coloring. .
- the green pigment according to the present invention is used as a colorant in, for example, painting, printing plate printing, dyeing, textile printing, character recording, drawing, ink jet printing, electrophotographic printing, and electrostatic printing.
- CF pixel forming ink painting with paint, resin coloring with resin colorants, colorants such as printing ink, dyeing agent, and printing agent, stationery such as stationery and paint, ink for inkjet, electrophotography
- coloring components such as information recording materials, such as a developer for printing or a developer for electrostatic printing, is mentioned.
- a colorant comprising the green pigment according to the present invention.
- a pigment composition may be prepared, and the pigment composition may include the green pigment according to the present invention.
- a pigment dispersion composition comprising the green pigment according to the present invention.
- the form of the pigment dispersion composition may be an aqueous pigment dispersion composition, an oily pigment dispersion composition, a resin-dispersed processed pigment, an energy beam curable pigment dispersion composition, or the like.
- the pigment concentration is usually set to a high value of 10% to 50%, and the pigment may be finely dispersed in advance so that the colorant can be easily produced.
- the pigment composition according to the present invention contains the green pigment according to the present invention, and an appropriate liquid medium of an organic solvent system, an aqueous system or a water-hydrophilic organic solvent mixed solvent system as a medium; a polymerizable oligomer, a polymerizable monomer, etc.
- Appropriate materials selected from the pigment dispersion composition according to the present invention further selected from a dilution medium, a thermoplastic polymer acting as a film-forming material, a reactive polymer, a reactive oligomer, a polymerizable monomer, and a crosslinking agent. And the like, and a curing catalyst, a polymerization catalyst and the like are further added as necessary, and the mixture is uniformly mixed and dispersed to produce the target colorant.
- additives may be added as required in addition to the film-forming polymer.
- additives include ionic pigment derivatives known as pigment dispersion stabilizers and their counterionic ionic polymer-based dispersants, surfactants, antifoaming agents, smoothing agents, adhesive agents, Various additives such as a silane coupling agent are included.
- Examples of the pigment dispersing machine used in the production of the pigment dispersion composition and the colorant include known dispersing machines, such as vertical media dispersing machines such as a ball mill, a sand mill and a bead mill, horizontal media dispersing machines such as a dyno mill and a horizontal bead mill, a roll mill, An ultrasonic mill, a high-pressure collision disperser, etc. are used.
- Dispersion processing is performed by a method of performing dispersion processing a plurality of times using one kind of the above-mentioned dispersers or a method of combining two or more kinds of dispersers.
- the average particle size is usually about 5 to 130 nm, preferably 10 to 110 nm.
- the resin as the film forming material contained in the colorant according to the present invention may also be a known resin component depending on the application.
- known coating film forming materials such as synthetic rubber resin, acrylic resin, vinyl resin, chlorinated rubber resin, alkyd resin, urethane resin, epoxy resin, silicon resin, fluorine resin, and ultraviolet curable resin system, electron beam curable Examples include resin-based energy ray-curable coating film forming materials.
- the film-forming material may further have a reactive group, and examples of the reactive group include a methylol group, an alkylmethylol group, an isocyanate group, a masked isocyanate group, and an epoxy group.
- oligomers and monomers are used depending on the application, and a cross-linking agent such as a methylol melamine-based, isocyanate-based, or epoxy-based cross-linking agent is also used in combination.
- the colorant according to the present invention is a color filter colorant
- any conventionally known film-forming material can be used and is not particularly limited.
- the image forming ink is a photolithographic development type
- an energy beam irradiation polymerization type ink collectively referred to as a photosensitive pixel forming ink is used.
- addition polymerization or addition crosslinkable inks include heat polymerization type, laser heat ray polymerization type, ultraviolet ray polymerization type, photocationic polymerization type, and electron beam polymerization type heating or energy ray curable inks.
- the film-forming material used for them is a monomer, oligomer and / or polymer having an unsaturated double bond or a polymerizable cyclic ether group having a conventionally known addition polymerization or addition crosslinkability, and further added if necessary.
- a polymerization initiator, an addition polymerization or addition crosslinkable fixing agent comprising a liquid medium.
- film forming materials include pentaerythritol di (meth) acrylate (“(meth) acrylate” indicates acrylate and methacrylate), dipentaerythritol poly (4-6) (meth) acrylate, bisphenol type epoxy resin— Monomers such as di (meth) acrylate; (meth) acrylic acid ester- (meth) acrylic acid (co) polymer, (meth) acrylic acid ester-styrene- (meth) acrylic acid copolymer, etc .; polyester acrylate type Resins, polyepoxy acrylate resins, polyurethane acrylate resins, polyether acrylate resins, polyol acrylate resins, and the like; photosensitive phenol resins, unsaturated polyester resins, and the like. These may be used alone or in combination of two or more.
- photopolymerization initiator examples include known photopolymerization initiators such as 1-hydroxy-cyclohexylphenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-di- Ethoxyacetophenone, 2-methyl-1- (4- (methyl-thio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2- (N, N-dimethylamino) -1- (4-morphe And linophenyl) -butanone-1. These may be used alone or in combination of two or more.
- Various articles can be colored using the pigment dispersion composition according to the present invention and a colorant using the same.
- a conventionally known green color resist is prepared in combination with a yellow pigment as known, and a conventionally known photoresist method on a CF substrate together with a red resist and a blue resist, Green, red, and blue pixels are formed by a method such as a transfer method, a pasting method, an ink jet printing method, or a printing method, but is not particularly limited thereto.
- the photosensitive pixel forming ink is coated on the substrate using, for example, a spin coater, a roll coater, a slit coater, a printing machine, etc. Then, after pre-drying, a photomask is adhered, and exposure is performed using an ultra-high pressure mercury lamp to print a pattern. Subsequently, development and washing are performed, and post-baking is performed as necessary to form a color filter pattern.
- azo pigments such as insoluble azo, soluble azo and high molecular weight azo, quinacridone red and quinacridone magenta quinacridone pigments, diketopyrrolopyrrole pigments, anthraquinone pigments, perylene pigments, phthalocyanines Blue-based phthalocyanine pigments, isoindolinone pigments, dioxazine pigments such as dioxazine violet, quinophthalone yellow pigments, complex pigments such as nickel azo yellow, and the like are used.
- pigments representative for transmissive R, G, and B pixels include PR177, PR242, and PR254 as red pigments, and PY83, PY138, PY139, PY150, as yellow pigments for complementary colors or single colors, PY185 and the like, PB15: 6, PB60, etc. as blue pigments, PV23 etc. as purple pigments for complementary colors or single colors, and the above-mentioned red pigments and yellow pigments, and blue pigments and purple pigments Examples include coprecipitated pigments, solid solution pigments, and mixed crystal pigments.
- the pigment dispersion composition and the colorant according to the present invention are used in various other applications such as synthetic or natural resins, paints, plastic films, various papers, As printing inks for synthetic paper, etc., it is also suitable as colorants for paper, textile printing agents, writing inks, color copier toners, ink jet printer inks, thermal transfer ribbon inks, etc. Gives an excellent green colored article.
- the present invention will be described in more detail with specific examples.
- the part and% in a sentence are a mass reference
- the number of bromine substitutions in the following polybromo non-zinc metal phthalocyanine indicates the number from the charge ratio of the condensation reaction.
- Production Example 1 (Production of composite stacked green pigment of PG58 molecule and 16 bromocopper phthalocyanine molecule)
- 16 bromocopper phthalocyanine pigment As a synthetic reaction apparatus, a reaction vessel equipped with a stirrer, a backflow cooler, and a thermometer and a heating apparatus were prepared. Tetrabromophthalic anhydride having a bromine content of 69.0% and a bromine substitution number of 4.0 per molecule was prepared as a raw material.
- the average bromine substitution number per molecule calculated from the analytical value of the obtained 16 bromocopper phthalocyanine green pigment was 16.1, indicating that the phthalocyanine skeleton was completely substituted with 16 bromines.
- this is referred to as “16 bromo copper phthalocyanine coarse particle pigment”.
- Production Example 2 (Production of composite stacked green pigment of PG58 and 16 bromocopper phthalocyanine molecule) (1) Stacking of PG58 molecule and 16 bromocopper phthalocyanine molecule It was obtained by the synthesis reaction of 16.81 g (0.00985 mol) of PG58 used in Production Example 1 (2) and Production Example 1 (1). 16.19 g (0.00173 mol) of 16 bromocopper phthalocyanine coarse particle pigment was dissolved in 200 g of 20% fuming sulfuric acid, stirred at 70 ° C. for 2 hours and allowed to cool to room temperature.
- the solution was poured into 2000 g of ice water containing 100 g of butyl cellosolve charged to Sumitomo Heavy Industries, Ltd., and filtered and washed with water.
- the press cake was dried and pulverized to obtain a green pigment.
- this is referred to as “green stacked pigment-2”.
- Production Example 3 (Production of composite stacked green pigment of PG58 molecule and PG36 molecule) (1) Stacking of PG58 molecule and PG36 molecule In the same manner as in Production Example 2, 18.00 g (0.01054 mol) of PG58 used in Production Example 1 (2) and the average number of bromine substitutions were approximately 13. 2.00 g (0.00117 mol) of PG36 having an average number of chlorine substitutions of 3 was dissolved in 200 g of 20% fuming sulfuric acid, stirred at 70 ° C. for 2 hours, and allowed to cool to room temperature. .
- Production Example 4 (Production of composite stacked green pigment of PG58 molecule and 16 bromoaluminum phthalocyanine molecule) (1) Synthesis of 16 bromoaluminum phthalocyanine pigment In the same manner as in Production Example 1 (1), the same number of nitrobenzene, tetrabromophthalic anhydride, urea, and titanium tetrachloride was changed to a reaction vessel, and aluminum chloride was replaced with copper chloride. 3.34 parts were charged. The reaction temperature was raised from 100 ° C. to 175 ° C. and stirred for 5 hours, and the final reaction temperature was 200 ° C. The yield of crude pigment was 40.0 parts, and the crude pigment yield was 87.1%.
- the obtained crude pigment was purified by sulfuric acid in the same manner as in Production Example 1 (1), and the pigment precipitate was filtered, washed with water, dried and pulverized.
- the pigment thus obtained is hereinafter referred to as “16 bromoaluminum phthalocyanine pigment”.
- Production Example 5 (Production of composite stacked green pigment of PG58 molecule and 16 bromomagnesium phthalocyanine molecule) (1) Synthesis of 16 bromomagnesium phthalocyanine pigment In the same manner as in Production Example 1 (1), the same number of nitrobenzene, tetrabromophthalic anhydride, urea, and titanium tetrachloride was changed to a reaction vessel, and magnesium chloride was replaced with copper chloride. 2.39 parts were charged. The reaction temperature was raised from 100 ° C. to 175 ° C. and stirred for 4 hours, and the final reaction temperature was 195 ° C. The yield of crude pigment was 39.9 parts, and the crude pigment yield was 88.7%.
- the obtained crude pigment was purified by sulfuric acid in the same manner as in Production Example 1 (1), and the pigment precipitate was filtered, washed with water, dried and pulverized.
- the pigment thus obtained is hereinafter referred to as “16 bromomagnesium phthalocyanine pigment”.
- Example 1 Preparation of high concentration dispersion of green pigment
- a pigment dispersant 30% propylene glycol monomethyl ether acetate of butyl acrylate-styrene-hydroxyethyl acrylate-methacrylic acid (mass ratio: 50: 15: 10: 25, average molecular weight: 12,000) copolymer ( Hereinafter, abbreviated as “PGMA”.)
- PGMA solution-1 As a pigment dispersant, 30% propylene glycol monomethyl ether acetate of butyl acrylate-styrene-hydroxyethyl acrylate-methacrylic acid (mass ratio: 50: 15: 10: 25, average molecular weight: 12,000) copolymer
- PGMA solution-1 As a pigment dispersant, 30% propylene glycol monomethyl ether acetate of butyl acrylate-styrene-hydroxyethyl acrylate-methacrylic acid (mass ratio: 50: 15: 10: 25, average mo
- Example 2 Preparation of high concentration dispersion of each color pigment
- PR254, PY138, PB15-6 and PV23 were prepared.
- Each pigment powder was charged into a kneader equipped with a pressure lid together with sodium chloride powder and diethylene glycol, and kneaded and ground in accordance with the salt milling refinement treatment of the composite stacked green pigment in Production Example 1 (3).
- the obtained ground product was similarly dissolved in salt and solvent, filtered and washed with water to obtain press cakes of the respective finer pigments.
- the average particle size of the fine pigments of each color was 30 to 40 nm.
- the press cake was dried and pulverized to obtain fine powder powder pigments.
- Example 3 (Preparation of color filter) A glass substrate treated with a silane coupling agent was set on a spin coater, and the condition of “red pigment photosensitive dispersion-1” in Example 2 (3) was initially 300 rpm for 5 seconds and then 1200 rpm for 5 seconds. Spin coated with. Next, prebaking was performed at 80 ° C. for 10 minutes, a photomask having a mosaic pattern was brought into close contact, and exposure was performed using an ultrahigh pressure mercury lamp at a light amount of 100 mJ / cm 2 . Next, development and washing were performed with a dedicated developer and a dedicated rinse to form a red mosaic pattern on the glass substrate.
- RGB Color filter has excellent spectral curve characteristics, excellent fastness such as light resistance and heat resistance, and excellent light transmission properties, and is excellent as a color filter for liquid crystal color displays. Showed the properties.
- Example 4 (Preparation of color filter)
- the green stacked pigment-2 to 5 obtained in Production Examples 2 to 5 were used, and the same operations as in Examples 1 and 2 were performed.
- a green color pigment photosensitive dispersion which is used together with the red color pigment photosensitive dispersion-1 and the blue color pigment photosensitive dispersion-1 to prepare a color filter in the same manner as in Example 3.
- a color filter for a liquid crystal color display was obtained having excellent spectral curve characteristics, excellent fastness such as light resistance and heat resistance, and excellent light transmission properties.
- Example 5 (gravure ink and gravure printing) 12 parts of a vinyl chloride-vinyl acetate-acrylic acid (89: 6.7: 4.3) copolymer having a carboxyl group (weight average molecular weight is about 30,000) is butyl acetate-methyl isobutyl ketone-xylene (43:20 20) Dissolved in 68 parts of the mixed solvent, added 5 parts of the green stacked pigment-1 obtained in Production Example 1 (3), charged into a ball mill and dispersed for 16 hours.
- a yellow green gravure ink was prepared in the same manner as described above using the green stacked pigments 2 to 5 obtained in Production Examples 2 to 5 instead of the green stacked pigment 1 used above.
- gravure printing was performed on the film to obtain a beautiful multicolored printing film.
- Example 6 (paint and painting) 45 parts of ethyl acetate solution (solid content 60%) of methyl methacrylate-ethyl methacrylate-octyl methacrylate-hydroxyethyl methacrylate-methacrylic acid (44: 20: 10: 5) copolymer having a carboxyl group, 19.9 parts of xylene, 5 parts of green stacked pigment-1 obtained in Production Example 1 (3) and 15 parts of titanium oxide white pigment were added to a ball mill and dispersed for 16 hours.
- a yellow-green acrylic paint having a formulation of 15 parts of a 20% solution of a multi-branched polycarbodiimide-based crosslinking agent used in Example 5 and 0.1 part of a color separation preventing agent was prepared. Apply yellow-green paint to information-related products such as mobile phones and personal computers, various wooden products such as office supplies and household goods, metal products, and plastic products, and perform excellent coating such as weather resistance, durability, and water resistance. I was able to.
- a green-green acrylic paint was prepared in the same manner as described above using the green stacked pigment-2 to 5 obtained in Production Examples 2 to 5, Similarly, various components were painted to obtain a beautiful yellow-green painted product.
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Abstract
Description
本発明の記載において、平均ハロゲン基置換数が12~16であるポリハロゲノ亜鉛フタロシアニンを、ポリ(12~16)ハロゲノ亜鉛フタロシアニンと、また平均ハロゲン基置換数が12~16であるポリハロゲノ非亜鉛金属フタロシアニンを、ポリ(12~16)ハロゲノ非亜鉛金属フタロシアニンと表記することがある。すなわち、これら表記中の「(12~16)」は、それぞれの顔料分子における置換されているハロゲン基の平均個数を示す。また以下においても、用語「ハロゲノ」、「ブロモ」、および「クロロ」の前にカッコ書きとともに表記された数字は、同様に、顔料分子中の「ハロゲン基」、「臭素基」、および「塩素基」の置換基の平均の個数を示す。
本発明による緑色顔料は、例えば、以下の方法により調製される。すなわち、ポリ(12~16)ハロゲノ亜鉛フタロシアニン顔料(A顔料)と、ポリ(12~16)ハロゲノ非亜鉛金属フタロシアニン顔料(B顔料)とを、両顔料を溶解する媒体中に溶解し、A顔料のA分子およびB顔料のB分子の両分子が複合重積するように共析させて緑色顔料を得る。両顔料を溶解する媒体としては、酸、好ましくは硫酸、更に好ましくは発煙硫酸あるいは100%硫酸などが使用される。
(1)A顔料とB顔料を溶解した酸溶液(好ましくは高濃度酸溶液)中に、含水酸を添加して酸濃度を低下させて、両分子を析出させる方法、
(2)A顔料とB顔料を溶解した高濃度酸溶液中に、水分を吸収させて酸濃度を低下させて溶解度を低下させて、両分子を析出させる方法、
(3)A顔料とB顔料を溶解した高濃度酸溶液を、激しく撹拌された、あるいは噴流している大量の水中あるいは氷水中に注入し、瞬間的に両分子を析出させ、重積させる方法
などが挙げられる。
本発明による緑色顔料を構成するポリハロゲノ亜鉛フタロシアニン顔料において、置換基としてのハロゲン基は、塩素基、臭素基またはその双方の基を意味する。特にポリハロゲノ亜鉛フタロシアニン顔料に期待される色調が鮮明な黄味の緑色であることから、臭素基が主体のフタロシアニングリーン顔料が好ましく、臭素基と塩素基の導入された(12以上16未満、好ましくは12~15.9)ブロモ・(0超過4以下、好ましくは0.1~4)クロロ亜鉛フタロシアニン顔料、および臭素基のみの(12~16)ブロモ亜鉛フタロシアニン顔料が好ましい。より具体的な好ましい顔料はPG58である。
PG36顔料、PG58顔料、および本発明による緑色顔料を準備した。また比較としてPG36顔料とPG58顔料をメタノールペーストにして混練した、単純な顔料混合物も準備した。夫々の顔料をキシレン溶媒中で添加し、加熱、沸騰させて顔料を溶剤処理し、処理顔料の粒子径および結晶状態の変化を調べた。
溶剤処理前のPG36顔料、PG58顔料、本発明による緑色顔料、および単純な顔料混合物を6万倍で電子顕微鏡写真を撮影した。写真は、顔料が夫々ほぼ30~50nm(0.03~0.05μm)の大きさの微粒子状ないし球状のものであることを示した。
本発明による緑色顔料は、着色剤として、例えば塗装、印刷版印刷、染色、捺染、文字記録、描絵画、インクジェット印刷、電子写真印刷、静電印刷に使用される。また、CF画素形成用インクのほか、塗料による塗装、樹脂着色剤を用いた樹脂着色、印刷インク、染色剤、捺染剤などの着色剤、文房具、絵の具などの文具類、インクジェット用インク、電子写真印刷用現像剤あるいは静電印刷用現像剤などの情報記録材料などの着色成分としての用途が挙げられる。
本発明による顔料分散組成物に、さらに希釈媒体、塗膜形成材料として作用する熱可塑性重合体、反応性重合体、反応性オリゴマー、重合性単量体および架橋剤などから選ばれた適切な材料などを配合し、必要に応じてさらに硬化触媒、重合触媒などを添加し、均一に混合、分散して、目的の着色剤を製造することができる。本発明の一つの態様によれば、本発明による着色剤において、顔料(P)と塗膜形成材料(V)との配合質量比は、用途、要求される性能などを考慮して適宜決定されてよいが、一般的にはP:V=80:20~1:99の範囲であり、好ましくは70:30~10:90である。
(1)16ブロモ銅フタロシアニン顔料の合成
合成反応装置として、攪拌装置、逆流冷却器、および温度計を装填した反応容器並びに加熱装置を準備した。原料として臭素の含有率が69.0%であり、1分子あたりの臭素の置換個数が4.0であるテトラブロモ無水フタル酸を用意した。反応容器へ、反応媒体のニトロベンゼン140.0部、上記のテトラブロモ無水フタル酸46.4部、尿素27.0部、四塩化チタン7.1部および塩化第二銅3.4部を添加した。反応温度は100℃から175℃に徐々に昇温し、そのまま4時間攪拌し、反応を続けた。反応終了直前の反応温度は195℃であった。粗製顔料の得量は44.8部で、粗製顔料収率は97.4%であった。別に、95%硫酸と20%発煙硫酸を配合し、100%硫酸を調製した。得られた粗製顔料10部を100%硫酸100部に溶解し、70℃にて1時間攪拌し、10倍の氷水中に析出し、濾過し、水洗を行った(以下、「硫酸精製」と称する)。次いで水酸化ナトリウム希水溶液およびエタノールおよびジメチルホルムアミドで洗浄した。精製顔料の収率は94.9%であった。元素分析により、銅元素の含有率は3.44%(理論値:3.456%)、臭素の含有率は69.8%(理論値:69.52%)であった。得られた16ブロモ銅フタロシアニングリーン顔料の分析値から計算した1分子当りの平均臭素置換個数は16.1であり、フタロシアニン骨格が完全に16個の臭素で置換されていることが示された。以下、これを「16ブロモ銅フタロシアニン粗粒子顔料」と称する。
臭素の平均置換数がほぼ13個、塩素の平均置換数がほぼ3個のPG58を16.39g(平均置換基数からの計算値として0.00960モル、以下同様)と、上記の(1)の合成反応によって得られた16ブロモ銅フタロシアニン粗粒子顔料3.61g(0.00196モル)とを、20%発煙硫酸140gに溶解し、70℃にて2時間攪拌して、室温まで放冷した。アスピレーターで水を高速で噴流させ、減圧された細管を通じて上記の顔料の発煙硫酸溶液を吸引させ、高速噴流する水と接触させ、希釈させて顔料粒子を析出させ、濾過および水洗を行った。次いでキシレン-エマルジョン法にて顔料化を行い、緑色顔料を得た。以下、これを「緑色重積粗製顔料-1」と称する。
上記の(2)で得られた緑色重積粗製顔料-1の100部を塩化ナトリウム粉末600部およびジエチレングリコール110部と共に加圧蓋を装着したニーダーに仕込んだ。ニーダー内に均一に湿潤された塊ができるまで予備混合し、次いで加圧釜を閉じて圧力6kg/cm2で内容物を押さえ込みながら混練および摩砕を行った。内容物が92~98℃になるように温度を管理しながら2時間混練・摩砕処理を行った。得られた摩砕物を80℃に加温した3000部の2%硫酸中で1時間の攪拌処理を行った後、濾過および水洗をして塩化ナトリウムおよびジエチレングリコールを除去し、微細化した複合重積化緑色顔料のプレスケーキを得た。得られた顔料の粒子径を測定するために、顔料プレスケーキにノニオン活性剤を顔料に対して200%添加し、水で希釈し、超音波分散して顔料分散液を調製し、粒度測定機器「ModelN-4」(コールター社製)で平均粒子径を測定したところ、平均粒子径は凡そ25~35nmであった。プレスケーキを乾燥、粉砕して緑色顔料を得た。得られた顔料を有機溶媒中で加熱処理しても顔料の粒子径および結晶状態に実質的な変化は見られなかった。以下、これを「緑色重積顔料-1」と称する。
(1)PG58分子と16ブロモ銅フタロシアニン分子の重積化
製造例1(2)で使用したPG58の16.81g(0.00985モル)と、製造例1(1)の合成反応によって得られた16ブロモ銅フタロシアニン粗粒子顔料3.19g(0.00173モル)とを、20%発煙硫酸200gに溶解し、70℃にて2時間攪拌して、室温まで放冷した後、マックスブレンド撹拌槽(住友重機械工業社製)に仕込んだ100gのブチルセロソルブを含有する2000gの氷水中に注入し、濾過および水洗を行った。プレスケーキを乾燥、粉砕して緑色顔料を得た。以下、これを「緑色重積顔料-2」と称する。
(1)PG58分子とPG36分子の重積化
製造例2と同様にして、製造例1(2)で使用したPG58の18.00g(0.01054モル)と、臭素の平均置換数がほぼ13個、塩素の平均置換数がほぼ3個のPG36を2.00g(0.00117モル)とを、20%発煙硫酸200gに溶解し、70℃にて2時間攪拌して、室温まで放冷した。アスピレーターで水を高速で噴流させ、減圧された細管を通じて上記の顔料の発煙硫酸溶液を吸引させ、高速噴流する水と接触させ、希釈させて顔料粒子を析出させ、濾過および水洗を行った。次いでキシレン-エマルジョン法にて顔料化を行い、緑色顔料を得た。以下、これを「緑色重積粗製顔料-3」と称する。
製造例1(3)と同様にして、上記(1)で得られた緑色重積粗製顔料-3の100部を塩化ナトリウム粉末600部およびジエチレングリコール110部と共に加圧蓋を装着したニーダーに仕込み、同様にして混練および摩砕を行った。同様にして2%硫酸中で攪拌処理を行った後、濾過および水洗をして塩化ナトリウムおよびジエチレングリコールを除去し、微細化した複合重積化緑色顔料のプレスケーキを得た。平均粒子径は凡そ30nmであった。プレスケーキを乾燥、粉砕して緑色顔料を得た。得られた顔料を有機溶媒中で加熱処理しても顔料の粒子径および結晶状態に実質的な変化は見られなかった。以下、これを「緑色重積顔料-3」と称する。
(1)16ブロモアルミニウムフタロシアニン顔料の合成
製造例1(1)と同様にして、反応容器へニトロベンゼン、テトラブロモ無水フタル酸、尿素、および四塩化チタンの同じ部数を、また塩化銅に変えて塩化アルミニウム3.34部を仕込んだ。反応温度は100℃から175℃に昇温して5時間攪拌し、最終の反応温度は200℃だった。粗製顔料の得量は40.0部で、粗製顔料収率は87.1%であった。得られた粗製顔料を製造例1(1)と同様にして硫酸精製し、顔料析出液を濾過、水洗し、乾燥、粉砕した。こうして得た顔料を、以下、「16ブロモアルミニウムフタロシアニン顔料」と称する。
製造例1(2)と同様にして、PG58を14.75g(0.00864モル)と上記(1)の16ブロモアルミニウムフタロシアニン顔料5.24g(0.00288モル)とを20%発煙硫酸140gに溶解し、70℃にて攪拌し、放冷した。アスピレーターを使用して上記の顔料の発煙硫酸溶液を吸引させ、高速噴流する水と接触させ、希釈させて顔料粒子を析出させた。析出液を濾過し、水洗を行い、次いでキシレン-エマルジョン法にて顔料化を行い、緑色顔料を得た。以下、これを「緑色重積粗製顔料-4」と称する。
製造例1(3)と同様にして、上記の(2)で得られた緑色重積粗製顔料-4を塩化ナトリウム粉末およびジエチレングリコールと共にニーダーに仕込み、予備混合の後、混練・摩砕処理を行った。得られた摩砕物を2%希硫酸中で攪拌処理を行った後、濾過および水洗し、乾燥、粉砕して緑色顔料を得た。得られた顔料を有機溶媒中で加熱処理しても顔料の粒子径および結晶状態に実質的な変化は見られなかった。以下、これを「緑色重積顔料-4」と称する。
(1)16ブロモマグネシウムフタロシアニン顔料の合成
製造例1(1)と同様にして、反応容器へニトロベンゼン、テトラブロモ無水フタル酸、尿素、および四塩化チタンの同じ部数を、また塩化銅に変えて塩化マグネシウム2.39部を仕込んだ。反応温度は100℃から175℃に昇温して4時間攪拌し、最終の反応温度は195℃だった。粗製顔料の得量は39.9部で、粗製顔料収率は88.7%であった。得られた粗製顔料を製造例1(1)と同様にして硫酸精製し、顔料析出液を濾過、水洗し、乾燥、粉砕した。こうして得られた顔料を、以下、「16ブロモマグネシウムフタロシアニン顔料」と称する。
製造例1(2)と同様にして、PG58を6.43g(0.00377モル)と、上記(1)の16ブロモマグネシウムフタロシアニン顔料13.57g(0.00754モル)とを20%発煙硫酸140gに溶解し、70℃にて攪拌し、放冷した。アスピレーターを使用して上記の顔料の発煙硫酸溶液を吸引させ、高速噴流する水と接触させ、希釈させて顔料粒子を析出させた。析出液を濾過し、水洗を行い、次いでキシレン-エマルジョン法にて顔料化を行い、緑色顔料を得た。以下、これを「緑色重積粗製顔料-5」と称する。
製造例1(3)と同様にして、上記の(2)で得られた緑色重積粗製顔料-4を塩化ナトリウム粉末およびジエチレングリコールと共にニーダーに仕込み、予備混合の後、混練・摩砕処理を行った。得られた摩砕物を2%希硫酸中で攪拌処理を行った後、濾過および水洗し、乾燥、粉砕して緑色顔料を得た。得られた顔料を有機溶媒中で加熱処理しても顔料の粒子径および結晶状態に実質的な変化は見られなかった。以下、これを「緑色重積顔料-5」と称する。
予め、顔料の分散剤として、ブチルアクリレート-スチレン-ヒドロキシエチルアクリレート-メタクリル酸(質量比:50:15:10:25、平均分子量:12,000)共重合体の30%プロピレングリコールモノメチルエーテルアセテート(以下、「PGMA」と略す。)溶液を準備した。以下、「樹脂分散剤PGMA溶液-1」と称する。
製造例1(3)で得た「緑色重積顔料-1」を19部、緑色顔料スルホン化誘導体1部、カチオン性高分子系分散剤(ポリエステルアミド化ポリエチレンイミン、50%溶液)12部、上記に示す「樹脂分散剤PGMA溶液-1」を50部およびPGMA18部を配合し、ディゾルバーで2時間攪拌して、顔料の塊がなくなったことを確認後、横型アニューラー型ビーズミル分散機にジルコニア製ビーズ(径0.65mm)を使用し、周速14m/sで分散処理を行い、緑色の高濃度顔料分散液、「緑色重積顔料高濃度分散液-1」を得た。
(1)微細化処理による各色微粒子顔料の調製
PR254、PY138、PB15-6およびPV23を準備した。製造例1(3)の複合重積化緑色顔料のソルトミリング微細化処理に準じて、各顔料粉末を塩化ナトリウム粉末およびジエチレングリコールと共に加圧蓋を装着したニーダーに仕込み、混練および摩砕を行った。得られた摩砕物を同様に塩、溶剤を溶解、濾過および水洗をし、夫々の微細化顔料のプレスケーキを得た。この各色の微細化顔料の平均粒子径は30~40nmであった。プレスケーキを乾燥、粉砕して夫々顔料の微細化粉末顔料を得た。
実施例1と同様にして、緑色重積顔料-1および緑色顔料スルホン化誘導体に替えて、上記(1)で得たPR254、PY138、PB15-6およびPV23の微粒子顔料およびそれぞれ公知の顔料スルホン化誘導体を使用し、同様にカチオン性高分子系分散剤、アクリル樹脂およびPGMAを配合し、ディゾルバーで攪拌、解膠し、アニューラー型ビーズミル分散機で分散処理を行い、夫々の顔料の高濃度分散液を得た。以下、「高濃度分散液-1」にそれぞれの色名をつけて表示する。
カラーフィルターのガラス基板にRGB画素を形成するために、下記の表3の配合に従い、「グリーン色顔料感光性分散液-1」、「レッド色顔料感光性分散液-1」および「ブルー色顔料感光性分散液-1」を得た。
シランカップリング剤処理を行ったガラス基板をスピンコーターにセットし、上記実施例2(3)の「レッド色顔料感光性分散液-1」を最初300rpmで5秒間、次いで1200rpmで5秒間の条件でスピンコートした。次いで80℃で10分間プリベークを行い、モザイク状のパターンを有するフォトマスクを密着させ、超高圧水銀灯を用い100mJ/cm2の光量で露光を行った。次いで専用現像液および専用リンスで現像および洗浄を行い、ガラス基板上に赤色のモザイク状パターンを形成させた。
引き続いて緑色モザイク状パターンおよび青色モザイク状パターンを表3の「グリーン色顔料感光性分散液-1」および「ブルー色顔料感光性分散液-1」を用いて上記の方法に準じて塗布および焼き付けを行って形成し、RGBのカラーフィルターを得た。得られたカラーフィルターは優れた分光カーブ特性を有し、耐光性、耐熱性などの堅牢性に優れ、また、光の透過性にも優れた性質を有し、液晶カラーディスプレイ用カラーフィルターとして優れた性質を示した。
上記実施例1で使用した緑色重積顔料-1に代えて、製造例2~5で得られた緑色重積顔料-2~5を使用して上記実施例1および実施例2と同様な操作を行い、グリーン色顔料感光性分散液を得て、レッド色顔料感光性分散液-1およびブルー色顔料感光性分散液-1と共に使用し、実施例3と同様にしてカラーフィルターを調製し、優れた分光カーブ特性を有し、耐光性、耐熱性などの堅牢性に優れ、また、光の透過性にも優れた性質を有し、液晶カラーディスプレイ用カラーフィルターを得た。
カルボキシル基を有する塩化ビニル-酢酸ビニル-アクリル酸(89:6.7:4.3)共重合体(重量平均分子量は凡そ3万)12部を酢酸ブチル-メチルイソブチルケトン-キシレン(43:20:20)混合溶媒68部に溶解し、製造例1(3)で得られた緑色重積顔料-1を5部加えてボールミルに仕込み16時間分散させた。シリカを3部添加し、さらに多分岐型ポリカルボジイミド系架橋剤(ポリヘキサメチレンカルボジイミド・ジイソシアネートとジペンタエリスリトールモノラウレートとの反応生成物)20%トルエン溶液を12部加え、混合し、黄緑色グラビアインクとした。鮮明な黄緑色の特別色のグラビアインクとして、他の赤色、青色、黄色、茶色および黒色グラビアインクと共に塩化ビニルフィルムなどにグラビア印刷を行ない、綺麗な多色印刷塩化ビニルなどのフィルムを得た。
カルボキシル基を有するメチルメタクリレート-エチルメタクリレート-オクチルメタクリレート-ヒドロキシエチルメタクリレート-メタクリル酸(44:20:10:5)共重合体の酢酸エチル溶液(固形分60%)45部、キシレン19.9部、製造例1(3)で得られた緑色重積顔料-1を5部および酸化チタン白色顔料15部を加えてボールミルに仕込み16時間分散させた。実施例5で使用した多分岐型ポリカルボジイミド系架橋剤20%溶液15部、および色別れ防止剤0.1部の配合処方の黄緑色のアクリル塗料を調製した。携帯電話、パーソナルコンピューターなどの情報関連製品、事務用品や家庭用品など各種の木製品、金属製品、プラスチック製品に黄緑色の塗装を行ない、耐候性、耐久性、耐水性などの優れた塗装を行なうことができた。
Claims (24)
- 平均ハロゲン基置換数が12~16であるポリハロゲノ亜鉛フタロシアニンと、平均ハロゲン基置換数が12~16であるポリハロゲノ非亜鉛金属フタロシアニンとの複合重積物であることを特徴とする、緑色顔料。
- 前記ポリハロゲノ亜鉛フタロシアニンと、前記ポリハロゲノ非亜鉛金属フタロシアニンとのモル比率が30:70~95:5である、請求項1に記載の緑色顔料。
- 前記ポリハロゲノ亜鉛フタロシアニンのハロゲン基が、塩素基もしくは臭素基またはその双方である、請求項1に記載の緑色顔料。
- 前記ポリハロゲノ亜鉛フタロシアニンが、平均臭素基置換数が12以上16未満でかつ平均塩素基置換数が0超過4以下であるブロモクロロ亜鉛フタロシアニンである、請求項1に記載の緑色顔料。
- 前記ポリハロゲノ亜鉛フタロシアニンが、C.I.ピグメントグリーン58である、請求項1に記載の緑色顔料。
- 前記ポリハロゲノ非亜鉛金属フタロシアニンの非亜鉛金属が、アルミニウム、マグネシウム、チタン、スズ、鉄、コバルト、ニッケル、および銅からなる群から選ばれる1種またはそれ以上の金属である、請求項1に記載の緑色顔料。
- 前記ポリハロゲノ非亜鉛金属フタロシアニンのハロゲン基が、塩素基もしくは臭素基またはその双方である、請求項1に記載の緑色顔料。
- 前記ポリハロゲノ非亜鉛金属フタロシアニンが、平均臭素基置換数が12以上16未満でかつ平均塩素基置換数が0超過4以下であるブロモクロロ非亜鉛金属フタロシアニンである、請求項1に記載の緑色顔料。
- 前記ポリハロゲノ非亜鉛金属フタロシアニンが、ポリハロゲノアルミニウムフタロシアニン、ポリハロゲノマグネシウムフタロシアニン、ポリハロゲノチタニルフタロシアニン、ポリハロゲノスズフタロシアニンおよびポリハロゲノ銅フタロシアニンからなる群から選ばれる1種またはそれ以上のものである、請求項8に記載の緑色顔料。
- 有機溶剤中で加熱または沸騰処理された前後で、顔料粒子の粒子径が大きく伸長することなく、またX線回折の回折角度および回折強度も実質的に変化しない、請求項1に記載の緑色顔料。
- 前記ポリハロゲノ亜鉛フタロシアニン顔料と前記ポリハロゲノ非亜鉛金属フタロシアニン顔料とを媒体中に溶解し、該溶液からポリハロゲノ亜鉛フタロシアニンとポリハロゲノ非亜鉛金属フタロシアニンを複合重積物として共析させることを特徴とする、請求項1に記載の緑色顔料の製造方法。
- 前記ポリハロゲノ亜鉛フタロシアニン顔料と、前記ポリハロゲノ非亜鉛金属フタロシアニン顔料とを、モル比率30:70~95:5で酸中に溶解し、該溶液中の酸濃度を低下させることによってポリハロゲノ亜鉛フタロシアニンとポリハロゲノ非亜鉛金属フタロシアニンを複合重積物として共析させる、請求項11に記載の製造方法。
- 前記溶液中の酸濃度の低下が、該溶液に含水酸を添加するもしくは水分を吸収させることにより行われるか、または該溶液を、激しく撹拌されているまたは噴流している大量の水中あるいは氷水中に注入することにより行われる、請求項12に記載の緑色顔料の製造方法。
- 前記ポリハロゲノ非亜鉛金属フタロシアニン顔料の非亜鉛金属が、アルミニウム、マグネシウム、チタン、スズ、鉄、コバルト、ニッケル、および銅からなる群から選ばれる1種またはそれ以上の金属である請求項12に記載の緑色顔料の製造方法。
- 前記酸が、発煙硫酸または100%硫酸である、請求項12に記載の緑色顔料の製造方法。
- 前記共析と同時に、または共析の後に顔料化処理および/または顔料の微細化工程が行なわれる、請求項12に記載の緑色顔料の製造方法。
- 前記顔料化処理が、共析と同時に、または共析の後に、共析中のあるいは共析した物と、疎水性有機溶剤および/または親水性有機溶剤を含む水または氷水と接触させる、または前記有機溶剤と接触させる処理である、請求項11に記載の緑色顔料の製造方法。
- 請求項1~10のいずれか一項に記載の緑色顔料と、有機溶剤系、水系または水-親水性有機溶剤混合溶剤系液体媒体と、重合性オリゴマーまたは重合性単量体からなる重合性液状媒体と、可塑剤、オリゴマーまたは合成樹脂からなる樹脂媒体とを含んでなり、必要に応じて分散助剤として重合体系分散剤または低分子分散助剤をさらに含んでなることを特徴とする、緑色顔料分散組成物。
- 請求項18に記載の緑色顔料分散組成物と、希釈媒体と、塗膜形成材料としての熱可塑性重合体、反応性重合体、反応性オリゴマー、重合性単量体および架橋剤からなる群から選ばれた1種またはそれ以上の材料とを含んでなり、必要に応じてさらに硬化触媒または重合触媒を含んでなることを特徴とする、着色剤。
- カラーフィルター画素形成用インク、塗料、樹脂着色剤、印刷インク、染色剤、捺染剤、文房具、絵の具、インクジェット用インク、電子写真印刷用現像剤あるいは静電印刷用現像剤として用いられる、請求項19に記載の着色剤。
- 請求項18に記載の顔料分散組成物または請求項19に記載の着色剤を使用して物品を着色することを特徴とする、物品の着色方法。
- 前記の物品の着色が、カラーフィルター基板上に公知のフォトレジスト法、転写法、貼付け法、インクジェットプリント法、印刷法により画素形成する方法により行われる、請求項21に記載の物品の着色方法。
- 前記の物品の着色方法が、塗装、樹脂着色、印刷版印刷、染色、捺染、文字記録、描絵画、インクジェット印刷、電子写真印刷あるいは静電印刷により行われる、請求項21に記載の物品の着色方法。
- 請求項21~23のいずれか1項に記載の着色方法によって形成された着色物品。
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