NO131174B - - Google Patents
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- Publication number
- NO131174B NO131174B NO243971A NO243971A NO131174B NO 131174 B NO131174 B NO 131174B NO 243971 A NO243971 A NO 243971A NO 243971 A NO243971 A NO 243971A NO 131174 B NO131174 B NO 131174B
- Authority
- NO
- Norway
- Prior art keywords
- phthalocyanine
- metal
- alpha
- beta
- free phthalocyanine
- Prior art date
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- 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 description 36
- 238000010586 diagram Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000000049 pigment Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229940117389 dichlorobenzene Drugs 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LHYQAEFVHIZFLR-UHFFFAOYSA-L 4-(4-diazonio-3-methoxyphenyl)-2-methoxybenzenediazonium;dichloride Chemical compound [Cl-].[Cl-].C1=C([N+]#N)C(OC)=CC(C=2C=C(OC)C([N+]#N)=CC=2)=C1 LHYQAEFVHIZFLR-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000001905 inorganic group Chemical group 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- 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
- C09B67/0025—Crystal modifications; Special X-ray patterns
- C09B67/0026—Crystal modifications; Special X-ray patterns of phthalocyanine pigments
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
- G03G5/0528—Macromolecular bonding materials
- G03G5/0532—Macromolecular bonding materials obtained by reactions only involving carbon-to-carbon unsatured bonds
- G03G5/0535—Polyolefins; Polystyrenes; Waxes
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- G—PHYSICS
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- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
- G03G5/0528—Macromolecular bonding materials
- G03G5/0532—Macromolecular bonding materials obtained by reactions only involving carbon-to-carbon unsatured bonds
- G03G5/0539—Halogenated polymers
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- G—PHYSICS
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- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
- G03G5/0528—Macromolecular bonding materials
- G03G5/0532—Macromolecular bonding materials obtained by reactions only involving carbon-to-carbon unsatured bonds
- G03G5/0542—Polyvinylalcohol, polyallylalcohol; Derivatives thereof, e.g. polyvinylesters, polyvinylethers, polyvinylamines
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
- G03G5/0528—Macromolecular bonding materials
- G03G5/0532—Macromolecular bonding materials obtained by reactions only involving carbon-to-carbon unsatured bonds
- G03G5/0546—Polymers comprising at least one carboxyl radical, e.g. polyacrylic acid, polycrotonic acid, polymaleic acid; Derivatives thereof, e.g. their esters, salts, anhydrides, nitriles, amides
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
- G03G5/0528—Macromolecular bonding materials
- G03G5/0532—Macromolecular bonding materials obtained by reactions only involving carbon-to-carbon unsatured bonds
- G03G5/0553—Polymers derived from conjugated double bonds containing monomers, e.g. polybutadiene; Rubbers
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- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
- G03G5/0528—Macromolecular bonding materials
- G03G5/0557—Macromolecular bonding materials obtained otherwise than by reactions only involving carbon-to-carbon unsatured bonds
- G03G5/0567—Other polycondensates comprising oxygen atoms in the main chain; Phenol resins
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- G—PHYSICS
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- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
- G03G5/0528—Macromolecular bonding materials
- G03G5/0557—Macromolecular bonding materials obtained otherwise than by reactions only involving carbon-to-carbon unsatured bonds
- G03G5/0575—Other polycondensates comprising nitrogen atoms with or without oxygen atoms in the main chain
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/0664—Dyes
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/0664—Dyes
- G03G5/0696—Phthalocyanines
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/08—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/08—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic
- G03G5/082—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic and not being incorporated in a bonding material, e.g. vacuum deposited
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- G—PHYSICS
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- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/08—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic
- G03G5/087—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic and being incorporated in an organic bonding material
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Photoreceptors In Electrophotography (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Developing Agents For Electrophotography (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Description
I tillegg til det metallfrie ftalocyanin med en ovenfor an-gitte struktur er det kjent flere metallderivater av ftalocyanin hvor de to hydrogenatomer i midten av molekylet er erstattet av me-taller fra hvilken som helst gruppe i det periodiske system. Det er også kjent at fra to til seksten av de perifere hydrogenatomer i de fire benzenringer i ftalocyaninmolekylet kan erstattes med halogenatomer og av tallrike organiske og uorganiske grupper. In addition to the metal-free phthalocyanine with a structure stated above, several metal derivatives of phthalocyanine are known in which the two hydrogen atoms in the middle of the molecule are replaced by metals from any group in the periodic table. It is also known that from two to sixteen of the peripheral hydrogen atoms in the four benzene rings in the phthalocyanine molecule can be replaced by halogen atoms and by numerous organic and inorganic groups.
Det er kjent at ftalocyanin eksisterer i minst tre polymorfe former som det lett kan skilles mellom ved sammenlikning av deres røntgendiagrammer og/eller infrarødspektra. Pigmentets farge varierer også i samsvar med den polymorfe form, idet betaformen er grønnere enn alfa- eller gammaformene. Som angitt mer i detalj nedenfor, er det litt tvil om gammaformen virkelig er en særskilt polymorf form eller er en mindre krystallinsk form av alfa-ftalocyanin. I tillegg til disse tre kjente former som eksisterer i både metallinneholdende og metallfritt ftalocyanin er det kjent ytterligere polymorfe former av metallinneholdende ftalocyanin, nemlig en "R"-form som angitt i US-patentskrift 3.051.721, en "delta"-form som beskrevet i US-patentskrift 3.160.635 og en annen "delta"-form som beskrevet i US-patentskrift 3.150.150. Phthalocyanine is known to exist in at least three polymorphic forms which can be easily distinguished by comparison of their X-ray diagrams and/or infrared spectra. The color of the pigment also varies according to the polymorphic form, the beta form being greener than the alpha or gamma forms. As indicated in more detail below, there is some doubt as to whether the gamma form is really a distinct polymorphic form or is a less crystalline form of alpha-phthalocyanine. In addition to these three known forms that exist in both metalline-containing and metal-free phthalocyanine, further polymorphic forms of metalline-containing phthalocyanine are known, namely an "R" form as indicated in US Patent 3,051,721, a "delta" form as described in US Patent 3,160,635 and another "delta" form as described in US Patent 3,150,150.
Det er nå blitt funnet at metallfritt ftalocyanin eksisterer i ytterligere en form, heretter betegnet "X"-form ftalocyanin. Som påpekt mer fullstendig nedenfor, avviker røntgenspektra og infrarødspektra for denne form betydelig fra tilsvarende spektra for de tidligere kjente former. Som beskrevet i norsk patentskrift 124.709 har "X"-formftalocyaninet anvendelighet som fotoledende materiale i elektrofotografi når det blandes med et bindemiddel og belegges på et underlag. Den resulterende elektrofotografiske plate har forbausende høy fotofølsomhet når ftalocyaninet er enten i sin helhet'"X"-form eller en blanding av "X"-form og alfa-form ftalocyanin. It has now been found that metal-free phthalocyanine exists in a further form, hereinafter referred to as "X" form phthalocyanine. As pointed out more fully below, the X-ray and infrared spectra of this form differ significantly from the corresponding spectra of the previously known forms. As described in Norwegian patent document 124,709, the "X"-form phthalocyanine has utility as a photoconductive material in electrophotography when it is mixed with a binder and coated on a substrate. The resulting electrophotographic plate has surprisingly high photosensitivity when the phthalocyanine is either entirely "X" form or a mixture of "X" form and alpha-form phthalocyanine.
Ifølge oppfinnelsen er det frembrakt et metallfritt ftalocyanin i "X"-formen som kjennetegnes ved at det har et røntgen-diagram som oppviser sterke linjer ved Braggvinkler 7,5, 9,1, According to the invention, a metal-free phthalocyanine in the "X" form has been produced, which is characterized by having an X-ray diagram showing strong lines at Bragg angles 7.5, 9.1,
16,7, 17,3 og 22,3. 16.7, 17.3 and 22.3.
Metallfritt ftalocyanin i "X" form, fremstilles ved følgende trinn: Fremskaffing av et ftalocyanin, fjerning av forurensninger og ethvert metallatom fra ftalocyaninet og formaling av ftalocyaninet inntil dets røntgendiagram oppviser sterke linjer ved Bragg-vinkler 7,5, 9,1, 16,7, 17,3 og 22,3. Metal-free phthalocyanine in "X" form, is prepared by the following steps: Obtaining a phthalocyanine, removing impurities and any metal atom from the phthalocyanine, and grinding the phthalocyanine until its X-ray pattern exhibits strong lines at Bragg angles 7.5, 9.1, 16, 7, 17.3 and 22.3.
Forskjellene mellom den nye "X"-form av metallfritt ftalocyanin og de tidligere kjente alfa-, beta- og gamma-former vil bli ytterligere klargjort ved henvisning til tegningen som viser sammenliknende røntgendiagrammer for de forskjellige polymorfe former av metallfritt ftalocyanin. The differences between the new "X" form of metal-free phthalocyanine and the previously known alpha, beta and gamma forms will be further clarified by reference to the drawing showing comparative X-ray diagrams of the various polymorphic forms of metal-free phthalocyanine.
Tegningen viser røntgendiagrammer for alfa-, beta- og X-form polymorfe former av prøver fremstilt på laboratoriet. The drawing shows X-ray diagrams of alpha, beta and X-form polymorphic forms of samples prepared in the laboratory.
Tegningen viser et sett kurver som sammenlikner alfa-, beta-og gammaformen av metallfritt ftalocyanin, ordnet i vertikal oppstilling på linje for lettvint sammenlikning. Prøvene av hver form av ftalocyanin testet med røntgenstråling ble fremstilt på laboratoriet og analysert med samme utstyr av samme ope-ratør for derved å være sikker på samsvar mellom prøvene. Prøven som ble brukt til å frembringe kurven for alfaformen ble fremstilt av kommersielt "Monolite Fast Blue GS", en blanding av alfa og beta metallfritt ftalocyanin. Dette pigment ble helt omdannet til alfaform før testing ved løsningsmiddelsektraksjon med diklorbenzen, vasking med aceton og utfelling fra svovelsyre i isvann. Prøven av betaformen som ga kurven som er vist på tegningen, ble fremstilt ved å suspendere kommersielt "Monolite East Blue G-S" i trietylentetramin i en konsentrasjon av 1 vektdel pigment til 5 vektdeler trietylentetramin i fire dager ved 23°C. Pigmentet ble deretter vasket med metanol og tørket. "X"-formen ftalocyanin som ga kurven som vist på tegningen, ble fremstilt som følger: Kommersielt "Monolite Fast Blue G-S" ble løsningsmiddelekstrahert med diklorbenzen, deretter vasket med aceton og tørket. Pigmentet ble deretter løst i svovelsyre og utfelt i isvann. Utfellingen ble vasket med metanol og tørket. Pigmentet ble deretter omhyggelig malt i en kulemølle i sju dager, vasket med dimetyl-formamid og deretter med metanol. The drawing shows a set of curves comparing the alpha, beta and gamma forms of metal-free phthalocyanine, arranged vertically in line for easy comparison. The samples of each form of phthalocyanine tested with X-ray radiation were prepared in the laboratory and analyzed with the same equipment by the same operator in order to be sure of conformity between the samples. The sample used to generate the curve for the alpha form was prepared from commercial "Monolite Fast Blue GS", a mixture of alpha and beta metal-free phthalocyanine. This pigment was completely converted to the alpha form prior to testing by solvent extraction with dichlorobenzene, washing with acetone and precipitation from sulfuric acid in ice water. The sample of the beta form which gave the curve shown in the drawing was prepared by suspending commercial "Monolite East Blue G-S" in triethylenetetramine at a concentration of 1 part by weight of pigment to 5 parts by weight of triethylenetetramine for four days at 23°C. The pigment was then washed with methanol and dried. The "X" form phthalocyanine which gave the curve shown in the drawing was prepared as follows: Commercial "Monolite Fast Blue G-S" was solvent extracted with dichlorobenzene, then washed with acetone and dried. The pigment was then dissolved in sulfuric acid and precipitated in ice water. The precipitate was washed with methanol and dried. The pigment was then carefully milled in a ball mill for seven days, washed with dimethylformamide and then with methanol.
Røntgendiagrammene for alfa- og betaftalocyanin, fremstilt på laboratoriet, stemmer som vist på tegningen overens med de diagrammer som er referert i litteraturen. The X-ray diagrams for alpha- and beta-phthalocyanine, prepared in the laboratory, agree, as shown in the drawing, with the diagrams referred to in the literature.
Som det kan sees på tegningen, avviker "X"-formen av ftalocyanin oppsiktsvekkende fra alfa- og betaformene. Spektret for "X"-formen har topper ved Bragg-vinkler 17,5 og 22,3 som ikke eksisterer for de alfa- og beta-polymorfe former. "X"-formen viser også en topp ved 9,1 som ikke er til stede for alfa-formen og som har lavere intensitet enn tilsvarende topp for beta-formen. As can be seen in the drawing, the "X" form of phthalocyanine deviates strikingly from the alpha and beta forms. The spectrum for the "X" form has peaks at Bragg angles 17.5 and 22.3 which do not exist for the alpha and beta polymorphic forms. The "X" form also shows a peak at 9.1 which is not present for the alpha form and which is of lower intensity than the corresponding peak for the beta form.
Videre har beta-formen topper ved omkring 26,2, 18,0, 14,1 og Furthermore, the beta form peaks at around 26.2, 18.0, 14.1 and
7,0, og alfa-formen har topper ved omkring 26,7, 13,6 og 6,8 som ikke opptrer hos "X"-formen. I tillegg har "X"-formen topper ved 7,5 og 16.7. 7.0, and the alpha form has peaks at about 26.7, 13.6 and 6.8 which do not appear in the "X" form. In addition, the "X" shape has peaks at 7.5 and 16.7.
Spesielle fremstillingsmåter for alfa-, beta- og X-formene av ftalocyanin er som følger: Special methods of preparation for the alpha, beta and X forms of phthalocyanine are as follows:
Fremstilling av alfa metallfritt ftalocyanin. Preparation of alpha metal-free phthalocyanine.
86,7 g litiumftalocyanin ble tilsatt til 600 ml godt 86.7 g of lithium phthalocyanine was added to a 600 ml well
omrørt konsentrert svovelsyre ved 0°C. Blandingen ble deretter omrørtved denne temperatur i to timer. Den resulterende løsning ble deretter filtrert gjennom en grov, sintret glasstrakt og tømt sakte og under omrøring i 4 liter"isvann. Etter setting i flere timer ble blandingen filtrert og filterkaken vasket til nøytralt med vann. Filterkaken ble til slutt skyllet med metanol atskillige ganger og tørket i luft. Det resulterende pulver ble deretter ekstrahert med aceton i et kontinuerlig ekstraksjonsapparat i tjuefire timer og fikk tørke i luften til dannelse av et blått pulver. stirred concentrated sulfuric acid at 0°C. The mixture was then stirred at this temperature for two hours. The resulting solution was then filtered through a coarse, sintered glass funnel and emptied slowly and with stirring into 4 liters of ice water. After setting for several hours, the mixture was filtered and the filter cake washed until neutral with water. The filter cake was finally rinsed with methanol several times and dried in air The resulting powder was then extracted with acetone in a continuous extractor for twenty-four hours and allowed to air dry to form a blue powder.
For å sikre seg mot rester av litiumsalt ble utfellingen gjentatt. Det ble oppnådd 55,4 g av et blått pulver hvis røntgen-diagram svarte til det kjente, publiserte diagram for alfa metallfritt ftalocyanin. To ensure against residual lithium salt, the precipitation was repeated. There was obtained 55.4 g of a blue powder whose X-ray pattern corresponded to the known published pattern for alpha metal-free phthalocyanine.
Fremstilling av beta metallfritt ftalocyanin. Preparation of beta metal-free phthalocyanine.
10 g kommersielt "Monolite Fast Blue GS" ble plassert i en "Vycor" skål som ble innført i et 50 mm's glassrør egnet for opp-varming i en forbrenningsovn. Temperaturen i ovnen ble langsomt hevet til 350°C under den første 1-jjr time for å unngå at prøven ødelegges og til slutt holdt ved 350 - 430°C i de fire neste timer. En strøm av tørr nitrogen ble ledet gjennom røret under varmebehandlingen. Den behandlete prøve ble overført til et tørkeapparat for kjøling. Resultatet var 9,45 g blåsvart pulver som ga et røntgendiagram som svarte til det for beta-formen. Fremstilling av " X"- form metallfritt ftalocyanin. 10 g of commercial "Monolite Fast Blue GS" was placed in a "Vycor" dish which was inserted into a 50 mm glass tube suitable for heating in an incinerator. The temperature in the oven was slowly raised to 350°C during the first one-hour hour to avoid spoiling the sample and finally held at 350-430°C for the next four hours. A stream of dry nitrogen was passed through the tube during the heat treatment. The treated sample was transferred to a drying apparatus for cooling. The result was 9.45 g of blue-black powder which gave an X-ray pattern corresponding to that of the beta form. Preparation of "X"-form metal-free phthalocyanine.
En 9 grams prøve av alfa metallfritt ftalocyanin, fremstilt ved felling fra svovelsyre, og 90 g natriumklorid ble plas- A 9-gram sample of alpha metal-free phthalocyanine, prepared by precipitation from sulfuric acid, and 90 g of sodium chloride were placed
sert i en ca. 1 liters porselenkulemølle og malt i 72 timer med 70 omdreininger pr. minutt. served in an approx. 1 liter porcelain ball mill and ground for 72 hours at 70 revolutions per minute.
Det malte pulver ble fjernet manuelt fra møllen og ekstrahert med 1500 ml 1 prosentig saltsyre vad 70 -80°C i en time. The ground powder was removed manually from the mill and extracted with 1500 ml of 1 percent hydrochloric acid at 70-80°C for one hour.
Det resulterende slam ble 'filtrert og filterkaken vasket gjentatte ganger med destillert vann for fjerning av gjenværende natriumklorid. Filterkaken ble til slutt skyllet med metanol flere ganger og tørket i luft. Resultatet ble 8,8 g blått pulver. Rønt-gendiagrammet til dette materiale kan ikke bringes i samsvar med noen av de publiserte strukturer for forskjellige polymorfe former for metallfrie ftalocyaniner, men stemmer overens med de fast-satte diagrammer for "X"-formen som vist på den medfølgende teg-ning, og følgelig må det ansees at materialet er "X"-formen av metallfritt ftalocyanin. The resulting sludge was filtered and the filter cake washed repeatedly with distilled water to remove residual sodium chloride. The filter cake was finally rinsed with methanol several times and dried in air. The result was 8.8 g of blue powder. The X-ray diagram of this material cannot be reconciled with any of the published structures for various polymorphic forms of metal-free phthalocyanines, but is consistent with the established diagrams for the "X" form as shown in the accompanying drawing, and therefore, the material must be considered to be the "X" form of metal-free phthalocyanine.
Selv om de mest effektive elektrofotografiske plater blir fremstilt ved blanding av "X"-formen av metallfritt pigment i harpiksbindemiddel, kan også meget gode plater fremstilles med den alfa metallfrie form, spesielt hvis denne omdannes til betaformen ved omkrystallisering i løsningsmiddel eller til "X"-formen i et belegg, som vil bli beskrevet senere. For å bestemme krystallformen til ftalocyaninpigmentet slik som det virkelig foreligger i det fotoledende lag etter at dette er tørket og her-det, blir laget skrapet av fra sitt underlag og pulverisert uten noe forsøkt på å fjerne den omgivende harpiks (sistnevnte påvirker ikke i nevneverdig grad målingen). Pulveret fylles deretter i et kapillar og forskjellige forsøk foretas med komprimerte pulverpellets. Resultatene av disse forsøk er gjengitt som angitt ovenfor (på alfa-, beta-, gamma- og "X"-formen av metallfrie ftalocyaninpigmenter). Although the most effective electrophotographic plates are made by mixing the "X" form of metal-free pigment in resin binder, very good plates can also be made with the alpha metal-free form, especially if this is converted to the beta form by solvent recrystallization or to "X" -the form in a coating, which will be described later. In order to determine the crystal form of the phthalocyanine pigment as it actually exists in the photoconductive layer after it has been dried and cured, the layer is scraped off from its substrate and pulverized without any attempt to remove the surrounding resin (the latter does not significantly affect the measurement). The powder is then filled into a capillary and various tests are carried out with compressed powder pellets. The results of these tests are reproduced as indicated above (on the alpha, beta, gamma and "X" forms of metal-free phthalocyanine pigments).
Til alle Bragg-vinkler som er nevnt i beskrivelsen til To all Bragg angles mentioned in the description of
denne oppfinnelse ble det benyttet stråling som svarer til kobber-K-bølgelengden, 1.54050 Å. Hvis det er ønskelig, kan verdier som er målt i Bragg-vinkler regnes om til absolutte avstander (d) ved følgende likning: N-A. = 2 d sin 0, hvor N er graden av diffrak-sjon (her 2). X er røntgenstrålingens bølgelengde (her 1,54050 A), d er avstanden som fremkaller interferensfenomenet og 0 er Bragg-spredningsvinkelen. this invention, radiation corresponding to the copper K wavelength, 1.54050 Å, was used. If desired, values measured in Bragg angles can be converted to absolute distances (d) by the following equation: N-A. = 2 d sin 0, where N is the degree of diffraction (here 2). X is the wavelength of the X-ray radiation (here 1.54050 A), d is the distance that causes the interference phenomenon and 0 is the Bragg scattering angle.
Claims (1)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US37519164A | 1964-06-15 | 1964-06-15 |
Publications (2)
Publication Number | Publication Date |
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NO131174B true NO131174B (en) | 1975-01-06 |
NO131174C NO131174C (en) | 1975-04-16 |
Family
ID=23479871
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
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NO15846965A NO124709B (en) | 1964-06-15 | 1965-06-14 | |
NO243971A NO131174C (en) | 1964-06-15 | 1971-06-28 |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
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NO15846965A NO124709B (en) | 1964-06-15 | 1965-06-14 |
Country Status (16)
Country | Link |
---|---|
JP (1) | JPS494338B1 (en) |
AT (2) | AT297883B (en) |
BE (1) | BE664883A (en) |
CA (1) | CA950251A (en) |
CH (1) | CH479094A (en) |
CY (1) | CY496A (en) |
DE (2) | DE1497205C3 (en) |
ES (1) | ES313979A1 (en) |
FR (1) | FR1447277A (en) |
GB (2) | GB1116554A (en) |
IL (2) | IL33063A (en) |
LU (1) | LU48728A1 (en) |
MY (1) | MY6900153A (en) |
NL (1) | NL153339B (en) |
NO (2) | NO124709B (en) |
SE (2) | SE316682B (en) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3573904A (en) * | 1967-01-09 | 1971-04-06 | Xerox Corp | Combination of electrography and manifold imaging |
JPS5364040A (en) * | 1976-11-19 | 1978-06-08 | Hitachi Ltd | Photosensitive plate for xerography |
GB1599430A (en) * | 1977-06-27 | 1981-09-30 | Konishiroku Photo Ind | Photoconductive composition for use in the preparation of an electrophotographic material |
JPS58166355A (en) * | 1982-03-29 | 1983-10-01 | Toyo Ink Mfg Co Ltd | Electrophotographic receptor |
JPS58182639A (en) * | 1982-04-20 | 1983-10-25 | Hitachi Ltd | Electrophotographic receptor |
JPS59232348A (en) * | 1983-06-15 | 1984-12-27 | Mita Ind Co Ltd | Laminated photosensitive body and its production |
JPS6050539A (en) * | 1983-08-31 | 1985-03-20 | Toyo Ink Mfg Co Ltd | Electrophotographic sensitive body |
DE3417951A1 (en) * | 1984-05-15 | 1985-11-21 | Hoechst Ag, 6230 Frankfurt | ELECTROPHOTOGRAPHIC RECORDING MATERIAL |
US4975350A (en) * | 1986-10-20 | 1990-12-04 | Konica Corporation | Photoreceptor having a metal-free phthalocyanine charge generating layer |
EP0458651B1 (en) * | 1990-05-25 | 1994-03-09 | Matsushita Electric Industrial Co., Ltd. | Photosensitive materials comprising organic photoconductive substances in a binder polymer having aromatic rings, OH groups and bromine joined at the aromatic ring or rings |
DE4234922A1 (en) * | 1992-10-16 | 1994-04-21 | Basf Ag | Metal-free phthalocyanine of the gamma modification |
WO2005085365A1 (en) | 2004-03-04 | 2005-09-15 | Mitsubishi Chemical Corporation | Phthalocyanine composition, and photoconductive material, electrophotographic photoreceptor, electrophotographic photoreceptor cartridge, and image-forming apparatus each employing the composition |
-
1965
- 1965-03-29 JP JP1786765A patent/JPS494338B1/ja active Pending
- 1965-04-12 IL IL3306365A patent/IL33063A/en unknown
- 1965-04-12 IL IL2334265A patent/IL23342A/en unknown
- 1965-04-30 CA CA929,519,A patent/CA950251A/en not_active Expired
- 1965-05-31 LU LU48728D patent/LU48728A1/xx unknown
- 1965-06-02 SE SE723565A patent/SE316682B/xx unknown
- 1965-06-03 BE BE664883D patent/BE664883A/xx unknown
- 1965-06-03 CH CH779565A patent/CH479094A/en not_active IP Right Cessation
- 1965-06-04 DE DE1965R0040803 patent/DE1497205C3/en not_active Expired
- 1965-06-04 DE DE19651794329 patent/DE1794329B2/en active Granted
- 1965-06-08 ES ES0313979A patent/ES313979A1/en not_active Expired
- 1965-06-08 FR FR19943A patent/FR1447277A/en not_active Expired
- 1965-06-10 AT AT568569A patent/AT297883B/en active
- 1965-06-10 AT AT526065A patent/AT293165B/en not_active IP Right Cessation
- 1965-06-14 NO NO15846965A patent/NO124709B/no unknown
- 1965-06-15 NL NL6507664A patent/NL153339B/en not_active IP Right Cessation
- 1965-06-15 GB GB259368A patent/GB1116554A/en not_active Expired
- 1965-06-15 GB GB2243165A patent/GB1116553A/en not_active Expired
-
1969
- 1969-05-24 CY CY49669A patent/CY496A/en unknown
- 1969-08-12 SE SE11202/69A patent/SE339730B/xx unknown
- 1969-12-30 MY MY6900153A patent/MY6900153A/en unknown
-
1971
- 1971-06-28 NO NO243971A patent/NO131174C/no unknown
Also Published As
Publication number | Publication date |
---|---|
DE1794329B2 (en) | 1974-05-30 |
DE1497205C3 (en) | 1979-04-12 |
GB1116554A (en) | 1968-06-06 |
LU48728A1 (en) | 1965-12-01 |
ES313979A1 (en) | 1966-03-01 |
CA950251A (en) | 1974-07-02 |
CY496A (en) | 1969-05-24 |
BE664883A (en) | 1965-12-03 |
IL23342A (en) | 1970-06-17 |
NL6507664A (en) | 1965-12-16 |
JPS494338B1 (en) | 1974-01-31 |
DE1794329C3 (en) | 1975-02-06 |
IL33063A (en) | 1970-06-17 |
AT293165B (en) | 1971-09-27 |
NL153339B (en) | 1977-05-16 |
MY6900153A (en) | 1969-12-31 |
GB1116553A (en) | 1968-06-06 |
NO124709B (en) | 1972-05-23 |
FR1447277A (en) | 1966-07-29 |
DE1794329A1 (en) | 1971-12-30 |
SE339730B (en) | 1971-10-18 |
DE1497205B2 (en) | 1978-08-03 |
SE316682B (en) | 1969-10-27 |
CH479094A (en) | 1969-09-30 |
NO131174C (en) | 1975-04-16 |
AT297883B (en) | 1972-04-10 |
DE1497205A1 (en) | 1969-04-30 |
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