WO2015019659A1 - ハロゲン化有機顔料の製造方法、その製造方法により得られるハロゲン化有機顔料およびそれを含む着色組成物 - Google Patents
ハロゲン化有機顔料の製造方法、その製造方法により得られるハロゲン化有機顔料およびそれを含む着色組成物 Download PDFInfo
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- WO2015019659A1 WO2015019659A1 PCT/JP2014/058343 JP2014058343W WO2015019659A1 WO 2015019659 A1 WO2015019659 A1 WO 2015019659A1 JP 2014058343 W JP2014058343 W JP 2014058343W WO 2015019659 A1 WO2015019659 A1 WO 2015019659A1
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- Prior art keywords
- organic pigment
- pigment
- acid
- halogenated organic
- parts
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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
- C09B68/00—Organic pigments surface-modified by grafting, e.g. by establishing covalent or complex bonds, in order to improve the pigment properties, e.g. dispersibility or rheology
- C09B68/40—Organic pigments surface-modified by grafting, e.g. by establishing covalent or complex bonds, in order to improve the pigment properties, e.g. dispersibility or rheology characterised by the chemical nature of the attached groups
- C09B68/44—Non-ionic groups, e.g. halogen, OH or SH
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/50—Iso-indoles; Hydrogenated iso-indoles with oxygen and nitrogen atoms in positions 1 and 3
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/08—Copper compounds
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- 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
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
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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
- C09B19/00—Oxazine dyes
- C09B19/02—Bisoxazines prepared from aminoquinones
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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
- C09B25/00—Quinophthalones
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
- C09B47/061—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide having halogen atoms linked directly to the Pc skeleton
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
- C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
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Definitions
- the present invention relates to a method for producing a halogenated organic pigment. More specifically, the present invention relates to a method for producing a halogenated organic pigment excellent in safety and productivity by halogenating an organic pigment with a specific N-haloimide compound. Moreover, it is related with the halogenated organic pigment obtained by the manufacturing method, and a coloring composition containing the same.
- Organic pigments are widely used as coloring compositions for offset inks, gravure inks, flexo inks, plastic colorants, paints, color toners, color filter resist inks for color filters, and inkjet inks because of their usefulness as color materials. It is used for These organic pigments have color characteristics such as coloring power, sharpness and hue, durability such as light resistance, heat resistance, acid resistance, alkali resistance, solvent resistance and migration resistance, and dispersion depending on the application. Characteristics such as property and fluidity are required.
- halogenated organic pigments containing a halogen in the structure are often used for adjusting the hue and improving durability such as weather resistance, light resistance, heat resistance and chemical resistance.
- Representative halogenated organic pigments include halogenated quinacridone pigments, C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Violet 23, C.I. I. Pigment Red254, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 109, C.I. I. Pigment Yellow 110, etc. (Non-Patent Document 1).
- Halogenated quinacridone pigment is a generic name for compounds in which quino [2,3-b] acridine-7,14 (5H, 12H) -dione is a basic skeleton and a part of the hydrogen atoms are substituted with halogen atoms. .
- halogenated quinacridone pigments include 2,9-dichloroquinacridone and 3,10-dichloroquinacridone, as described in Non-Patent Document 1, respectively.
- a solid solution of unsubstituted quinacridone and 4,11-dichloroquinacridone is C.I. I. It is registered and disclosed as Pigment Red207.
- halogenated quinacridones other than the above-mentioned halogenated quinacridone pigments, sodium 3,10-dichloroquinacridone sulfonate and phthalimidomethylated 3,10-dichloroquinacridone are disclosed in Patent Document 1, and pigments for inkjet inks The use as a dispersion aid is described.
- Quinacridone compounds other than these halogenated quinacridones include unsubstituted quinacridone which is quino [2,3-b] acridine-7,14 (5H, 12H) -dione itself, and 2,9 substituted with 2 methyl groups.
- -Dimethylquinacridone respectively C.I. I. Pigment Violet 19 and C.I. I. It is known as Pigment Red122.
- Patent Document 2 discloses quinacridone substituted with a phthalimidomethyl group
- Patent Document 3 discloses quinacridone substituted with a sulfonic acid group
- Patent Document 4 discloses —SO 2 NH— (CH 2 ) 3 —.
- Quinacridone substituted with an N (C 2 H 5 ) 2 group is disclosed.
- the basic skeleton of quino [2,3-b] acridine-7,14 (5H, 12H) -dione possessed by a quinacridone compound has a relatively simple chemical structure. Therefore, when the quinacridone compound is used as a pigment, there are essential problems that the range of the color tone that can be adjusted is narrow and that it is difficult to prepare fine particles because of good crystallinity. However, the aforementioned C.I. I. As a result of the discovery of many solid solution pigments, such as Pigment Red207, in which two or more kinds of quinacridone mainly composed of dichloroquinacridone are homogeneously mixed, the color range has been expanded, and at the same time, the crystallinity is lowered due to the mixture.
- solid solution pigments such as Pigment Red207
- halogenated quinacridone into which one or more halogen atoms have been introduced has become an increasingly important compound in the industry. Under such circumstances, attention has also been paid to the manufacturing issues.
- chloroaniline used as a starting material for the production of chlorinated quinacridone has a safety problem of suspected carcinogenicity, and is relatively expensive and difficult to obtain as an industrial chemical.
- chlorinated quinacridone using chloroaniline there is a problem of productivity such that the total yield is lower than when producing unsubstituted quinacridone using aniline as a starting material. is there.
- chlorinated quinacridone is substantially only dichloroquinacridone and its solid solution, and is used for coloring compositions such as inks, paints, plastics, color toners, inkjet inks and color filter resist inks.
- coloring compositions such as inks, paints, plastics, color toners, inkjet inks and color filter resist inks.
- the range of the color tone that can be adjusted is still narrow and it is difficult to prepare fine particles.
- the halogenated organic pigment containing the halogenated quinacridone can be produced by various methods. These methods can be broadly classified into a method for producing a base organic pigment by halogenation with a halogenating agent and a method for producing a pigment using a raw material having a halogen atom. In the latter method, generally, it is difficult to obtain a raw material having a halogen atom and it is often expensive. Moreover, since the obtained halogenated organic pigment is also a single compound, it is difficult to adjust the hue and the like by controlling the number of halogen substitution of the pigment, and a halogenated organic pigment having excellent color characteristics can be obtained. Often not. Therefore, the former method is generally employed industrially.
- the former method includes (1) a method of halogenating an organic pigment using chlorine or bromine as a halogenating agent (for example, Patent Document 5), and (2) an organic pigment using N-bromosuccinimide as a halogenating agent.
- a method of halogenating for example, Patent Document 6
- the method (1) uses highly toxic chlorine and bromine, a large-scale special production facility in consideration of safety is required.
- equipment for treating a large amount of by-produced hydrogen halide gas is required.
- the metal element iron, aluminum, calcium, etc.
- a part of the desired halogenated organic pigment is replaced or raked with the metal element.
- the obtained crude halogenated organic pigment has a large particle size and tends to be inferior in color characteristics such as coloring power and sharpness. Therefore, it is difficult to use as it is as a coloring material. Therefore, in order to finish a pigment form having a high utility value as a coloring material, a pigmentation process such as acid pasting is often required once a crude halogenated organic pigment is produced.
- a method for obtaining a halogenated organic pigment useful as a coloring material without going through such a pigmentation step has been demanded.
- the conventional method for producing a halogenated organic pigment preferably uses a highly toxic raw material such as chlorine, bromine, chloroaniline, a low reaction yield, hydrogen halide gas, succinimide, etc.
- a highly toxic raw material such as chlorine, bromine, chloroaniline, a low reaction yield, hydrogen halide gas, succinimide, etc.
- the problem to be solved by the present invention is to provide a novel method for producing a halogenated organic pigment excellent in safety and productivity.
- Another object of the present invention is to provide a halogenated organic pigment having a wide range of color tones and prepared into fine particles, and a coloring composition using the same.
- the present invention is a method for producing a halogenated organic pigment, comprising a halogenation step of halogenating an organic pigment with a halogenating agent, wherein the halogenating agent is trichloroisocyanuric acid, dichloroisocyanuric acid metal salt,
- the present invention relates to a method for producing a halogenated organic pigment containing one or more N-haloimide compounds selected from the group consisting of bromoisocyanuric acid and dibromoisocyanuric acid metal salts.
- the present invention relates to a halogenated organic pigment obtained by the above method for producing a halogenated organic pigment.
- the present invention also relates to a coloring composition comprising the halogenated organic pigment and a vehicle component. Furthermore, the present invention relates to a color toner, an ink-jet ink and a color filter resist ink containing the coloring composition. The present invention relates to a printed matter printed using the color toner or the inkjet ink. The present invention relates to a color filter having a filter segment formed using the color filter resist ink.
- the present invention does not use highly toxic raw materials such as chlorine, bromine, chloroaniline, etc., and uses a N-haloimide compound that is safe and easy to handle as a halogenating agent. Therefore, it is possible to provide a method for producing a halogenated organic pigment that is excellent in safety and has a high total yield and excellent productivity because it does not require special production equipment and by-product treatment equipment. Moreover, since the halogenated organic pigment obtained by the production method of the present invention has a wide range of color tones that can be adjusted, it is possible to provide a colored composition that is versatile and excellent in usefulness.
- halogenated organic pigment As a coloring material, it is necessary to go through a two-stage manufacturing process, that is, a halogenation process and a pigmentation process. Further, halogenation and pigmentation by acid pasting treatment can be performed simultaneously, the production process can be shortened, and a method for producing a halogenated organic pigment having excellent productivity can be provided.
- the present invention is a method for producing a halogenated organic pigment, comprising a halogenation step of halogenating an organic pigment with a halogenating agent, wherein the halogenating agent is trichloroisocyanuric acid, dichloroisocyanuric acid metal salt, tribromoisocyanuric
- a halogenated organic pigment comprising one or more N-haloimide compounds selected from the group consisting of acids and metal salts of dibromoisocyanuric acid.
- the N-haloimide compound contains one or more N-chloroimide compounds selected from the group consisting of trichloroisocyanuric acid and sodium dichloroisocyanurate.
- the halogenation step is preferably performed in the presence of a solvent, and the solvent preferably contains at least one of a strong acid and a eutectic salt.
- the strong acid preferably contains one or more selected from the group consisting of sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, polyphosphoric acid and methanesulfonic acid.
- the eutectic salt is preferably a eutectic salt of aluminum chloride and sodium chloride.
- the organic pigment is at least one selected from the group consisting of quinacridone pigments, phthalocyanine pigments, anthraquinone pigments, quinophthalone pigments, perylene pigments, isoindolinone pigments, dioxazine pigments and indanthrone pigments. It is preferable to include.
- CI means a color index
- the halogenating agent used in the present invention includes one or more N-haloimide compounds selected from the group consisting of trichloroisocyanuric acid, dichloroisocyanuric acid metal salt, tribromoisocyanuric acid and dibromoisocyanuric acid metal salt.
- N-chloroimide compound used in the chlorination reaction is widely used as a disinfectant for swimming pool water, and can be said to be easy to handle and highly safe.
- the metal salt as the N-haloimide compound is not particularly limited, but from the viewpoint of cost and availability, an alkali metal salt is preferable, a sodium salt or potassium salt is more preferable, and a sodium salt is particularly preferable. . Therefore, as a more preferable embodiment of the halogenating agent used in the present invention, one or more N-haloimide compounds selected from the group consisting of trichloroisocyanuric acid, sodium dichloroisocyanurate, tribromoisocyanuric acid and sodium dibromoisocyanurate are included. An embodiment is mentioned. Of the halogenated organic pigments, chlorinated organic pigments are important compounds widely used in industry. Therefore, an embodiment including one or more N-chloroimide compounds selected from the group consisting of trichloroisocyanuric acid and sodium dichloroisocyanurate used as a chlorinating agent is particularly preferable.
- the amount of the N-haloimide compound used is preferably 1 to 2 molar equivalents of the theoretical amount corresponding to the desired number of halogen atom substitutions with respect to the organic pigment.
- the reaction conditions such as reaction temperature and addition of catalyst can be adjusted. By adjusting appropriately, it can be reduced to the theoretical amount of 1 to 1.2 molar equivalents. That is, the amount of the N-haloimide compound used is preferably 1 to 2 molar equivalents based on the effective halogen.
- the halogenation step is preferably carried out in the presence of a solvent.
- the solvent is not particularly limited as long as it does not inhibit the halogenation reaction and does not cause the decomposition of the skeleton of the organic pigment. From the viewpoint of the reaction yield and the like, at least any of strong acid and eutectic salt is acceptable. It is preferable to use a solvent containing these.
- strong acids include inorganic acids such as sulfuric acid, fuming sulfuric acid, chlorosulfonic acid and polyphosphoric acid, and organic acids such as trifluoroacetic acid, dichloroacetic acid, methanesulfonic acid and ethanesulfonic acid.
- Inorganic acids and methanesulfonic acid are preferable from the viewpoint of cost, reaction yield, advantages in the production process, and the like, and sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, polyphosphoric acid, methanesulfonic acid and mixtures thereof are more preferable.
- sulfuric acid may cause decomposition of the organic pigment skeleton when the water content is high, sulfuric acid having a high concentration of 90% by mass or more is preferable.
- Examples of eutectic salts include eutectic salts of aluminum chloride and sodium chloride.
- the solvent may be a mixture of a strong acid and a eutectic salt.
- the amount of the solvent is not particularly limited, but when a strong acid is used, it is preferable to use 2 to 50 times by mass with respect to the organic pigment, and the solubility of the organic pigment and the substitution of halogen atoms to be halogenated From the viewpoint of number and industrial economy, it is more preferable to use 3 to 20 times by mass. When a eutectic salt is used as a solvent, it is preferable to use 2 to 30 times by mass with respect to the organic pigment.
- the organic pigment that can be used as a raw material in the production method of the present invention is not particularly limited as long as it can be halogenated with the N-haloimide compound used in the present invention.
- the organic pigment in the present invention include quinacridone pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, dioxazine pigments, diketopyrrolopyrrole pigments, quinophthalone pigments, anthrapyrimidine pigments, ansanthrone pigments, Violanthrone pigments, indanthrone pigments, flavanthrone pigments, perinone pigments, perylene pigments, isoindoline pigments, isoindolinone pigments, thiazine indigo pigments, thioindigo pigments and pyranthrone pigments, etc.
- organic pigments may be pigments having halogen as a substituent in the structure as long as they have at least one hydrogen atom that can be substituted by halogen.
- halogen as a substituent in the structure as long as they have at least one hydrogen atom that can be substituted by halogen.
- at least one selected from the group consisting of quinacridone pigments, phthalocyanine pigments, anthraquinone pigments, quinophthalone pigments, perylene pigments, isoindolinone pigments, dioxazine pigments and indanthrone pigments is included. Those are preferred.
- the quinacridone pigment used as a raw material for the production method of the present invention is preferably a quinacridone compound represented by the following formula I.
- R 1 to R 4 , R 6 , R 8 to R 11 , and R 13 are each independently a hydrogen atom, a chlorine atom, a bromine atom, or a C (carbon number) 1 to C 4 alkyl group. , C1-C4 alkoxyl group, phthalimidomethyl group, —CH 2 NHCOCH 2 Cl, —SO 2 Cl, —SO 3 M, and —X1-X2-N (X3) 2 .
- M is .
- X1 represents a hydrogen atom or an alkali metal, -SO 2 NH- or -CH 2 NHCOCH .
- X2 representing a 2 NH- is .
- X3 representing an alkylene group of C1 ⁇ C4 may contain a hetero atom X 3 may be linked to each other to form a ring, provided that at least one of R 1 to R 4 , R 6 , R 8 to R 11 , and R 13 may be represented.
- examples of the C1-C4 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
- Examples of the C1-C4 alkoxyl group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group.
- M represents a hydrogen atom or an alkali metal, and examples of the alkali metal include lithium, sodium, and potassium.
- Examples of the C1-C4 alkylene group include a methylene group, an ethylene group, an ethylidene group, a trimethylene group, a propylene group, an isopropylidene group, a tetramethylene group, and a 2-methyl-1,3-propanediyl group.
- the phthalimidomethyl group means a group represented by the following (formula II).
- the C1-C4 alkyl group which may have a hetero atom includes, in addition to the above-mentioned C1-C4 alkyl group, a dimethylaminomethyl group, a dimethylaminoethyl group, a methoxymethyl group, an ethoxyethyl group, a methylthiomethyl group. Groups and the like.
- X3 may be connected to each other to form a ring. In this case, since a nitrogen atom is bonded to X3, the moiety represented by —N (X3) 2 in formula I has a cyclic amino group structure.
- Examples of the ring in the case where X3 are connected to each other to form a ring include a pyrrolidine ring, a piperidine ring, a piperazine ring, a morpholine ring, and a thiazolidine ring. Therefore, examples of the moiety represented by —N (X3) 2 in formula I include a piperidino group and a morpholino group.
- any one or two of R 2 , R 3 , R 9 and R 10 are atoms or substituents other than hydrogen atoms
- other R Examples include a case where 1 to R 4 , R 6 , R 8 to R 11 , and R 13 are all hydrogen atoms.
- R 2 , R 3 , R 9 and R 10 are atoms or substituents other than hydrogen atoms
- R 2 and R 9 , or R 3 and R 10 are other than hydrogen atoms.
- the other R 1 to R 4 , R 6 , R 8 to R 11 , and R 13 are all hydrogen atoms.
- R 2 and R 9 , or R 3 and R 10 are one selected from the group consisting of a chlorine atom, a bromine atom, a C1-C4 alkyl group and a C1-C4 alkoxyl group, and the other R A case where 1 to R 4 , R 6 , R 8 to R 11 , and R 13 are all hydrogen atoms is a particularly preferable embodiment.
- quinacridone compounds examples include 2,9-dimethylquinacridone (CI Pigment Red122), dialkylquinacridones such as 2,9-diethylquinacridone, dialkoxyquinacridones such as 2,9-dimethoxyquinacridone, 2,9 Examples thereof include dichloroquinacridone such as dichloroquinacridone (CI Pigment Red 202) and 3,10-dichloroquinacridone (CI Pigment Red209).
- R 1 to R 4 , R 6 , R 8 to R 11 , and R 13 are all hydrogen atoms is also a particularly preferable embodiment.
- the present invention In the method for producing a halogenated organic pigment of the present invention, at least one hydrogen atom of R 1 to R 4 , R 6 , R 8 to R 11 , and R 13 of the quinacridone compound represented by the above formula I is substituted with a halogen atom. be able to. Since the reaction yield is extremely high, the present invention can be applied to various quinacridone compounds represented by Formula I. Among them, it is an industrial advantage to use unsubstituted quinacridone, which is a hydrogen atom in all of R 1 to R 4 , R 6 , R 8 to R 11 , and R 13 as a raw material. Many are preferable.
- organic pigments other than quinacridone pigments used as raw materials for the method for producing a halogenated organic pigment of the present invention are listed below, but are not necessarily limited thereto.
- azo pigments C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 180, C.I. I. Pigment Red 146, C.I. I. Pigment Red 269 and the like.
- phthalocyanine pigments C.I. I. Pigment Red 15, C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3, C.I. I.
- anthraquinone pigments C.I. I. Pigment Yellow 147 and the like.
- dioxazine pigments C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 37 and the like.
- diketopyrrolopyrrole pigments C.I. I. Pigment Red254 and the like.
- quinophthalone pigments C.I. I. Pigment Yellow 138 and the like.
- anthrapyrimidine pigments C.I. I. Pigment Yellow 108 and the like.
- ansanthrone pigments C.I. I. Pigment Red168 and the like.
- Examples of isoviolanthrone pigments C.I. I. Pigment Violet 31 and the like.
- Examples of indanthrone pigments C.I. I. Pigment Blue 60 and the like.
- Examples of flavanthrone pigments C.I. I. Pigment Yellow 24, etc.
- Examples of perinone pigments C.I. I. Pigment Orange 43 and the like.
- Examples of perylene pigments C.I. I. Pigment Red178 and the like.
- Examples of isoindoline pigments C.I. I. Pigment Yellow 139 and the like.
- Examples of isoindolinone pigments C.I. I. Pigment Yellow 109, C.I. I. Pigment Yellow 110 and the like.
- thiazine indigo pigments C.I. I. Pigment Red 279, C.I. I. Pigment Orange 80
- thioindigo pigments C.I. I. Pigment Red 88 and the like.
- pyranthrone pigments C.I. I. Pigment Orange 40 and the like.
- the halogenated organic pigment in the present invention is one in which a part of the substituent of the pigment is substituted with halogen, or one having halogen as a substituent in the basic skeleton of the pigment.
- the halogen is at least one of bromine and chlorine.
- Specific examples of the halogenated organic pigment in the invention include C.I. I. Pigment Red 202, C.I. I. Quinacridone pigments such as Pigment Red209; C. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Blue 15: 1, or C.I. I. Phthalocyanine pigments such as Pigment Blue 15: 2; C. I.
- Dioxazine pigments such as Pigment Violet 23; C. I. Diketopyrrolopyrrole pigments such as Pigment Red254; C. I. Quinophthalone pigments such as Pigment Yellow 138; C. I. Ansanthrone pigments such as Pigment Red168; C. I. Isoviolanthrone-based pigments such as Pigment Violet 31; C. I. Indanthrone pigments such as Pigment Blue 64; C. I. Isoindoline pigments such as Pigment Orange 66; C. I. Pigment Yellow 109, C.I. I. Pigment Yellow 110, or C.I. I. I. Isoindolinone pigments such as Pigment Orange 61; C. I.
- Thiazine indigo pigments such as Pigment Red279; C. I. Pigment Red 88, C.I. I. Thioindigo pigments such as Pigment Red181; C. I. Pigment Orange 51, C.I. I. Pigment Red 216, or C.I. I. Pigment Red 226 and the like; and a halogenated compound of these pigments.
- Pigment Red279 C. I. Pigment Red 88, C.I. I. Thioindigo pigments
- Pigment Red181 C. I. Pigment Orange 51, C.I. I. Pigment Red 216, or C.I. I. Pigment Red 226 and the like
- a halogenated compound of these pigments such as Pigment Red279; C. I. Pigment Red 88, C.I. I. Thioindigo pigments such as Pigment Red181; C. I. Pigment Orange 51, C.I. I. Pigment Red 216, or C.I. I. Pigment Red 226 and
- the reaction temperature of the halogenation in the halogenation step of the production method of the present invention is preferably a temperature at which side reactions such as a decomposition reaction of the organic pigment to be used, a sulfonation reaction and a chlorosulfonation reaction can be suppressed.
- a target product is introduced with a sulfonium group, a chlorosulfonium group, or the like, at least one of sulfonation and chlorosulfonation is performed on the organic pigment as a raw material. Saddle and halogenation may be performed simultaneously.
- the reaction temperature of the halogenation can be appropriately determined according to the type of organic pigment, solvent, N-haloimide compound, the presence or absence of a catalyst, and the desired number of halogen atom substitutions, but is generally 0 to 150 ° C., preferably Is 10 to 100 ° C. Since the halogenation reaction time is also affected by the dissolution rate of the N-haloimide compound in the solvent, depending on the particle size of the N-haloimide compound and the stirring speed of the reaction solution in the reaction vessel, As long as the particles of the N-haloimide compound are sufficiently stirred at several millimeters, 30 minutes to 10 hours are preferable, and 1 hour to 5 hours are more preferable.
- sulfonation when sulfuric acid and / or chlorosulfonic acid is used as a solvent, sulfonation (when sulfuric acid is used) and / or chlorosulfonation (when chlorosulfonic acid is used) can be performed simultaneously with halogenation at higher reaction temperatures. There is a tendency to be.
- the reaction temperature when sulfonation and halogenation are performed using a phthalocyanine pigment as a raw material, the reaction temperature may be increased at the same time as described above, or the raw material and 5% fuming sulfuric acid are first mixed and reacted. Sulfonation treatment is carried out at a temperature of 100 to 120 ° C.
- reaction temperature is lowered than the sulfonation treatment and a halogenating agent is added, preferably at a reaction temperature of 10 to 20 ° C. for 3 to 4 hours. It is also possible to carry out in two steps, that is, halogenation treatment.
- a catalyst can be added during the halogenation reaction in order to improve the reaction rate.
- Catalysts include sulfur compounds such as sulfur and disulfur dichloride, iodine compounds such as iodine, iodine chloride and iodine bromide, ferric chloride, cuprous chloride, cupric chloride, aluminum chloride, antimony chloride, etc. A metal chloride etc. are mentioned.
- the halogenated organic pigment obtained by the present invention is a mixture of a plurality of halogenated organic pigments having different halogen atom substitution numbers.
- mass analysis of a reaction product obtained by halogenating a non-halogenated organic pigment so that the average number of halogen atom substitutions is 2, and in many cases, substitution of halogen atoms Molecular ion peaks corresponding to 1, 2, and 3 halogenated organic pigments are detected, and the content ratio calculated from the peak intensity of the mass spectrum is about 1: 2: 1 (molar ratio). .
- the chlorinated organic pigment obtained by the present invention has a hue different from that of an organic pigment having the same average number of substitution of chlorine atoms obtained by a conventional production method of two. Although approximate, it has the advantage of excellent clarity and tinting power. That is, while the halogenated organic pigment having two halogen atom substitutions is a single component, the chlorinated organic pigment obtained by the present invention has one, two and three chlorine atom substitutions. It is presumed that since it is obtained as a three-component mixture composed of individual organic pigments (about 1: 2: 1 (molar ratio)), the crystallinity is lowered and fine pigment particles are produced to show excellent color tone.
- the halogenated organic pigment having two halogen atom substitutions is a single component
- the chlorinated organic pigment obtained by the present invention has one, two and three chlorine atom substitutions. It is presumed that since it is obtained as a three-component mixture composed of individual organic pigments (about 1: 2: 1 (molar ratio)), the crystallinity is
- the halogenated organic pigment obtained according to the present invention can be adjusted to a wide range of colors by changing the number of halogen atom substitutions.
- the hydrogen atom of the organic pigment is substituted with a halogen atom, in many cases, the visible absorption becomes longer, so that the color becomes deeper as the number of halogen atom substitutions is increased.
- the halogenated quinacridone obtained by the present invention becomes a maroon color when up to about 8 chlorine atoms are introduced into unsubstituted quinacridone.
- the productivity can be further improved by incorporating the production method of the present invention into the conventional production method of quinacridone.
- the halogenation reaction according to the present invention is performed, so that the isolation operation of unsubstituted quinacridone is unnecessary. become.
- both the ring closure reaction and the halogenation reaction can be carried out continuously using polyphosphoric acid as a solvent, excellent productivity can be obtained.
- the sodium dichloroquinacridone sulfonate disclosed as the dispersion aid is obtained by sulfonating dichloroquinacridone.
- sulfuric acid as a solvent
- chlorination reaction and Since both sulfonation reactions can be performed simultaneously, it is possible to produce in one step.
- the production method of the present invention is clearly superior in safety because it does not use chloroaniline, a toxic chlorine gas, bromine gas, or the like which is suspected to be carcinogenic, which is a conventional production method.
- chloroaniline is obtained by chlorination reaction, nitration reaction and reduction reaction of benzene with chlorine gas, but it requires the use of highly toxic chlorine gas and the treatment of a large amount of by-product hydrogen chloride gas. There are dangers such as being present and disadvantages in the manufacturing process.
- the production method of the present invention since there is no byproduct of harmful hydrogen halide gas, there is an advantage that safety is high and a large-scale processing apparatus is not required.
- the production method of the present invention has a higher reaction yield than the conventional method and is excellent in productivity.
- the production conditions affect the reaction yield, but according to the knowledge of the present inventors, The reaction yield is about 80%.
- the reaction yield is about 90%.
- the halogenated organic pigment obtained by the production method of the present invention preferably satisfies at least one of the following (1) to (3).
- the obtained halogenated pigment has color characteristics such as coloring power and sharpness, and durability such as light resistance, heat resistance and migration resistance as a colorant.
- the average number of halogen substitutions is 0.05 or more and 7.0 or less.
- the halogen distribution width is 3 or more.
- the average particle size is 0.1 ⁇ m or less, preferably 0.06 ⁇ m or less. The measurement of the average particle diameter will be described later.
- the obtained halogenated organic pigment is a phthalocyanine pigment
- the content of aluminum phthalocyanine and aluminum halide phthalocyanine is 1.0% by mass or less.
- the central element is at least one selected from the group consisting of hydrogen, manganese, iron, cobalt, zinc, nickel and copper.
- the production method of the present invention is excellent in productivity even for solid solution pigments containing halogenated organic pigments.
- a conventional method for preparing a solid solution pigment for example, a non-halogenated organic pigment and a halogenated organic pigment are dissolved in an organic solvent containing sulfuric acid or a strong base and mixed uniformly. Is added, precipitated and isolated, and if necessary, heat treatment as a slurry with a solvent, or addition of inorganic salt and polyhydric alcohol to form a pigment by solvent salt milling.
- the production method of the present invention for example, when halogenating an organic pigment as a raw material using sulfuric acid as a solvent, a portion of the raw material is halogenated and the rest of the raw material is not halogenated.
- -A solid solution pigment having the same color tone as described above can be obtained by making the addition amount of the haloimide compound small with respect to the raw material. Therefore, the production method of the present invention can simultaneously perform both the halogenation reaction and the preparation of the solid solution pigment.
- halogenation and pigmentation by acid pasting treatment are simultaneously performed, it is possible to shorten the production process and obtain a halogenated organic pigment in the form of a pigment having high use value.
- it may further have another pigmentation process (also referred to as a conditioning or finishing process) for finishing the pigment material according to the application as a coloring material.
- the solvent is distilled off from the reaction solution, or the reaction solution is diluted with a large amount of water to precipitate the halogenated organic pigment, and filtered to obtain a hydrous cake of the halogenated organic pigment.
- separated as a dry product it is preferable to perform the isolation
- the known pigmentation process include heat treatment in the presence of an organic solvent, solvent salt milling treatment in which an inorganic salt and a polyhydric alcohol are added, or acid pace that is dissolved in sulfuric acid and then diluted with a large amount of water. And the like processing process.
- a resin, an activator, an extender pigment, a pigment dispersant, and the like may be added to increase the utility value of the pigment.
- the pigment dispersant refers to a compound in which an acidic substituent or a basic substituent is introduced into the pigment skeleton, and a polymer compound having a partial structure having a large interaction with the pigment in the molecule. Is a general term for compounds having
- the method for producing a halogenated organic pigment of the present invention is a method having excellent safety and productivity.
- the halogenated organic pigment obtained by the production method of the present invention is mixed with a vehicle component to form a coloring composition, and printing ink, paint, colorant for plastic, printing agent, color toner, inkjet ink, and color filter resist ink It can use suitably as coloring materials, such as. In particular, it can be suitably used for plastic colorants, color toners, inkjet inks, color filter resist inks, and the like.
- the halogenated organic pigment obtained by the production method of the present invention has a wide range of color tones and can be finely dispersed, it can be used for coloring compositions such as color toners, inkjet inks, and color filter resist inks. It is possible to provide final products such as printed materials, coated materials, and color filters that exhibit high properties and high coloring power.
- the colored composition of the present invention contains a halogenated organic pigment and a vehicle component obtained by the production method of the present invention.
- the coloring composition mixes a halogenated organic pigment and a vehicle component, disperses the halogenated organic pigment with a dispersing device such as a ball mill, a bead mill, a roll mill, or a high-speed impact mill, and various additives such as, for example, , A dispersant, a color tone adjusting material, a physical property adjusting material, and the like.
- the content of the halogenated organic pigment in the coloring composition is preferably in the range of 0.1% by mass to 80% by mass.
- the content of the vehicle component in the coloring composition is preferably in the range of 20% by mass to 99.9% by mass.
- Vehicle components used in the coloring composition include vehicles for offset inks, vehicles for gravure inks, vehicles for paints, vehicles used for colorants for plastics, vehicles for printing, resins for color toners, vehicles for inkjet inks, and color filter resists. Examples include an ink vehicle.
- known additives such as an ink solvent, a drier, a leveling improver, and a thickener can be appropriately blended as necessary.
- the resin include gum rosin, wood rosin, tall oil rosin, lime rosin, rosin ester, maleic acid resin, gilsonite, dammar, shellac, polyamide resin, vinyl resin, nitrocellulose, cyclized rubber, chlorinated rubber, ethyl cellulose, cellulose acetate, Examples thereof include an ethylene-vinyl acetate copolymer resin, a urethane resin, a polyester resin, and an alkyd resin.
- the solvent examples include aliphatic hydrocarbons such as n-hexane, aromatic hydrocarbons such as toluene, alcohols such as methanol, ethanol and isopropyl alcohol, ketones such as acetone and methyl ethyl ketone, ethyl acetate and ethyl lactate. , Ester systems such as ethyl acetoacetate, ether systems such as diethyl ether, ether / alcohol systems such as ethylene glycol monoethyl ether, ethylene glycol monomethyl ether and ethylene glycol monobutyl ether, aromatic halide systems such as chlorobenzol, etc. It is done.
- aliphatic hydrocarbons such as n-hexane
- aromatic hydrocarbons such as toluene
- alcohols such as methanol, ethanol and isopropyl alcohol
- ketones such as acetone and methyl ethyl ketone
- gravure ink if necessary, for example, barium sulfate, barium carbonate, calcium carbonate, gypsum, alumina white, clay, silica, silica white, talc, calcium silicate, precipitated magnesium carbonate and other extender pigments, auxiliary agents
- known additives such as pigment dispersants, plasticizers, UV inhibitors, antioxidants, and antistatic agents can be appropriately blended.
- the resin include nitrocellulose, amino alkyd resin, acrylic resin, amino acrylic resin, urethane resin, polyvinyl acetal resin, epoxy resin, polyester resin, polyvinyl chloride resin, vinylidene fluoride resin, vinyl fluoride resin, polyether.
- examples include sulfone resins.
- Solvents include aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ketones, esters, ethers, ethers / alcohols, ethers / esters and other organic solvents, water, etc. Is mentioned. If necessary, known additives such as extender pigments, pigment dispersants, leveling improvers, thickeners, and curing agents can be appropriately blended in the paint.
- Vehicles used in colorants for plastics include aromatic carboxylic acids, aliphatic carboxylic acid aromatic carboxylic acid metal salts, aliphatic carboxylic acid metal salts, aliphatic carboxylic acid esters, polyethylene wax, low density polyethylene (LDPE) and Examples include high density polyethylene (HDPE).
- the plastic can be colored using the colorant for plastic and / or the halogenated organic pigment of the present invention, and the colored plastic can be molded.
- Plastic resins for plastic molding include polypropylene resin, polyethylene resin, ethylene / propylene copolymer, copolymer of ⁇ -olefin and acrylic acid or maleic acid, ethylene / vinyl acetate copolymer, ethylene and acrylic acid Or a polyolefin resin such as a copolymer with maleic anhydride, a vinyl resin such as polyvinyl chloride resin or polyvinyl acetate, an acetal resin such as formal resin or butyral resin, an acrylic resin such as polyacrylonitrile or methacrylic resin, polystyrene, Polystyrene resins such as acrylonitrile / butadiene / styrene copolymers, polyester resins such as polyethylene terephthalate and polycarbonate, nylons such as 6-nylon, unsaturated polyester resins, epoxy resins, urea resins, melamine resins Cellulose resins. These resins can also be used as vehicles used in plastic colorants.
- the resin include an acrylic resin, an amino acrylic resin, and a urethane resin.
- the solvent examples include aliphatic hydrocarbon-based, aromatic hydrocarbon-based, alcohol-based, ketone-based, ester-based, ether-based, ether-alcohol-based, ether-ester-based organic solvents, water, and the like.
- Known additives such as pigment dispersants, antifoaming agents, thickeners, and surfactants can be appropriately blended with the textile printing agent as necessary.
- Color toner resins include polystyrene resin, styrene-acrylic acid copolymer, polyvinyl chloride resin, styrene-vinyl acetate copolymer, rosin-modified maleic acid resin, phenol resin, epoxy resin, polyester resin, low molecular polyethylene, Low molecular polypropylene, ionomer resin, polyurethane resin, silicone resin, rosin ester, rosin and the like can be mentioned.
- known additives such as a pigment dispersant, a charge control agent, and a release agent can be appropriately blended as necessary.
- the resin include an acrylic resin, a styrene-acrylic acid copolymer, a polyester resin, a polyamide resin, a polyurethane resin, a fluorine resin, and the like, a resin that is soluble in water, an emulsion that is dispersible in water, and a colloidal dispersion resin. . These resins are added with neutralizing agents such as ammonia, amines and inorganic alkalis as required.
- the solvent examples include water, ethylene glycol, polyethylene glycol, ethylene glycol monomethyl ether, and substituted pyrrolidone.
- alcohols such as methanol, ethanol and isopropyl alcohol can be used for the purpose of accelerating the drying property of the ink-jet ink.
- Ink-jet inks may contain preservatives, penetrants, chelating agents, anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric agents to improve the dispersion stability of pigments as necessary.
- Known additives such as ionic surfactants can be appropriately blended.
- Inkjet ink can also be used for the production of color filters.
- thermoplastic resins include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene resin, chlorinated polypropylene resin, polyvinyl chloride resin, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate resin, polyurethane series
- thermoplastic resins include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene resin, chlorinated polypropylene resin, polyvinyl chloride resin, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate resin, polyurethane series
- resins polyester resins, acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, cellulose resins, polyethylene resins, polybutadiene resins, and polyimide resins.
- thermosetting resin examples include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.
- active energy ray-curable resins include linear polymers having reactive substituents such as hydroxyl groups, carboxyl groups, and amino groups, (meth) acrylic compounds, and cinnamon via isocyanate groups, aldehyde groups, and epoxy groups. Examples thereof include a resin into which a photocrosslinkable group such as an acid is introduced.
- Monomers and oligomers include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, ⁇ -carboxyethyl (meth) acrylate , Polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol Tri (meth) acrylate, 1, 6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, Opentyl glycol diglycidyl ether di (meth) acrylate,
- Solvents include aliphatic hydrocarbons, aromatic hydrocarbons such as ethylbenzene, xylene and toluene, halogenated hydrocarbons, alcohols such as ethanol, propanol, butanol, ethylene glycol, diethylene glycol and glycerin, cyclohexanone, methyl ethyl ketone, etc.
- Organic solvents such as ketones, esters such as ethyl acetate, ethers such as diethylene glycol dimethyl ether and ethylene glycol diethyl ether, ethers / alcohols such as ethylene glycol monomethyl ether, ethers / esters such as ethyl cellosolve acetate, etc. .
- known additives such as a pigment dispersant, a photopolymerization initiator, and a sensitizer can be appropriately blended as necessary.
- the printed matter of the present invention is printed using the color toner or the inkjet ink.
- the printed matter of the present invention can be obtained by applying to a film or sheet-like substrate using a known printing method such as gravure printing or flexographic printing, and fixing the film by drying with an oven.
- the base material include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polycarbonate and polylactic acid, polystyrene resins such as polystyrene, AS resin and ABS resin, nylon, polyamide, polyvinyl chloride, polyvinylidene chloride and cellophane. , Paper, aluminum or the like, or a composite material thereof.
- the color filter of the present invention comprises a filter segment formed using the color filter resist ink.
- the color filter includes at least one red filter segment, at least one green filter segment, and at least one blue filter segment, and further includes a magenta filter segment, a cyan filter segment, and a yellow filter segment. It may be a thing.
- the color filter of the present invention can be produced by a known printing method or photolithography method.
- part and % represent “part by mass” and “% by mass”, respectively.
- identification of the compound is the same between the molecular ion peak of the mass spectrum obtained using a time-of-flight mass spectrometer (autoflex III (TOF-MS), manufactured by Bruker Daltonics) and the mass number obtained by calculation.
- TOF-MS time-of-flight mass spectrometer
- the ratio of carbon, hydrogen and nitrogen obtained using an elemental analyzer (2400CHN elemental analyzer, manufactured by Perkin Elmer) was matched with the theoretical value.
- the amount of the halogen atom was calculated by burning the compound by an oxygen combustion flask method and quantifying the content of the liquid absorbed in water by ion chromatography and converting it into the number of halogen substitutions.
- the content (molar ratio) of each component (halogenated compound) in the obtained halogenated organic pigment is the ratio of the signal intensity (peak) of each component of the mass spectrum obtained by TOF-MS measurement. The molar ratio of each component.
- the average particle diameter of the pigment particles was measured and calculated by the following method. Propylene glycol monomethyl ether acetate was added to the pigment powder, a small amount of Disperbyk-161 (manufactured by Big Chemie) was added as a resin-type dispersant, and the sample for measurement was prepared by dispersing in a water bath of an ultrasonic cleaner for 1 minute. . This sample was photographed with a transmission electron microscope (TEM) to photograph six leaves (for six fields of view) at a magnification of 50,000 to 100,000, allowing observation of primary particles of 200 or more pigments. The length (minor axis diameter and major axis diameter of the particles) was measured in units of 1 nm, and the average value was defined as the average particle diameter of the pigment particles.
- TEM transmission electron microscope
- Example 1 99 parts of 98% sulfuric acid and 21 parts of 30% fuming sulfuric acid were mixed to prepare 120 parts of 99.5% sulfuric acid. After adding 0.1 part of iodine as a catalyst to this, 20 parts of copper phthalocyanine (CI Pigment Blue 15, T-99 CRUDE BLUE, manufactured by Zhuhai Toyo Kaimi Chemical Co., Ltd.) as a phthalocyanine pigment was added at 30 ° C. While maintaining the following, it was added while cooling in an ice water bath. Subsequently, it heated up to 50 degreeC, 2.7 parts of trichloroisocyanuric acid was added, and it stirred at the same temperature for 3 hours.
- copper phthalocyanine CI Pigment Blue 15, T-99 CRUDE BLUE, manufactured by Zhuhai Toyo Kaimi Chemical Co., Ltd.
- the amount of trichloroisocyanuric acid is 0.33 times mol with respect to copper phthalocyanine, and is 1.00 mol equivalent on the basis of effective chlorine.
- the reaction solution is poured into 600 parts of water while stirring, heated to 70 ° C., treated in the order of filtration, hot water washing, 1% sodium hydroxide aqueous solution washing, hot water washing, and then dried. 18.6 parts of chlorinated copper phthalocyanine having an average number of chlorine substitutions of 0.9 were obtained. The yield was 89%.
- the average particle size was 0.06 ⁇ m.
- the halogen distribution width was 4. The inclusion of aluminum phthalocyanine and chlorinated aluminum phthalocyanine was not observed.
- the halogen distribution width, the content of aluminum phthalocyanine and the content of aluminum phthalocyanine were measured using a time-of-flight mass spectrometer (autoflex III (TOF-MS), manufactured by Bruker Daltonics) as follows.
- the content of aluminum phthalocyanine and halogenated aluminum phthalocyanine is determined based on the signal intensity (each peak value) of the molecular ion peak corresponding to each component and each peak in the mass spectrum of the pigment obtained by mass spectrometry using the above apparatus.
- a value (total peak value) obtained by integrating the values was calculated and obtained from the ratio of each peak value to the total peak value.
- the halogen distribution width was defined as the halogen distribution width by counting the number of peaks in which the ratio of each peak value to the total peak value was 1% or more.
- Examples 2 to 10 Each halogenated phthalocyanine was obtained in the same manner as in Example 1 except that the conditions shown in Tables 1 and 2 were changed. 2% fuming sulfuric acid was prepared by mixing 86 parts of 98% sulfuric acid and 34 parts of 30% fuming sulfuric acid. The molar equivalents of the amounts shown in Table 1 are molar equivalents based on the effective halogen. Table 2 shows the number of chlorine substitutions, the number of bromine substitutions, and the yield of the obtained halogenated phthalocyanine. All the N-haloimide compounds used were granular white solids, which were easy to handle, no gas was generated during the reaction, and the series of operations was extremely easy. When the chlorinated copper phthalocyanines obtained in Examples 2 to 10 were confirmed with an electron microscope, all had an average particle size of 0.06 ⁇ m. The inclusion of aluminum phthalocyanine and chlorinated aluminum phthalocyanine was not observed.
- the reaction solution is poured into 1000 parts of water, and processed in the order of filtration, warm water washing, 1% hydrochloric acid aqueous solution washing, warm water washing, 1% sodium hydroxide aqueous solution washing, hot water washing, and then drying to obtain a chlorine substitution number.
- chlorine gas was blown in, hydrogen chloride gas and aluminum chloride sublimates were generated, and these traps were required.
- Comparative Example 2 The crude chlorinated copper phthalocyanine obtained in Comparative Example 1 was used for pigmentation by acid pasting. 20 parts of crude chlorinated copper phthalocyanine was dissolved in 120 parts of 98% sulfuric acid and stirred at 50 ° C. for 3 hours. Next, the solution is poured into 600 parts of water while stirring, heated to 70 ° C., filtered, washed with warm water, washed with 1% sodium hydroxide aqueous solution, washed with warm water, dried and averaged 2.0 chlorine substitutions. 19.2 parts of chlorinated copper phthalocyanine was obtained. The yield was 96%.
- Comparative Example 4 The crude chlorinated copper phthalocyanine obtained in Comparative Example 3 was used for pigmentation by acid pasting. 20 parts of crude chlorinated copper phthalocyanine was dissolved in 120 parts of 98% sulfuric acid and stirred at 50 ° C. for 3 hours. Next, the solution is poured into 600 parts of water while stirring and heated to 70 ° C., followed by filtration, washing with warm water, washing with 1% aqueous sodium hydroxide, washing with warm water, followed by drying and chlorine. 19.3 parts of chlorinated copper phthalocyanine having an average number of substitutions of 3.0 were obtained. The yield was 96%.
- the halogenated organic pigment obtained by the conventional production method As shown in Comparative Examples 1 to 4, in order to use the halogenated organic pigment obtained by the conventional production method as a coloring material, it is necessary to go through a two-stage production process of a halogenation process and a pigmentation process. was there. On the other hand, the halogenated organic pigment obtained by the production method of the present invention can be used as a coloring material without going through the pigmentation step, so that the production step can be shortened and the production method is excellent in productivity. It can be said that there is.
- a halogenated phthalocyanine produced using the method described in Patent Document 6 is shown.
- a phthalocyanine pigment a mixture of 20 parts of copper phthalocyanine (CI Pigment Blue 15, T-99 CRUDE BLUE, manufactured by Zhuhai Toyo Kaimi Co., Ltd.) and 28 parts of N-bromosuccinimide was added to 1400 mL of trifluoroacetic acid and 98%. The mixture was stirred at room temperature for 24 hours in a solution of 420 mL of sulfuric acid.
- the amount of N-bromosuccinimide is 4.52 times the molar amount of copper phthalocyanine and 4.52 molar equivalents based on the effective bromine.
- the resulting dark blue solution was poured into 5000 parts of ice water. The obtained solid was washed with water, filtered, and dried to obtain 17.5 parts of brominated copper phthalocyanine. The yield was 58%, which was lower than those of Examples 7 and 8, which were also brominated. Moreover, the average number of bromine substitutions was 3.76, which was lower than the theoretically obtained number of bromine substitutions.
- Example 11 is an anthraquinone pigment.
- I After adding 10 parts of Pigment Yellow 147 (Filestar Yellow RNB, manufactured by BASF) to 150 parts of chlorosulfonic acid, 2.6 parts of trichloroisocyanuric acid was added and stirred at 20 ° C. for 2 hours. At this time, trichloroisocyanuric acid is 0.66 times mole with respect to Pigment Yellow147, and 2.0 mole equivalent on the basis of effective chlorine.
- the reaction solution is poured into 600 parts of water while stirring, heated to 70 ° C., treated in the order of filtration, hot water washing, 1% sodium hydroxide aqueous solution washing, hot water washing, and then dried. 10.8 parts of chlorinated Pigment Yellow 147 having an average of 1.9 chlorine substitutions were obtained. The yield was 97%.
- Example 6 As a conventional technique, an example of a manufacturing method using chlorine gas will be shown. A halogenation reaction was performed in the same manner as in Example 11 except that chlorine gas was used instead of trichloroisocyanuric acid in Example 11. Chlorine gas was introduced into the bottom of the reaction solution through a glass tube at a rate of about 2 parts / hour until the chlorine substitution number was 2.0. The total amount of chlorine gas introduced at this time was 6.1 parts. Since the required theoretical amount of chlorine gas when the number of chlorine substitutions was 2.0 was 3.2 parts, the yield based on chlorine gas was 52%. The yield of the halogenated compound was 10.3 parts, and the yield was 92%, which was lower than that in Example 11. Furthermore, in order to capture unreacted chlorine gas and hydrogen chloride gas by-produced, a device for absorbing in alkaline water in addition to the production device of Example 11 was required.
- C.I. is a quinophthalone pigment.
- I. After adding 10 parts of Pigment Yellow 138 (Paliotol Yellow K0961HDK, manufactured by BASF) to 80 parts of chlorosulfonic acid, 1.1 parts of trichloroisocyanuric acid was added and stirred at 10 ° C. for 3 hours. At this time, trichloroisocyanuric acid is 0.33 times mole with respect to Pigment Yellow138, and is 1.00 mole equivalent on the basis of effective chlorine. Next, the reaction solution is poured into 600 parts of water while stirring, heated to 70 ° C., treated in the order of filtration, hot water washing, 1% sodium hydroxide aqueous solution washing, hot water washing, and then dried. As a result, 9.6 parts of chlorinated Pigment Yellow 138 having an average number of chlorine substitutions of 0.3 were further obtained. The yield was 94%. The average (total) number of chlorine substitutions was 8.3. The average particle size was 0.06 ⁇ m.
- Example 13 is a perylene pigment.
- Example 14 is an isoindolinone pigment.
- I After adding 10 parts of Pigment Yellow 109 (Irgazin Yellow L1030, manufactured by BASF) to 80 parts of chlorosulfonic acid, 1.19 parts of trichloroisocyanuric acid was added and stirred at 10 ° C. for 3 hours. At this time, trichloroisocyanuric acid is 0.33 times mole with respect to Pigment Yellow109, and is 1.00 mole equivalent on the basis of effective chlorine.
- the reaction solution is poured into 600 parts of water while stirring, heated to 70 ° C., treated in the order of filtration, hot water washing, 1% sodium hydroxide aqueous solution washing, hot water washing, and then dried. 8.8 parts of chlorinated Pigment Yellow 109 further substituted with an average of 0.25 chlorine substitutions were obtained. The yield was 88%. The average (total) number of chlorine substitutions was 8.25, and the average particle size was 0.04 ⁇ m.
- Example 15 is an isoindolinone pigment.
- I. Pigment Yellow 110 (Irgazin Yellow L2060, manufactured by BASF) and 0.05 parts of iodine were dissolved in 80 parts of 98% sulfuric acid, 1.21 parts of trichloroisocyanuric acid was added, and the mixture was stirred at 10 ° C. for 3 hours. did. At this time, trichloroisocyanuric acid is 0.33 times mole with respect to Pigment Yellow 110, and is 1.00 mole equivalent on the basis of effective chlorine.
- reaction solution is poured into 600 parts of water while stirring, heated to 70 ° C., treated in the order of filtration, hot water washing, 1% sodium hydroxide aqueous solution washing, hot water washing, and then dried.
- 8.5 parts of chlorinated Pigment Yellow 110 further substituted with an average of 0.78 chlorine substitutions were obtained.
- the yield was 91%.
- the average (total) number of chlorine substitutions was 2.78.
- Example 16 is a dioxazine pigment.
- I. 10 parts of Pigment Violet 23 (Lionogen Violet FG-6240, manufactured by Toyocolor Co., Ltd.) was added to 100 parts of methanesulfonic acid and dissolved, then 1.32 parts of trichloroisocyanuric acid was added and stirred at 20 ° C. for 2 hours. At this time, trichloroisocyanuric acid is 0.33 times mole with respect to Pigment Violet 23, and is 1.00 mole equivalent on the basis of effective chlorine.
- reaction solution is poured into 600 parts of water while stirring, heated to 70 ° C., treated in the order of filtration, hot water washing, 1% sodium hydroxide aqueous solution washing, hot water washing, and then dried. 10.4 parts of chlorinated Pigment Violet 23 further substituted with an average of 0.23 chlorine substitutions were obtained. The yield was 98%. The average (overall) number of chlorine substitutions was 2.23, and the average particle size was 0.03 ⁇ m.
- Example 17 is an indanthrone pigment.
- Pigment Blue 60 Lionogen Blue 6510, manufactured by Toyocolor Co., Ltd.
- reaction solution is poured into 600 parts of water while stirring, heated to 70 ° C., treated in the order of filtration, hot water washing, 1% sodium hydroxide aqueous solution washing, hot water washing, and then dried. 9.8 parts of chlorinated Pigment Blue 60 having an average number of chlorine substitutions of 0.71 were obtained. The yield was 90%. The average particle size was 0.05 ⁇ m.
- a paint was prepared and applied to evaluate the sharpness and durability.
- the chlorinated copper phthalocyanine described in Example 5 the crude chlorinated copper phthalocyanine described in Comparative Example 1 and Comparative Example 2 having substantially the same number of chlorine substitutions. Comparative evaluation was carried out using three kinds of the described chlorinated copper phthalocyanines.
- Example 18 A mixture of 6 parts of the halogenated phthalocyanine obtained in Example 5 and 56 parts of a coating vehicle (phthalkid 133-60 (manufactured by Hitachi Chemical Co., Ltd.), 28 parts of melan 20 (manufactured by Hitachi Chemical Co., Ltd.) and 10 parts of xylene. 94 parts were dispersed with 3 mm steel balls to obtain a dark paint.
- a coating vehicle phthalkid 133-60 (manufactured by Hitachi Chemical Co., Ltd.)
- melan 20 manufactured by Hitachi Chemical Co., Ltd.
- xylene 10 parts
- the above-mentioned light color paint is applied to the coated surface of a metal plate (cold rolled steel plate SPCC-SD, single-sided water lab coating plate, gray electrodeposition coating) with a 6 mil applicator and cured in an oven at 150 ° C. Produced.
- a metal plate cold rolled steel plate SPCC-SD, single-sided water lab coating plate, gray electrodeposition coating
- C * 49.5.
- the numerical value was higher than that in the case of using the chlorinated copper phthalocyanine obtained in Comparative Example 2, and it was highly clear.
- Example 7 For comparison, the same procedure as in Example 18 was performed except that the crude chlorinated copper phthalocyanine obtained in Comparative Example 1 was used instead of the chlorinated copper phthalocyanine obtained in Example 5, and a dark paint was obtained. Was made. However, since the resulting dark paint has a very high viscosity, it cannot be separated from the steel ball and cannot be evaluated as a paint.
- a colorant for plastic was prepared, and a colored plastic molding was prepared and evaluated using the colorant.
- the chlorinated copper phthalocyanine described in Example 5 the crude chlorinated copper phthalocyanine described in Comparative Example 1 and Comparative Example 2 having substantially the same number of chlorine substitutions. Comparative evaluation was carried out using three kinds of the described chlorinated copper phthalocyanines.
- Example 19 100 parts of chlorinated copper phthalocyanine obtained in Example 5 and 100 parts of calcium stearate were mixed in a mixer to obtain a colorant for plastic (dry color). 2 parts of the obtained plastic colorant (dry color) was mixed with 1000 parts of high-density polyethylene resin (product name: Hizex2208J, manufactured by Prime Polymer Co., Ltd.) and a few drops of the adhering agent. It was molded into a plate shape, and the hue was measured with a colorimeter (Minolta spectrocolorimeter CM-2002, manufactured by Konica Minolta).
- the obtained plate was sandwiched between white soft vinyl chloride sheets, pressurized and heated for 1 minute, and then migration to white soft vinyl chloride was confirmed, but no migration was observed.
- the migration resistance was excellent and the hue became reddish and clear.
- Example 9 As a comparison, the same operation as in Example 19 was performed except that the crude chlorinated copper phthalocyanine obtained in Comparative Example 1 was used instead of the chlorinated copper phthalocyanine obtained in Example 5, and a plate-shaped molded product was obtained. Got. However, the obtained plate had many green spots, and the result was that it was extremely inferior in color development as compared with the plate obtained in Example 19. Observation of the powder with a microscope confirmed that it was pigment particles of chlorinated copper phthalocyanine that could not be dispersed.
- Example 10 As a comparison, the same operation as in Example 19 was performed except that the chlorinated copper phthalocyanine obtained in Comparative Example 2 was used instead of the chlorinated copper phthalocyanine obtained in Example 5, and a plate-like molded product was obtained. Obtained. The obtained plate was color-measured. As a result, the sharpness C * was 38.8, the hue angle h was 255.9 °, and the greenness was unclear compared to Example 19. Further, when the migration property was confirmed, migration was recognized, that is, the migration resistance, which is one item of durability, was inferior to that of Example 19.
- Example 20 81 parts of aluminum chloride, 19 parts of sodium chloride, and 1 part of ferric chloride were heated and melted. After adding 0.1 part of iodine, 20 parts of copper phthalocyanine was added at 140 ° C. While maintaining the reaction solution at 130 ° C., 5.7 parts of trichloroisocyanuric acid was added with vigorous stirring, and the mixture was stirred at the same temperature for 4 hours. At this time, the amount of trichloroisocyanuric acid is 0.71 times mol with respect to copper phthalocyanine, and 2.1 mol equivalent based on effective chlorine.
- the reaction solution is poured into 1000 parts of water, and processed in the order of filtration, warm water washing, 1% hydrochloric acid aqueous solution washing, warm water washing, 1% sodium hydroxide aqueous solution washing, hot water washing, and then drying to obtain a chlorine substitution number. Yielded 21.1 parts of an average of 2.0 crude chlorinated copper phthalocyanines. The yield was 94%.
- Example 30 and Example 31 since the reaction product had a tertiary amino group, it interacted with sulfate ions, and the filterability of the reaction liquid (slurry) to which 600 parts of water was added was extremely poor. Sodium hydroxide was added to make it weakly alkaline, followed by filtration, washing with warm water, and drying to obtain a halogenated quinacridone.
- Diethylaminopropylaminosulfonylquinacridone used was a compound having 1.5 substituents obtained by the production method described in JP-A-56-118462.
- Diethylaminoethylaminomethylcarbonylaminomethylquinacridone used was a compound having 1.0 substituents obtained by the production method described in JP-A-51-18736.
- Example 34 An example of production of chlorinated quinacridone by chlorination reaction of quinacridone substituted with —SO 3 H group is shown.
- a production example of dichloroquinacridone sulfonic acid in which a sulfonation reaction and a chlorination reaction are continuously performed is shown. 10 parts of unsubstituted quinacridone was added to a mixed solution of 100 parts of 98% sulfuric acid and 50 parts of 30% fuming sulfuric acid, and the mixture was stirred at 60 ° C. for 2 hours for sulfonation reaction.
- This chlorinated quinacridone has 2.0 substitutions of chlorine atoms and 1.3 substitution of —SO 3 Na groups, and dichloroquinacridonesulfonic acid disclosed in JP-A-2005-206630. It was a compound of the same composition.
- Example 35 An example of production of chlorinated quinacridone by chlorination reaction of quinacridone substituted with —SO 2 Cl group is shown.
- a chlorosulfonation reaction and a chlorination reaction are continuously performed to produce dichloroquinacridonesulfonyl chloride, and then an amination reaction is shown.
- To 150 parts of chlorosulfonic acid 10 parts of unsubstituted quinacridone was added and stirred at 40 ° C. for 2 hours to carry out a chlorosulfonation reaction.
- chlorinated quinacridone has 2.0 chlorine atoms and 1.5 diethylaminopropylaminosulfonyl groups (—SO 2 NH (CH 2 ) 3 N (C 2 H 5 ) 2 ). 30 and the same composition.
- Example 36 An example of production of chlorinated quinacridone by chlorination reaction of quinacridone substituted with —CH 2 NHCOCH 2 Cl is shown.
- a chloroacetamide methylation reaction and a chlorination reaction are continuously performed to produce dichloro (chloroacetamidomethyl) quinacridone, and then an amination reaction is shown.
- To 150 parts of 98% sulfuric acid 10 parts of unsubstituted quinacridone, 4.5 parts of chloroacetamide and 1.5 parts of paraformaldehyde were added and stirred at 20 ° C. for 4 hours to carry out a chloroacetamide methylation reaction.
- This chlorinated quinacridone has 2.0 chlorine atom substitutions and 1.0 diethylaminoethylaminomethylcarbonylaminomethyl group (—CH 2 NHCOCH 2 NHC 2 H 4 N (C 2 H 5 ) 2 ).
- the compound had the same composition as Example 31.
- Example 37 The manufacture example which integrated the manufacturing method of this invention in the manufacturing process of quinacridone is shown.
- a production example of dichloroquinacridone in which a ring-closing reaction and a chlorination reaction are continuously performed, is shown.
- 10 parts of 2,5-dianilinoterephthalic acid was added to 150 parts of polyphosphoric acid, and the mixture was stirred at 125 ° C. for 3 hours to cyclize to obtain a polyphosphoric acid solution of unsubstituted quinacridone.
- Example 38 Next, the manufacture example which processed the chlorinated quinacridone by the solvent by the manufacturing method of this invention with the solvent, and finished it is shown. Chlorine finished in pigment by adding 100 parts of chlorinated quinacridone obtained in Example 21 to 2000 parts of N, N-dimethylformamide, stirring at 120-140 ° C. for 3 hours, filtering, washing with water and drying. A quinacridone was obtained. When the chlorinated quinacridone finished into this pigment was observed with an electron microscope, the average particle diameter of the pigment particles was 0.025 ⁇ m.
- the chlorinated quinacridone obtained by the conventional production method of Comparative Example 11 described later was also observed with an electron microscope, the average particle size of the pigment particles was 0.034 ⁇ m, and the chlorinated quinacridone according to the present invention was finer. .
- the chlorinated quinacridone of Comparative Example 11 is all dichloroquinacridone, whereas the chlorinated quinacridone according to the present invention is a mixture of monochloroquinacridone, dichloroquinacridone and trichloroquinacridone in a ratio of 1: 2: 1 (molar ratio). Therefore, it seems that the crystallinity is reduced and the particle size is reduced.
- an offset ink was prepared and the color tone was evaluated. From 0.5 part of chlorinated quinacridone finished to pigment and 0.45 part of rosin modified phenolic resin (Tamanol 340, manufactured by Arakawa Chemical Co., Ltd.), 1.05 part of AF solvent 7 (manufactured by JX Nippon Oil & Energy Corporation) as a solvent Two parts of the offset ink varnish thus formed were kneaded under a load of 150 pounds (68 kg) using a Hoover Mahler (manufactured by Toyo Seiki Co., Ltd.) to produce a red ink.
- rosin modified phenolic resin Temanol 340, manufactured by Arakawa Chemical Co., Ltd.
- AF solvent 7 manufactured by JX Nippon Oil & Energy Corporation
- Example 39 Using the chlorinated quinacridone obtained in Example 22 in place of the chlorinated quinacridone obtained in Example 21, the same operation as in Example 38 was performed to obtain a chlorinated quinacridone finished into a pigment.
- the chlorinated quinacridone finished into this pigment was subjected to X-ray diffraction measurement using an X-ray diffraction measurement apparatus (MiniFlex II, manufactured by Rigaku Corporation).
- the main peaks are CuK ⁇ ray Bragg angles of 6.2 °, 13.2 °, 24.0 °, and 26.4 °, and the peaks almost coincide with the solid solution described in Table 3 of US Pat. No. 3,160,510. Met.
- Example 40 Using the chlorinated quinacridone obtained in Example 23 instead of the chlorinated quinacridone obtained in Example 21, the same operation as in Example 38 was performed to obtain a chlorinated quinacridone finished in a pigment.
- the average particle diameter of the chlorinated quinacridone finished on this pigment as observed with an electron microscope was 0.14 ⁇ m.
- Comparative Example 12 which will be described later, is a non-chlorinated unsubstituted quinacridone treated with sulfuric acid according to Example 23, and then finished in the same manner as in Example 38.
- the average particle size of was 0.36 ⁇ m.
- the chlorinated quinacridone finished into the pigment according to the present invention has 0.2 chlorine substitutions, and as a result of analysis, most of the chlorinated quinacridone was unsubstituted quinacridone in which chlorine was not substituted, but a small amount was contained. It was confirmed that the particles were effectively refined by the presence of chlorinated quinacridone.
- Example 40 and Comparative Example 12 were ⁇ -type crystal forms.
- Table 7 shows the result of producing an offset ink and evaluating the color tone.
- the chlorinated quinacridone according to the present invention was not much different from the hue of Comparative Example 12, which will be described later, but was high in sharpness and excellent in coloring power. That is, by slightly chlorinating quinacridone by the production method of the present invention, it was possible to prepare an excellent color tone while maintaining the essential physical properties of quinacridone before chlorination.
- Example 41 As an example of a coloring composition containing the chlorinated quinacridone and vehicle components of the present invention, an example of using a color toner will be shown. 50 parts of the chlorinated quinacridone obtained in Example 38 and 50 parts of a polyester resin (polyester resin A described in Example 1 of JP2012-198438A) were mixed at 120 ° C. using a pressure kneader, and then A colored composition was obtained by kneading at 95 ° C. using three rolls.
- a polyester resin polyester resin A described in Example 1 of JP2012-198438A
- color toner B was obtained by performing the same operation using the chlorinated quinacridone obtained in Comparative Example 11 instead of the chlorinated quinacridone obtained in Example 38.
- color toner A was more transparent than color toner B.
- a developer is prepared by mixing 6 parts of these color toners and 100 parts of a carrier of ferrite (DFC-350C, manufactured by Dowa Iron Powder Co., Ltd.) coated with a silicone resin having an average particle diameter of 60 ⁇ m as a carrier.
- Example 42 As an example of the coloring composition containing the chlorinated quinacridone and the vehicle component of the present invention, an application example of ink jet ink will be shown. 19 parts of the chlorinated quinacridone obtained in Example 38 and 16.4 parts of a styrene-acrylic acid copolymer (John Cryl 61J, weight average molecular weight 10,000, acid value 195 mg KOH / g, solid content 31%, manufactured by BASF) And 5 parts of a nonionic surfactant (polyoxyethylene distyrenated phenyl ether, Emulgen A-90, manufactured by Kao Corporation) and 59.6 parts of ion-exchanged water are mixed, and zirconia beads (diameter 0.5 mm ⁇ ) Was added and dispersed with a paint shaker for 12 hours to prepare a concentrated solution.
- a nonionic surfactant polyoxyethylene distyrenated phenyl ether, Emulgen A-90, manufactured by Kao Corporation
- inkjet ink B was obtained in the same manner as above except that the chlorinated quinacridone obtained in Comparative Example 11 was used instead of the chlorinated quinacridone obtained in Example 38.
- These ink-jet inks are filled into an ink cartridge (HG5130, manufactured by Seiko Epson Corporation), and high-quality paper (npi quality, basis weight 64.0 g / m 2 , manufactured by Nippon Paper Industries Co., Ltd.) and coated paper (OK Top Coat N, Tsubo) Print a color chart image (ProfileMaker chart image “TC3.5 CMYK i1_iO”, manufactured by X-rite) at a resolution of 600 ⁇ 600 dpi on an amount of 104.7 g / m 2 , manufactured by Oji Paper Co., Ltd. Produced. When the printed matter printed was visually evaluated, the ink jet ink A was superior to the ink jet ink B and had a higher concentration.
- Example 43 As an example of the coloring composition containing the chlorinated quinacridone and the vehicle component of the present invention, an example of using a color filter resist ink will be shown. 10.5 parts of chlorinated quinacridone obtained in Example 38, 1.5 parts of chlorinated quinacridone prepared in Example 35 as a dispersion aid, and an acrylic resin solution (in the examples of JP2013-120309A) 23 parts of the described acrylic resin solution 1), 3.6 parts of Ajisper PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd.) and 61.4 parts of propylene glycol monomethyl ether acetate as a dispersant are mixed, and zirconia beads (diameter 0.1 mm ⁇ ) ) Was added and dispersed for 8 hours with Picomill (manufactured by Asada Tekko Co., Ltd.) to prepare a concentrated solution.
- Ajisper PB821 manufactured by Ajinomoto Fine Techno Co., Ltd.
- color filter resist ink A 40 parts of this concentrated liquid, 213.2 parts of an acrylic resin solution (acrylic resin solution 2 described in Examples of JP2013-120309A), and a photopolymerizable monomer (Aronix M400, manufactured by Toagosei Co., Ltd.) 2.8 parts, 2 parts of photopolymerization initiator (Irgacure 907, manufactured by BASF), 0.4 part of sensitizer (EAB-F, manufactured by Hodogaya Chemical Co., Ltd.), and ethylene glycol monomethyl ether acetate 39 6 parts were mixed and filtered through a 1 ⁇ m filter to prepare color filter resist ink A.
- color filter resist ink B was obtained in the same manner as in Example 38 except that the chlorinated quinacridone obtained in Comparative Example 11 was used instead of the chlorinated quinacridone obtained in Example 38.
- color filter resist inks were applied on a 0.7 mm thick glass plate to a thickness of 1.5 ⁇ m to prepare a coated plate, dried, and then irradiated with 300 mJ / cm 2 of ultraviolet rays. Furthermore, the color filter was obtained by heating at 230 degreeC for 1 hour. Evaluation of the obtained color filter was judged by a numerical value of contrast ratio. Contrast ratio is measured by using a color luminance meter (BM-5A, manufactured by Topcon Corporation) with a color filter sandwiched between two polarizing plates. It was calculated by dividing by the brightness. As a result, the contrast ratio of the color filter with the color filter resist ink A was 3500, and the contrast ratio of the color filter with the color filter resist ink B was 1700, and the color filter resist ink A was superior.
- BM-5A color luminance meter
- the method for producing a halogenated organic pigment of the present invention does not require special production equipment and by-product processing equipment, and is excellent in safety and productivity.
- the halogenated organic pigment obtained by the production method of the present invention has a wide range of color tones that can be adjusted, the present invention can provide a colored composition that is versatile and excellent in usefulness.
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Abstract
Description
しかしながら、(1)の方法では、毒性の強い塩素や臭素を用いるために、安全性に配慮した大規模な特別な製造設備が必要である。また、副生する大量のハロゲン化水素ガスを処理するための設備が必要である。さらに顔料の製造工程(製造設備や反応溶媒等)中で混入する金属元素(鉄、アルミニウム、カルシウム等)によって、所望とするハロゲン化有機顔料の一部が金属元素で置換やレーキ化された副生成物および好ましくない不純物が、得られるハロゲン化有機顔料中に混入してしまい、用途に求められる特性に悪影響を及ぼすといった問題があった。
一方、(2)の方法では、副生成物としてこはく酸イミドが副生される。そのため、得られたハロゲン化有機顔料中からこはく酸イミドを分離除去し、これを処理するための設備が必要である等の問題があった。また、多くの場合、トリフルオロ酢酸やクロロホルム等の環境上好ましくない有機溶媒を使用すること、および、ハロゲン化反応の収率に劣る等の問題があった。
したがって、本発明が解決しようとする課題は、安全性と生産性に優れた新規なハロゲン化有機顔料の製造方法を提供することである。また、広い範囲の色調を持ち、微細な粒子に調製されたハロゲン化有機顔料およびそれを用いた着色組成物等を提供することである。
さらに本発明は、上記着色組成物を含むカラートナー、インクジェットインキおよびカラーフィルタレジストインキに関する。
本発明は、上記カラートナーまたは上記インクジェットインキを用いて印刷される印刷物に関する。
本発明は、上記カラーフィルタレジストインキを用いて形成されるフィルタセグメントを具備するカラーフィルタに関する。
また、本発明の製造方法によって得られるハロゲン化有機顔料は、調整可能な色調の範囲が広いため、用途が広い、有用性に優れた着色組成物を提供できる。
上記ハロゲン化工程が溶媒存在下で行われ、上記溶媒が強酸および共融塩の少なくともいずれかを含むことが好ましい。
上記強酸は、硫酸、発煙硫酸、クロロスルホン酸、ポリリン酸およびメタンスルホン酸からなる群より選ばれる一種以上を含むことが好ましい。
上記共融塩が、塩化アルミニウムおよび塩化ナトリウムの共融塩であることが好ましい。
本発明で使用されるハロゲン化剤は、トリクロロイソシアヌル酸、ジクロロイソシアヌル酸金属塩、トリブロモイソシアヌル酸およびジブロモイソシアヌル酸金属塩からなる群より選ばれる一種以上のN-ハロイミド化合物を含む。
すなわち、N-ハロイミド化合物の使用量は、有効ハロゲン基準で1~2モル当量とすることが好ましい。
本発明の製造方法では、ハロゲン化工程が溶媒存在下で行われることが好ましい。該溶媒は、ハロゲン化反応を阻害せず、有機顔料の骨格の分解を引き起こす恐れがないものであれば、特に制限はないが、反応収率等の観点から、強酸および共融塩の少なくともいずれかを含む溶媒を使用することが好ましい。強酸としては、硫酸、発煙硫酸、クロロスルホン酸およびポリリン酸等の無機酸、トリフルオロ酢酸、ジクロロ酢酸、メタンスルホン酸およびエタンスルホン酸等の有機酸が挙げられる。強酸として、これらを単独もしくは混合して使用することができる。コストや反応収率、製造工程上の利点等の観点から無機酸およびメタンスルホン酸等が好ましく、硫酸、発煙硫酸、クロロスルホン酸、ポリリン酸、メタンスルホン酸およびこれらの混合物がより好ましい。硫酸は、含水率が多いと有機顔料骨格の分解を引き起こす恐れがあるので、90質量%以上の高濃度の硫酸が好ましい。
共融塩としては、塩化アルミニウムおよび塩化ナトリウムの共融塩等が挙げられる。
溶媒は、強酸と共融塩との混合物であってもよい。
溶媒として共融塩を使用する場合、有機顔料に対して2~30質量倍を使用することが好ましい。
本発明の製造方法で原料として使用できる有機顔料は、本発明で使用されるN-ハロイミド化合物でハロゲン化できる有機顔料であれば、特に限定されない。本発明における有機顔料としては、キナクリドン系顔料、アゾ系顔料、フタロシアニン系顔料、アントラキノン系顔料、ジオキサジン系顔料、ジケトピロロピロール系顔料、キノフタロン系顔料、アントラピリミジン系顔料、アンサンスロン系顔料、イソビオラントロン系顔料、インダンスロン系顔料、フラバンスロン系顔料、ペリノン系顔料、ペリレン系顔料、イソインドリン系顔料、イソインドリノン系顔料、チアジンインジゴ系顔料、チオインジゴ系顔料およびピラントロン系顔料等が挙げられる。これらの有機顔料は、ハロゲン置換されうる水素原子を少なくとも一つ有していれば、既に構造中に置換基としてハロゲンを持つ顔料であってもよい。これらの内、キナクリドン系顔料、フタロシアニン系顔料、アントラキノン系顔料、キノフタロン系顔料、ペリレン系顔料、イソインドリノン系顔料、ジオキサジン系顔料およびインダンスロン系顔料からなる群より選ばれる少なくともいずれかを含むものが好ましい。
したがって、式I中の-N(X3)2で表わされる部分としては、ピペリジノ基、モルホリノ基等が挙げられる。
アゾ系顔料の例:C.I.Pigment Yellow12、C.I.Pigment Yellow83、C.I.Pigment Yellow180、C.I.Pigment Red146、C.I.Pigment Red269等。
フタロシアニン系顔料の例:C.I.Pigment Red15、C.I.Pigment Blue15:1、C.I.Pigment Blue15:2、C.I.Pigment Blue15:3、C.I.Pigment Green58、アルミニウムフタロシアニン等。
アントラキノン系顔料の例:C.I.Pigment Yellow147等。
ジオキサジン系顔料の例:C.I.Pigment Violet23、C.I.Pigment Violet37等。
ジケトピロロピロール系顔料の例:C.I.Pigment Red254等。
キノフタロン系顔料の例:C.I.Pigment Yellow138等。
アントラピリミジン系顔料の例:C.I.Pigment Yellow108等。
アンサンスロン系顔料の例:C.I.Pigment Red168等。
イソビオラントロン系顔料の例:C.I.Pigment Violet31等。
インダンスロン系顔料の例:C.I.Pigment Blue60等。
フラバンスロン系顔料の例:C.I.Pigment Yellow24等。
ペリノン系顔料の例:C.I.Pigment Orange43等。
ペリレン系顔料の例:C.I.Pigment Red178等。
イソインドリン系顔料の例:C.I.Pigment Yellow139等。
イソインドリノン系顔料の例:C.I.Pigment Yellow109、C.I.Pigment Yellow110等。
チアジンインジゴ系顔料の例:C.I.Pigment Red279、C.I.Pigment Orange80
チオインジゴ系顔料の例:C.I.Pigment Red88等。
ピラントロン系顔料の例:C.I.Pigment Orange40等。
本発明におけるハロゲン化有機顔料とは、上記顔料の置換基の一部をハロゲンに置換したもの、もしくは顔料の基本骨格に置換基としてハロゲンを持つものである。ハロゲンとしては、臭素及び塩素の少なくとも一種である。
本発明におけるハロゲン化有機顔料として具体的には、例えば、C.I.Pigment Red202、C.I.Pigment Red209等のキナクリドン系顔料;
C.I.Pigment Green7、C.I.Pigment Green36、C.I.Pigment Blue15:1、またはC.I.Pigment Blue15:2等のフタロシアニン系顔料;
C.I.Pigment Violet23等のジオキサジン系顔料;
C.I.Pigment Red254等のジケトピロロピロール系顔料;
C.I.Pigment Yellow138等のキノフタロン系顔料;
C.I.Pigment Red168等のアンサンスロン系顔料;
C.I.Pigment Violet31等のイソビオラントロン系顔料;
C.I.Pigment Blue64等のインダンスロン系顔料;
C.I.Pigment Orange66等のイソインドリン系顔料;
C.I.Pigment Yellow109、C.I.Pigment Yellow110、またはC.I.Pigment Orange61等のイソインドリノン系顔料;
C.I.Pigment Red279等のチアジンインジゴ系顔料;
C.I.Pigment Red88、C.I.Pigment Red181等のチオインジゴ系顔料;
C.I.Pigment Orange51、C.I.Pigment Red216、またはC.I.Pigment Red226等のピラントロン系顔料;等が挙げられ、かつこれらの顔料をさらにハロゲン化された化合物も含む。ただし、必ずしもこれらに限定されるものではない。
本発明の製造方法のハロゲン化工程でのハロゲン化の反応温度は、使用する有機顔料の分解反応や、スルホン化反応およびクロロスルホン化反応等の副反応を抑制できる温度が好ましい。しかしながら、本発明の製造方法においては、目的とする生成物をスルホニウム基、クロロスルホニウム基等が導入したものとする場合は、原料である有機顔料に対し、スルホン化およびクロロスルホン化のうち少なくともいずれかとハロゲン化とを同時に行ってもよい。
ハロゲン化の反応温度は、有機顔料、溶媒、N-ハロイミド化合物の種類、並びに触媒の有無および所望のハロゲン原子の置換数に応じて、適宜、決めることができるが、概ね0~150℃、好ましくは10~100℃である。
ハロゲン化の反応時間は、溶媒へのN-ハロイミド化合物の溶解速度にも影響されるため、N-ハロイミド化合物の粒子の大きさや、反応槽中での反応液の撹拌速度に応じて、適宜、決めることができるが、N-ハロイミド化合物の粒子が数ミリメートルで十分な撹拌が行われる場合、30分間~10時間が好ましく、1時間~5時間がより好ましい。
例えば、原料としてフタロシアニン系顔料を用いてスルホン化とハロゲン化を行う場合、上記のように反応温度を高くして同時に行ってもよく、または、まず原料と5%発煙硫酸とを混合し、反応温度100~120℃で2~3時間でスルホン化処理をし、次いでスルホン化処理よりも反応温度を下げ、ハロゲン化剤を添加して、好ましくは反応温度10~20℃で3~4時間でハロゲン化処理をするという2段階で行うことも可能である。
(1)ハロゲン置換数の平均が0.05以上7.0以下である。
(2)ハロゲン分布幅が3以上であること。
(3)平均粒径が0.1μm以下、好ましくは0.06μm以下であること。平均粒径の測定については、後述する。
(4)アルミニウムフタロシアニンおよびハロゲン化アルミニウムフタロシアニンの含有量が、1.0質量%以下であること。
(5)中心元素が、水素、マンガン、鉄、コバルト、亜鉛、ニッケルおよび銅からなる群より選択されるいずれか一種以上であること。
本発明の製造方法は、ハロゲン化とアシッドペースティング処理による顔料化とを同時に行うことになるため、製造工程の短縮化が可能、かつ使用価値が高い顔料形態のハロゲン化有機顔料が得られる。しかしながら、色材として用途に応じた顔料形態に仕上げる他の顔料化工程(コンディショニングまたはフィニッシング工程とも称する)をさらに有してもよい。
顔料化工程を行う場合は、ハロゲン化工程後に、反応液から溶媒を留去、または反応液を多量の水で希釈してハロゲン化有機顔料を析出させ、濾過してハロゲン化有機顔料の含水ケーキまたは乾燥品として分離する分離工程を行い、次いで、公知の顔料化工程を行うことが好ましい。公知の顔料化工程の処理としては、例えば、有機溶剤存在下の加熱処理、無機塩と多価アルコール等を加えたソルベントソルトミリング処理あるいは硫酸等に溶解させた後に多量の水で希釈するアシッドペースティング処理等が挙げられる。また、顔料化工程中または前後で、樹脂、活性剤、体質顔料および顔料分散剤等を添加し、顔料の利用価値を高めてもよい。ここで顔料分散剤とは、顔料骨格に酸性置換基または塩基性置換基等が導入された化合物、並びに顔料と相互作用の大きい部分構造を分子内に有する高分子化合物等を指し、顔料分散能を持つ化合物の総称である。
本発明の製造方法で得られたハロゲン化有機顔料を、ビヒクル成分と混合することで着色組成物とし、印刷インキ、塗料、プラスチック用着色剤、捺染剤、カラートナー、インクジェットインキおよびカラーフィルタレジストインキ等の色材として好適に使用することができる。特に、プラスチック用着色剤、カラートナー、インクジェットインキおよびカラーフィルタレジストインキ等に好適に使用することができる。
オフセットインキには、必要に応じて、インキ溶剤、ドライヤー、レベリング改良剤、増粘剤等の公知の添加剤を適宜配合することができる。
樹脂としては、例えば、ガムロジン、ウッドロジン、トール油ロジン、ライムロジン、ロジンエステル、マレイン酸樹脂、ギルソナイト、ダンマル、セラック、ポリアミド樹脂、ビニル樹脂、ニトロセルロース、環化ゴム、塩化ゴム、エチルセルロース、酢酸セルロース、エチレン-酢酸ビニル共重合体樹脂、ウレタン樹脂、ポリエステル樹脂、アルキッド樹脂等が挙げられる。
溶剤としては、例えば、n-ヘキサン等の脂肪族炭化水素系、トルエン等の芳香族炭化水素系、メタノール、エタノール、イソプロピルアルコール等のアルコール系、アセトン、メチルエチルケトン等のケトン系、酢酸エチル、乳酸エチル、アセト酢酸エチル等のエステル系、ジエチルエーテル等のエーテル系、エチレングリコールモノエチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノブチルエーテル等のエーテル・アルコール系、クロルベンゾール等の芳香族ハロゲン化物系等が挙げられる。
グラビアインキには、必要に応じて、例えば硫酸バリウム、炭酸バリウム、炭酸カルシウム、石膏、アルミナホワイト、クレー、シリカ、シリカホワイト、タルク、珪酸カルシウム、沈降性炭酸マグネシウム等の体質顔料の他、補助剤として、顔料分散剤、可塑剤、紫外線防止剤、酸化防止剤、帯電防止剤等の公知の添加剤を適宜配合することができる。
樹脂としては、例えば、ニトロセルロース、アミノアルキド樹脂、アクリル樹脂、アミノアクリル樹脂、ウレタン樹脂、ポリビニルアセタール樹脂、エポキシ樹脂、ポリエステル樹脂、ポリ塩化ビニル樹脂、フッ化ビニリデン樹脂、フッ化ビニル樹脂、ポリエーテルスルホン樹脂等が挙げられる。
溶剤としては、脂肪族炭化水素系、芳香族炭化水素系、ハロゲン化炭化水素系、アルコール系、ケトン系、エステル系、エーテル系、エーテル・アルコール系、エーテル・エステル系等の有機溶剤、水等が挙げられる。
塗料には、必要に応じて、体質顔料、顔料分散剤、レベリング改良剤、増粘剤、硬化剤等の公知の添加剤を適宜配合することができる。
プラスチック用着色剤および/または本発明のハロゲン化有機顔料を用いてプラスチックを着色し、着色プラスチックを成型することができる。プラスチック成型のためのプラスチック用樹脂としては、ポリプロピレン樹脂、ポリエチレン樹脂、エチレン・プロピレン共重合体、αオレフィンとアクリル酸またはマレイン酸との共重合体、エチレン・酢酸ビニル共重合体、エチレンとアクリル酸または無水マレイン酸との共重合体等のポリオレフィン系樹脂、ポリ塩化ビニル樹脂、ポリ酢酸ビニル等のビニル樹脂、ホルマル樹脂やブチラール樹脂等のアセタール樹脂、ポリアクリロニトリルやメタクリル樹脂等のアクリル樹脂、ポリスチレンやアクリロニトリル・ブタジエン・スチレン共重合体等のスチロール樹脂、ポリエチレンテレフタレートやポリカーボネート等のポリエステル樹脂、6-ナイロン等のナイロン、不飽和ポリエステル樹脂、エポキシ樹脂、尿素樹脂、メラミン樹脂、セルロース樹脂等が挙げられる。これらの樹脂はプラスチック用着色剤に用いられるビヒクルとしても使用することもできる。
プラスチック用着色剤には、必要に応じて、可塑剤、紫外線防止剤、酸化防止剤、離型剤等の公知の添加剤を適宜配合することができる。
樹脂としては、アクリル樹脂、アミノアクリル樹脂、ウレタン樹脂等が挙げられる。溶剤としては、脂肪族炭化水素系、芳香族炭化水素系、アルコール系、ケトン系、エステル系、エーテル系、エーテル・アルコール系、エーテル・エステル系の有機溶剤、水等が挙げられる。
捺染剤には、必要に応じて、顔料分散剤、消泡剤、増粘剤、界面活性剤等の公知の添加剤を適宜配合することができる。
カラートナーには、必要に応じて、顔料分散剤、荷電制御剤、離型剤等の公知の添加剤を適宜配合することができる。
樹脂としては、アクリル樹脂、スチレン-アクリル酸共重合体、ポリエステル樹脂、ポリアミド樹脂、ポリウレタン樹脂、フッ素樹脂等の、水に溶解する樹脂、水に分散性のエマルションおよびコロイダルディスパージョン樹脂等が挙げられる。これらの樹脂には、必要に応じアンモニア、アミン、無機アルカリ等の中和剤が加えられる。
また、溶剤としては、例えば、水、エチレングリコール、ポリエチレングリコール、エチレングリコールモノメチルエーテル、置換ピロリドン等が挙げられる。また、インクジェットインキの乾燥性を速める目的で、メタノール、エタノール、イソプロピルアルコール等のアルコール類も使用できる。
インクジェットインキには、必要に応じて、防腐剤、浸透剤、キレート剤や、顔料の分散安定性を向上させるためにアニオン系界面活性剤、非イオン系界面活性剤、カチオン系界面活性剤、両性イオン系界面活性剤等の公知の添加剤を適宜配合することができる。なお、インクジェットインキは、カラーフィルタの製造に用いることもできる。
熱可塑性樹脂としては、例えば、ブチラール樹脂、スチレン-マレイン酸共重合体、塩素化ポリエチレン樹脂、塩素化ポリプロピレン樹脂、ポリ塩化ビニル樹脂、塩化ビニル-酢酸ビニル共重合体、ポリ酢酸ビニル樹脂、ポリウレタン系樹脂、ポリエステル樹脂、アクリル樹脂、アルキッド樹脂、ポリスチレン樹脂、ポリアミド樹脂、ゴム系樹脂、環化ゴム系樹脂、セルロース樹脂、ポリエチレン樹脂、ポリブタジエン樹脂、ポリイミド樹脂等が挙げられる。また、熱硬化性樹脂としては、例えば、エポキシ樹脂、ベンゾグアナミン樹脂、ロジン変性マレイン酸樹脂、ロジン変性フマル酸樹脂、メラミン樹脂、尿素樹脂、フェノール樹脂等が挙げられる。活性エネルギー線硬化性樹脂としては、水酸基、カルボキシル基、アミノ基等の反応性の置換基を有する線状高分子にイソシアネート基、アルデヒド基、エポキシ基等を介して、(メタ)アクリル化合物、桂皮酸等の光架橋性基を導入した樹脂等が挙げられる。
カラーフィルタレジストインキには、必要に応じて、顔料分散剤、光重合開始剤、増感剤等の公知の添加剤を適宜配合することができる。
本発明の印刷物は、上記カラートナーまたは上記インクジェットインキを用いて印刷されることを特徴とする。本発明の印刷物は、フィルム状もしくはシート状の基材にグラビア印刷、フレキソ印刷等の公知の印刷方式を用いて塗布し、オーブンによる乾燥によって被膜を定着することで、得ることができる。
上記基材としては、ポリエチレン、ポリプロピレン等のポリオレフィン、ポリエチレンテレフタレート、ポリカーボネート、ポリ乳酸等のポリエステル、ポリスチレン、AS樹脂、ABS樹脂等のポリスチレン系樹脂、ナイロン、ポリアミド、ポリ塩化ビニル、ポリ塩化ビニリデン、セロハン、紙、アルミ等、または、これらの複合材料等からなるものが挙げられる。
カラーフィルタは、少なくとも1つの赤色フィルタセグメントと、少なくとも1つの緑色フィルタセグメントと、および少なくとも1つの青色フィルタセグメントとを具備し、さらにマゼンタ色フィルタセグメント、シアン色フィルタセグメント、および黄色フィルタセグメントを具備するものであってもよい。
本発明のカラーフィルタは、公知の印刷法またはフォトリソグラフィー法により、製造することができる。
なお、化合物の同定は、飛行時間型質量分析装置(autoflexIII(TOF-MS)、ブルカー・ダルトニクス社製)を用いて得られたマススペクトラムの分子イオンピークと、計算によって得られる質量数との一致、並びに、元素分析装置(2400CHN元素分析装置、パーキン・エルマー社製)を用いて得られる炭素、水素および窒素の比率と、理論値との一致により行った。
ハロゲン原子の量は、化合物を酸素燃焼フラスコ法にて燃焼させ、水に吸収させた液体をイオンクロマトグラフィーにより含有量を定量してハロゲン置換数に変換して算出した。
また、得られたハロゲン化有機顔料中の各成分(ハロゲン化化合物)の含有率(モル比)は、TOF-MSの測定により得られたマススペクトラムの各成分の信号強度(ピーク)の比を、各成分のモル比とした。
[実施例1]
98%硫酸99部と30%発煙硫酸21部とを混合して99.5%硫酸120部を調製した。これに触媒としてヨウ素を0.1部加えた後、フタロシアニン系顔料として銅フタロシアニン(C.I.Pigment Blue15、T-99 CRUDE BLUE、珠海東洋科美化学有限公司社製)20部を、30℃以下を保ちながら氷水浴で冷却しながら加えた。次いで、50℃まで加温してトリクロロイソシアヌル酸2.7部を加え、同温度で3時間撹拌した。このとき、トリクロロイソシアヌル酸の量は、銅フタロシアニンに対して0.33倍モル、有効塩素基準では1.00モル当量である。次いで、水600部に上記反応液を撹拌しながら注ぎ入れ、70℃に加熱して、濾過、温水洗浄、1%水酸化ナトリウム水溶液洗浄、温水洗浄の順で処理をし、その後、乾燥して、塩素置換数が平均0.9個の塩素化銅フタロシアニン18.6部を得た。収率は89%であった。
この塩素化銅フタロシアニンを電子顕微鏡で確認したところ、平均粒径は0.06μmであった。また、ハロゲン分布幅は4であった。アルミニウムフタロシアニンおよび塩素化アルミニウムフタロシアニンの含有は認められなかった。
ハロゲン分布幅は全ピーク値に対する各ピーク値の割合が1%以上のピークの数をカウントし、ハロゲン分布幅とした。
表1~表2に示す条件に変更した以外は、実施例1と同様の方法によって、それぞれのハロゲン化フタロシアニンを得た。2%発煙硫酸は、98%硫酸86部と30%発煙硫酸34部を混合して調製した。表1に示す仕込量のモル当量は有効ハロゲン基準のモル当量である。得られたハロゲン化フタロシアニンの塩素置換数、臭素置換数、収率を併せて表2に示す。
なお、使用したN-ハロイミド化合物は、いずれも全て粒状の白色固体で、取り扱いは容易であり、反応中にガスの発生も認められず、一連の操作は極めて容易であった。
実施例2~10で得られた塩素化銅フタロシアニンを電子顕微鏡で確認したところ、いずれも平均粒径は0.06μmであった。アルミニウムフタロシアニンおよび塩素化アルミニウムフタロシアニンの含有は認められなかった。
従来法である塩素ガスを用いたハロゲン化フタロシアニンの製造例を示す。
塩化アルミニウム81部、塩化ナトリウム19部および塩化第二鉄1部を加温して溶融し、140℃で銅フタロシアニン(C.I.Pigment Blue15、T-99 CRUDE BLUE、珠海東洋科美化学有限公司社製)20部を加えた。160℃に昇温して塩素ガス5部を吹き込んだ。水1000部に上記反応液を注入し、濾過、温水洗浄、1%塩酸水溶液洗浄、温水洗浄、1%水酸化ナトリウム水溶液洗浄、温水洗浄の順で処理をし、その後、乾燥して塩素置換数が平均2.0個の粗製塩素化銅フタロシアニン20.6部を得た。収率は92%であった。塩素ガスを吹き込んでいるときに塩化水素ガスおよび塩化アルミニウムの昇華物が発生し、それらの捕捉装置が必要であった。
比較例1で得られた粗製塩素化銅フタロシアニンを用いて、アシッドペースティングによる顔料化を行った。98%硫酸120部に粗製塩素化銅フタロシアニン20部を溶解し、50℃で3時間撹拌した。次いで、水600部に撹拌しながら溶解液を注ぎ入れ、70℃に加熱して、濾過、温水洗浄、1%水酸化ナトリウム水溶液洗浄、温水洗浄、乾燥して塩素置換数が平均2.0個の塩素化銅フタロシアニン19.2部を得た。収率は96%であった。この塩素化銅フタロシアニンの一部を錠剤状に圧縮成型して蛍光X線および質量分析計による測定を行うと、アルミニウムフタロシアニン、1~4個塩素に置換されたアルミニウムフタロシアニンが検出され、その含有量は4.9質量%であった。
従来法であるハロゲン原子を有する原料を用いたハロゲン化フタロシアニンの製造例を示す。
無水フタル酸28部、クロロ無水フタル酸105部、塩化第一銅19部、尿素139部、モリブデン酸アンモニウム0.5部、溶媒としてtert-アミルベンゼン(商品名:ハイゾールP、アルキルベンゼン混合物、日本石油社製)210部をガラスオートクレーブ中に仕込み、200℃で圧力2.0kg/cm2・Gで4時間反応させた。精製したスラリーを減圧下で加熱することで溶剤を留去して回収した。残留物に2000部の5%硫酸をくわえ90℃で4時間撹拌して濾過し、乾燥して塩素置換数が平均3.0個の粗製塩素化銅フタロシアニン109.7部を得た。収率は85%であった。
比較例3で得られた粗製塩素化銅フタロシアニンを用いて、アシッドペースティングによる顔料化を行った。98%硫酸120部に粗製塩素化銅フタロシアニン20部を溶解し、50℃で3時間撹拌した。次いで、水600部に撹拌しながら溶解液を注ぎ入れ、70℃に加熱して、濾過、温水洗浄、1%水酸化ナトリウム水溶液洗浄、温水洗浄の順で処理をし、その後、乾燥して塩素置換数が平均3.0個の塩素化銅フタロシアニン19.3部を得た。収率は96%であった。
特許文献6に記載された方法を用いて製造したハロゲン化フタロシアニンの例を示す。
フタロシアニン系顔料として銅フタロシアニン(C.I.Pigment Blue15、T-99 CRUDE BLUE、珠海東洋科美化学有限公司社製)20部とN-ブロモスクシンイミド28部の混合物を、トリフルオロ酢酸1400mLと98%硫酸420mLの溶液中で、室温で24時間撹拌した。このとき、N-ブロモスクシンイミドの量は、銅フタロシアニンに対して4.52倍モル、有効臭素基準で4.52モル当量である。得られた暗青色溶液を5000部の氷水中に注いだ。得られた固体を水で洗浄し、濾過で取り出し、乾燥して、臭素化銅フタロシアニン17.5部を得た。収率は58%であり、同じく臭素化を行った実施例7、8よりも低かった。また、臭素置換数は平均3.76個であり、理論的に得られる臭素置換数よりも低かった。
アントラキノン系顔料であるC.I.Pigment Yellow147(Filestar Yellow RNB、BASF社製)10部を、クロロスルホン酸150部に加えて溶解させた後に、トリクロロイソシアヌル酸2.6部を加え、20℃で2時間撹拌した。このとき、トリクロロイソシアヌル酸はPigment Yellow147に対して0.66倍モル、有効塩素基準では2.0モル当量である。次いで、水600部に撹拌しながら反応液を注ぎ入れ、70℃に加熱して、濾過、温水洗浄、1%水酸化ナトリウム水溶液洗浄、温水洗浄の順で処理をし、その後、乾燥して、塩素置換数が平均1.9個の塩素化Pigment Yellow147を10.8部得た。収率は97%であった。
従来技術として、塩素ガスによる製造方法の例を示す。
実施例11のトリクロロイソシアヌル酸の代わりに塩素ガスを使用すること以外は、実施例11と同様にハロゲン化反応を行った。塩素ガスは反応液の底部にガラス管を通して約2部/時間の速度で、塩素置換数が2.0になるまで導入した。このときの塩素ガス導入量の合計は6.1部であった。塩素置換数が2.0のときの塩素ガスの必要理論量は3.2部であるので、塩素ガス基準の収率は52%であった。また、ハロゲン化化合物の収量は10.3部、収率は92%で、実施例11の場合よりも低かった。さらに、未反応の塩素ガスと副生する塩化水素ガスを捕捉するために、実施例11の製造装置に加えてアルカリ水に吸収させる装置が必要であった。
キノフタロン系顔料であるC.I.Pigment Yellow138(Paliotol Yellow K0961HDK、BASF社製)10部を、クロロスルホン酸80部に加えて溶解させた後に、トリクロロイソシアヌル酸1.1部を加え、10℃で3時間撹拌した。このとき、トリクロロイソシアヌル酸はPigment Yellow138に対して0.33倍モル、有効塩素基準では1.00モル当量である。次いで、水600部に撹拌しながら反応液を注ぎ入れ、70℃に加熱して、濾過、温水洗浄、1%水酸化ナトリウム水溶液洗浄、温水洗浄の順で処理をし、その後、乾燥して、塩素置換数が平均0.3個更に置換された塩素化Pigment Yellow138を9.6部得た。収率は94%であった。塩素置換数が平均(全体)は8.3個であった。平均粒径は0.06μmであった。
ペリレン系顔料であるC.I.Pigment Red178(Paliogen Red K3911、BASF社製)10部を、98%硫酸80部に加えて溶解させた後に、トリクロロイソシアヌル酸1.04部を加え、10℃で3時間撹拌した。このとき、トリクロロイソシアヌル酸はPigment Red178に対して0.33倍モル、有効塩素基準では1.00モル当量である。次いで、水600部に撹拌しながら反応液を注ぎ入れ、70℃に加熱して、濾過、温水洗浄、1%水酸化ナトリウム水溶液洗浄、温水洗浄の順で処理をし、その後、乾燥して、塩素置換数が平均1.00個の塩素化Pigment Red178を9.9部得た。収率は98%であった。平均粒径は0.05μmであった。
イソインドリノン系顔料であるC.I.Pigment Yellow109(Irgazin Yellow L1030、BASF社製)10部を、クロロスルホン酸80部に加えて溶解させた後に、トリクロロイソシアヌル酸1.19部を加え、10℃で3時間撹拌した。このとき、トリクロロイソシアヌル酸はPigment Yellow109に対して0.33倍モル、有効塩素基準では1.00モル当量である。次いで、水600部に撹拌しながら反応液を注ぎ入れ、70℃に加熱して、濾過、温水洗浄、1%水酸化ナトリウム水溶液洗浄、温水洗浄の順で処理をし、その後、乾燥して、塩素置換数が平均0.25個更に置換された塩素化Pigment Yellow109を8.8部得た。収率は88%であった。塩素置換数が平均(全体)は8.25個であり、平均粒径は0.04μmであった。
イソインドリノン系顔料であるC.I.Pigment Yellow110(Irgazin Yellow L2060、BASF社製)10部とヨウ素0.05部を、98%硫酸80部に加えて溶解させた後に、トリクロロイソシアヌル酸1.21部を加え、10℃で3時間撹拌した。このとき、トリクロロイソシアヌル酸はPigment Yellow110に対して0.33倍モル、有効塩素基準では1.00モル当量である。次いで、水600部に撹拌しながら反応液を注ぎ入れ、70℃に加熱して、濾過、温水洗浄、1%水酸化ナトリウム水溶液洗浄、温水洗浄の順で処理をし、その後、乾燥して、塩素置換数が平均0.78個更に置換された塩素化Pigment Yellow110を8.5部得た。収率は91%であった。塩素置換数が平均(全体)は2.78個であった。
ジオキサジン系顔料であるC.I.Pigment Violet23(Lionogen Violet FG-6240、トーヨーカラー社製)10部を、メタンスルホン酸100部に加えて溶解させた後に、トリクロロイソシアヌル酸1.32部を加え、20℃で2時間撹拌した。このとき、トリクロロイソシアヌル酸はPigment Violet23に対して0.33倍モル、有効塩素基準では1.00モル当量である。次いで、水600部に撹拌しながら反応液を注ぎ入れ、70℃に加熱して、濾過、温水洗浄、1%水酸化ナトリウム水溶液洗浄、温水洗浄の順で処理をし、その後、乾燥して、塩素置換数が平均0.23個更に置換された塩素化Pigment Violet23を10.4部得た。収率は98%であった。塩素置換数が平均(全体)は2.23個であり、平均粒径は0.03μmであった。
インダンスロン系顔料であるC.I.Pigment Blue60(Lionogen Blue 6510、トーヨーカラー社製)10部を、メタンスルホン酸100部に加えて溶解させた後に、トリクロロイソシアヌル酸1.76部を加え、20℃で3時間撹拌した。このとき、トリクロロイソシアヌル酸はPigment Blue60に対して0.33倍モル、有効塩素基準では1.00モル当量である。次いで、水600部に撹拌しながら反応液を注ぎ入れ、70℃に加熱して、濾過、温水洗浄、1%水酸化ナトリウム水溶液洗浄、温水洗浄の順で処理をし、その後、乾燥して、塩素置換数が平均0.71個の塩素化Pigment Blue60を9.8部得た。収率は90%であった。平均粒径は0.05μmであった。
実施例5で得られたハロゲン化フタロシアニン6部および塗料用ビヒクル(フタルキッド133-60(日立化成社製)56部と、メラン20(日立化成社製)28部と、キシレン10部と、の混合物)94部を3mmスチールボールで分散して濃色塗料を得た。これとは別に、体質顔料としてのタイペークCR-90(石原産業社製)25部および塗料用ビヒクル(フタルキッド133-60(日立化成社製)47部と、メラン20(日立化成社製)23部と、キシレン5部と、の混合物)75部を3mmφアルミナボールで分散して白塗料を得た。これら濃色塗料10部と白塗料24部を混合して淡色塗料を得た。
次に、濃色塗料を同じ金属板に6ミルのアプリケーターで塗工して150℃のオーブンで硬化させた塗板を作製し、更に6ミルのアプリケーターで白塗料を重ね塗りして180℃のオーブンで硬化させた塗板を作製した。塗工面を測色したところ、明度L*=96.6であった。後述するように、比較例2で得られた塩素化銅フタロシアニンを用いた場合よりも高い数値を示した。
比較例1や比較例2で得られた塩素化銅フタロシアニンは青色のアルミニウムフタロシアニンを不純物として含むため、この不純物が濃色塗膜から白塗膜にマイグレーション(=ブリード)して着色し、明度が小さくなったものと推定される。すなわち、本発明の塩素化銅フタロシアニンを用いた塗料は、耐久性の一種である耐マイグレーション性に優れていることが明らかとなった。
比較として、実施例5記載で得られた塩素化銅フタロシアニンの代わりに、比較例1で得られた粗製塩素化銅フタロシアニンを使用した以外は、実施例18と同様の操作を行い、濃色塗料を作製した。しかし、得られた濃色塗料の粘度が極めて高いため、スチールボールとの分離ができず、塗料としての評価はできなかった。
比較として、実施例5で得られた塩素化銅フタロシアニンの代わりに、比較例2で得られた塩素化銅フタロシアニンを用いて、実施例18と同様の方法で濃色塗料および淡色塗料を作製した。実施例18と同様の方法で、淡色塗料を用いて作製した塗板を測色したところ、鮮明性C*=45.3であった。また、濃色塗料を用いて作製した塗板に白塗料を重ね塗りした塗板を測色したところ、明度L*=92.4であった。
実施例5で得られた塩素化銅フタロシアニン100部と、ステアリン酸カルシウム100部とを混合機にて混合してプラスチック用着色剤(ドライカラー)を得た。得られたプラスチック用着色剤(ドライカラー)2部を高密度ポリエチレン樹脂(製品名:Hizex2208J、プライムポリマー社製)1000部、付着剤数滴をタンブリングして十分に混合した後、射出成型機でプレート状に成型し、測色計(ミノルタ分光測色計 CM-2002、コニカミノルタ社製)で色相を測定した。得られたプレートを白色軟質塩化ビニルのシートではさみ、加圧して1分間加熱し、その後、白色軟質塩化ビニルへのマイグレーション性を確認したが、マイグレーションは認められなかった。得られたプレートの鮮明性C*は39.2、色相角度hは256.2°であった。後述するように、比較例1、比較例2で得られた塩素化銅フタロシアニンを用いた場合よりも、耐マイグレーション性に優れ、色相は赤味鮮明となった。
比較として、実施例5で得られた塩素化銅フタロシアニンの代わりに、比較例1で得られた粗製塩素化銅フタロシアニンを使用した以外は、実施例19と同様の操作を行い、プレート状成型物を得た。しかしながら、得られたプレートは緑色のブツが多くみられ、実施例19で得られたプレートと比べ、極めて発色性に劣るという結果となった。ブツを顕微鏡で観察したところ、分散できていない塩素化銅フタロシアニンの顔料粒子であることが確認された。
比較として、実施例5で得られた塩素化銅フタロシアニンの代わりに、比較例2で得られた塩素化銅フタロシアニンを使用した以外は、実施例19と同様の操作を行い、プレート状成型物を得た。得られたプレートを測色したところ、鮮明性C*は38.8、色相角度hは255.9°であり、実施例19の場合と比較して緑味不鮮明であった。更にマイグレーション性を確認したところ、マイグレーションが認められ、すなわち耐久性の一つの項目である耐マイグレーション性については、実施例19の場合と比べて劣っていた。
塩化アルミニウム81部、塩化ナトリウム19部、および塩化第二鉄1部を加温して溶融し、ヨウ素0.1部を加えた後、140℃で銅フタロシアニン20部を加えた。反応液を130℃に保ち、激しく撹拌しながら、トリクロロイソシアヌル酸5.7部を加え、同温度で4時間撹拌した。このとき、トリクロロイソシアヌル酸の量は、銅フタロシアニンに対して0.71倍モル、有効塩素基準では2.1モル当量である。水1000部に上記反応液を注入し、濾過、温水洗浄、1%塩酸水溶液洗浄、温水洗浄、1%水酸化ナトリウム水溶液洗浄、温水洗浄の順で処理をし、その後、乾燥して塩素置換数が平均2.0個の粗製塩素化銅フタロシアニン21.1部を得た。収率は94%であった。
まず、キナクリドンの単純なハロゲン化反応によるハロゲン化キナクリドンの製造例を示す。
表3~4に記載の溶媒にキナクリドン、N-ハロイミド化合物および触媒を加え、表5に記載の反応条件でハロゲン化反応を行った。次いで、水600部に撹拌しながら反応液を注ぎ入れ、70℃に加熱して、濾過、温水洗浄、1%水酸化ナトリウム水溶液洗浄、温水洗浄の順で処理をし、その後、乾燥してハロゲン化キナクリドンを得た。実施例30および実施例31については、反応物が3級アミノ基を有するため硫酸イオンと相互作用し、水600部を加えた反応液(スラリー)の濾過性が極めて不良であったため、このスラリーに水酸化ナトリウムを加えて弱アルカリ性にした後に濾過、温水洗浄、乾燥してハロゲン化キナクリドンを得た。
-SO3H基が置換したキナクリドンの塩素化反応による塩素化キナクリドンの製造例を示す。本例では、スルホン化反応と塩素化反応を連続して行う、ジクロロキナクリドンスルホン酸の製造例を示す。
98%硫酸100部と30%発煙硫酸50部の混合液に無置換キナクリドン10部を加え、60℃で2時間撹拌してスルホン化反応を行った。次いで、25℃に温度を下げてトリクロロイソシアヌル酸5部を加え、同温度で3時間撹拌した。このとき、トリクロロイソシアヌル酸の量は、使用したキナクリドンに対して0.67倍モル、有効塩素基準では2.0モル当量である。水600部に撹拌しながら反応液を注ぎ入れ、濾過、水洗浄して得た水ペーストを水500部に加えてスラリーとした。25%水酸化ナトリウム水溶液を加えてpH11に調整して、濾過、水洗浄、乾燥して塩素化キナクリドン16.1部を得た(収率98%)。
この塩素化キナクリドンは、塩素原子の置換数が2.0個、-SO3Na基の置換数が1.3個で、特開2005-206630号公報に開示されている、ジクロロキナクリドンスルホン酸と同一組成の化合物であった。
-SO2Cl基が置換したキナクリドンの塩素化反応による塩素化キナクリドンの製造例を示す。本例では、クロロスルホン化反応と塩素化反応を連続して行って、ジクロロキナクリドンスルホニルクロリドを製造し、次いで、アミノ化反応を行う製造例を示す。
クロロスルホン酸150部に、無置換キナクリドン10部を加え、40℃で2時間撹拌してクロロスルホン化反応を行った。次いで、25℃に温度を下げてトリクロロイソシアヌル酸5部を加え、同温度で3時間撹拌した。このとき、トリクロロイソシアヌル酸の量は、使用したキナクリドンに対して0.67倍モル、有効塩素基準では2.0モル当量である。さらに、塩化チオニル6部を加え、同温度で1時間撹拌した。氷水1000部に反応液を注ぎ入れ、濾過、水洗浄して得た水ペーストを水500部に加えてスラリーとした。ジエチルアミノプロピルアミン13部を加え、60℃で5時間撹拌して、濾過、水洗浄、乾燥して塩素化キナクリドン20.6部を得た(収率98%)。この塩素化キナクリドンは、塩素原子の置換数が2.0個、ジエチルアミノプロピルアミノスルホニル基(-SO2NH(CH2)3N(C2H5)2)が1.5個で、実施例30と同一組成の化合物であった。
-CH2NHCOCH2Clが置換したキナクリドンの塩素化反応による塩素化キナクリドンの製造例を示す。本例では、クロロアセトアミドメチル化反応と塩素化反応を連続して行って、ジクロロ(クロロアセトアミドメチル)キナクリドンを製造し、次いで、アミノ化反応を行う製造例を示す。
98%硫酸150部に、無置換キナクリドン10部、クロロアセトアミド4.5部およびパラホルムアルデヒド1.5部を加え、20℃で4時間撹拌してクロロアセトアミドメチル化反応を行った。次いで、トリクロロイソシアヌル酸5部を加え、同温度で3時間撹拌した。このとき、トリクロロイソシアヌル酸の量は、使用したキナクリドンに対して0.67倍モル、有効塩素基準では2.0モル当量である。氷水1000部に反応液を注ぎ入れ、濾過、水洗浄して得た水ペーストを水500部に加えてスラリーとした。ジエチルアミノエチルアミン8部を加え、60℃で5時間撹拌して、濾過、水洗浄、乾燥して塩素化キナクリドン17.8部を得た(収率98%)。この塩素化キナクリドンは、塩素原子の置換数が2.0個、ジエチルアミノエチルアミノメチルカルボニルアミノメチル基(-CH2NHCOCH2NHC2H4N(C2H5)2)が1.0個で、実施例31と同一組成の化合物であった。
キナクリドンの製造工程に、本発明の製造方法を組み入れた製造例を示す。本例では、閉環反応と塩素化反応を連続して行う、ジクロロキナクリドンの製造例を示す。
常法にしたがい、ポリリン酸150部に2,5-ジアニリノテレフタル酸10部を加えて、125℃で3時間撹拌して閉環し、無置換キナクリドンのポリリン酸溶液を得た。次いで、50℃に温度を下げてトリクロロイソシアヌル酸4.5部を加え、同温度で2時間撹拌した。このとき、トリクロロイソシアヌル酸の量は、使用したキナクリドンに対して0.67倍モル、有効塩素基準では2.0モル当量である。反応液を50℃の水600部に注ぎ入れ、濾過、温水洗浄、1%水酸化ナトリウム水溶液洗浄、温水洗浄の順で処理をし、その後、乾燥して塩素化キナクリドン11.5部を得た(収率96%)。この塩素化キナクリドンは、塩素原子の置換数が2.0個で、実施例21と同一組成の化合物であった。
次に、本発明の製造方法による塩素化キナクリドンを溶剤で処理して顔料に仕上げた製造例を示す。
N,N-ジメチルホルムアミド2000部に、上記実施例21で得られた塩素化キナクリドン100部を加え、120~140℃で3時間撹拌して、濾過、水洗浄、乾燥して顔料に仕上げた塩素化キナクリドンを得た。
この顔料に仕上げた塩素化キナクリドンを電子顕微鏡で観察したところ、顔料粒子の平均粒径は0.025μmであった。後述する比較例11の従来の製造方法による塩素化キナクリドンも同様に電子顕微鏡で観察したところ、顔料粒子の平均粒径は0.034μmであり、本発明による塩素化キナクリドンの方が微細であった。また、比較例11の塩素化キナクリドンは全てジクロロキナクリドンであるの対して、本発明による塩素化キナクリドンは、モノクロロキナクリドン、ジクロロキナクリドンおよびトリクロロキナクリドンが1:2:1(モル比)の割合の混合物であるために、結晶性が低下して小さな粒径になったと思われる。
測色は測色計(Spectro Color Meter SE2000、日本電色社製)を用いて、L*値(明度)、h値(色相角度)、C*値(鮮明性)を測定した。ただし、赤色インキに対する白インキの混合割合を徐々に増やしていくとL*値が増大するが、h値も増大、すなわち黄味になるとともに、C*値が低下するので絶対的な評価は難しい。そこでL*値が一定値になるように白インキの混合割合を調整して測色し、そのときのh値およびC*値で色調を評価した。なお、着色力は白インキの混合割合の逆数を採用した。
表6は評価結果で、L*値が55のときの数値である。本発明による塩素化キナクリドンは後述する比較例11に対して、色相は大差なかったが、鮮明性が高く、着色力が優れていた。
クロロアニリンを原料に用いた従来の製造方法による塩素化キナクリドンを溶剤で処理して顔料に仕上げた製造例を示す。
98%硫酸1500部にジクロロキナクリドン(シンカシャマゼンタRT、BASF社製)100部を加えて溶解させ、20℃で3時間撹拌した後に、水6000部に撹拌しながら溶解液を注ぎ入れ、70℃に加熱して、濾過、温水洗浄、1%水酸化ナトリウム水溶液洗浄、温水洗浄の順で処理をし、その後、乾燥した。次いで、N,N-ジメチルホルムアミド2000部に加え、120~140℃で3時間撹拌して、濾過、水洗浄、乾燥して顔料に仕上げた塩素化キナクリドンを得た。
実施例21で得られた塩素化キナクリドンに替えて実施例22で得られた塩素化キナクリドンを用いて、実施例38と同一の操作を行い、顔料に仕上げた塩素化キナクリドンを得た。
この顔料に仕上げた塩素化キナクリドンを、X線回折測定装置(MiniFlexII、リガク社製)を用いて、X線回折測定を行った。主ピークはCuKα線のブラッグ角度が、6.2°、13.2°、24.0°、26.4°であって、米国特許3160510号公報の表3に記載の固溶体とほぼ一致したピークであった。また、顔料に仕上げる前の実施例22の塩素化キナクリドンをX線回折測定すると、その主ピークのブラッグ角度は上記と全く同一であった。この塩素化キナクリドンの塩素置換数は0.8個であって、分析の結果、約35%の無置換キナクリドンが含まれていたが、α型やγ型の無置換キナクリドンがX線回折測定で検出されなかったことから、固溶体を形成していることが確認できた。さらに、溶剤処理前後でX線回折のピークに変化が認められなかったことから、安定な結晶を持つ固溶体であることが確認できた。
実施例21で得られた塩素化キナクリドンに替えて実施例23で得られた塩素化キナクリドンを用いて、実施例38と同一の操作を行い、顔料に仕上げた塩素化キナクリドンを得た。
この顔料に仕上げた塩素化キナクリドンの電子顕微鏡観察による粒子の平均粒径は0.14μmであった。後述する比較例12は、塩素化されていない無置換キナクリドンを実施例23に準じて硫酸処理した後に実施例38と同一の操作を行って顔料に仕上げたものであって、電子顕微鏡観察による粒子の平均粒径は0.36μmであった。すなわち、本発明による顔料に仕上げた塩素化キナクリドンは塩素置換数が0.2個であって、分析の結果、その大部分が塩素が置換されていない無置換キナクリドンであったが、少量含まれる塩素化キナクリドンの存在によって粒子が効果的に微細化されていることが確認できた。
次に、実施例38と同様に、オフセットインキを作製して色調を評価した結果を表7に示す。
本発明による塩素化キナクリドンは後述する比較例12に対して、色相は大差なかったが、鮮明性が高く、着色力が優れていた。すなわち、本発明の製造方法によりキナクリドンを僅かに塩素化することで、塩素化前のキナクリドンの本質的な物性を保ちながら、優れた色調に調製することができた。
無置換キナクリドンを硫酸処理後に溶剤で処理して顔料に仕上げた製造例を示す。
98%硫酸150部に無置換キナクリドン(シンカシャレッドY、BASF社製)10部を加えて溶解させ、20℃で3時間撹拌した後に、水600部に撹拌しながら溶解液を注ぎ入れ、70℃に加熱して、濾過、温水洗浄、1%水酸化ナトリウム水溶液洗浄、温水洗浄の順で処理をし、その後、乾燥した。次いで、N,N-ジメチルホルムアミド200部に加え、120~140℃で3時間撹拌して、濾過、水洗浄、乾燥して顔料に仕上げた無置換キナクリドンを得た。
本発明の塩素化キナクリドンおよびビヒクル成分を含む着色組成物の例としてカラートナーの利用例を示す。
実施例38で得られた塩素化キナクリドン50部およびポリエステル樹脂(特開2012-198438号公報の実施例1に記載のポリエステル樹脂A)50部を加圧ニーダーを用いて120℃で混合し、次いで3本ロールを用いて95℃で混練して着色組成物を得た。この着色組成物10部、ポリエステル樹脂(特開2012-198438号公報の実施例1に記載のポリエステル樹脂A)87.5部、荷電制御剤(3,5-ジ-tert-ブチルサリチル酸カルシウム塩)1部および離型剤(エチレンホモポリマー、重量平均分子量850、分散度1.08、融点107℃)1.5部をヘンシェルミキサーで混合した後に、二軸混練押出機を用いて120℃で溶融混練し、次いで粉砕機で粉砕し、分級して平均粒径が5~10μmの微細なトナー母粒子を得た。さらに、疎水性酸化チタン(STT-30A、チタン工業社製)0.5部を加えて混合して、カラートナーAを得た。
これらのカラートナーを熱プレスにより溶融させてガラス板上に均一な薄層を作製し、目視で透明性を評価したところ、カラートナーAはカラートナーBよりも透明性が高かった。
また、これらのカラートナー6部およびキャリアとして平均粒径が60μmのシリコーンレジンでコーティングされたフェライトキャリア(DFC-350C、同和鉄粉社製)100部を混合して現像剤を作製し、複写機(CLC-730、キャノン社製)を用いて、コピー用紙(カラーアプリケーション用紙 Ncolor127、A4サイズ、127g/m2、富士ゼロックス社製)に画像を印刷して印刷物を作製した。これらの印刷物を、目視で評価したところ、カラートナーAを用いて作製した印刷物は、カラートナーBを用いて作製した印刷物よりも、鮮明性が優れ、高濃度であった。
本発明の塩素化キナクリドンおよびビヒクル成分を含む着色組成物の例としてインクジェットインキの利用例を示す。
実施例38で得られた塩素化キナクリドン19部と、スチレン-アクリル酸共重合体(ジョンクリル61J、重量平均分子量10000、酸価195mgKOH/g、固形分31%、BASF社製)16.4部と、非イオン界面活性剤(ポリオキシエチレンジスチレン化フェニルエーテル、エマルゲンA-90、花王社製)5部と、イオン交換水59.6部とを混合し、ジルコニアビーズ(直径0.5mmφ)を加えてペイントシェーカーで12時間分散して、濃縮液を作製した。この濃縮液12.5部と、スチレン-アクリル酸共重合体(エマポリーTYN-40、固形分44.8%、岐阜セラツク製造所社製)2.5部と、非イオン界面活性剤(ポリオキシエチレンジスチレン化フェニルエーテル、エマルゲンA-90、花王社製)2.0部と、イオン交換水64.9部とを混合し、ジエチレングリコールモノブチルエーテルを適宜加えて、粘度が2.5cps(E型粘度計による25℃での値)、表面張力40dyne/cmに調整後、1.0μmメンブランフィルターを用いてろ過し、更に0.45μmメンブランフィルターを用いてろ過して、インクジェットインキAを作製した。
本発明の塩素化キナクリドンおよびビヒクル成分を含む着色組成物の例としてカラーフィルタレジストインキの利用例を示す。
実施例38で得られた塩素化キナクリドン10.5部と、分散助剤として実施例35で製造した塩素化キナクリドン1.5部と、アクリル樹脂溶液(特開2013-120309号公報の実施例に記載のアクリル樹脂溶液1)23部と、分散剤としてアジスパーPB821(味の素ファインテクノ社製)3.6部と、プロピレングリコールモノメチルエーテルアセテート61.4部とを混合し、ジルコニアビーズ(直径0.1mmφ)を加えてピコミル(浅田鉄工社製)で8時間分散して、濃縮液を作製した。
これとは別に、実施例38で得られた塩素化キナクリドンに替えて、比較例11で得られた塩素化キナクリドンを使用した以外は、同様の操作を行い、カラーフィルタレジストインキBを得た。
得られたカラーフィルタの評価は、コントラスト比の数値で判断した。コントラスト比は、2枚の偏光板にカラーフィルタを挟み込み、色彩輝度計(BM-5A、トプコン社製)を用いて輝度を測定し、偏光板が平行のときの輝度を偏光板が直行のときの輝度で除算して算出した。
その結果、カラーフィルタレジストインキAによるカラーフィルタのコントラスト比は3500、カラーフィルタレジストインキBによるカラーフィルタのコントラスト比は1700であって、カラーフィルタレジストインキAの方が優れていた。
Claims (14)
- ハロゲン化有機顔料の製造方法であって、
有機顔料をハロゲン化剤でハロゲン化するハロゲン化工程を含み、
前記ハロゲン化剤が、トリクロロイソシアヌル酸、ジクロロイソシアヌル酸金属塩、トリブロモイソシアヌル酸およびジブロモイソシアヌル酸金属塩からなる群より選ばれる一種以上のN-ハロイミド化合物を含む、ハロゲン化有機顔料の製造方法。 - 前記N-ハロイミド化合物が、トリクロロイソシアヌル酸およびジクロロイソシアヌル酸ナトリウムからなる群より選ばれる一種以上のN-クロロイミド化合物を含む請求項1に記載のハロゲン化有機顔料の製造方法。
- 前記ハロゲン化工程が溶媒存在下で行われ、前記溶媒が強酸および共融塩の少なくともいずれかを含む請求項1または2に記載のハロゲン化有機顔料の製造方法。
- 前記強酸が、硫酸、発煙硫酸、クロロスルホン酸、ポリリン酸およびメタンスルホン酸からなる群より選ばれる一種以上を含む請求項3に記載のハロゲン化有機顔料の製造方法。
- 前記共融塩が、塩化アルミニウムおよび塩化ナトリウムの共融塩である請求項3または4に記載のハロゲン化有機顔料の製造方法。
- 前記有機顔料が、キナクリドン系顔料、フタロシアニン系顔料、アントラキノン系顔料、キノフタロン系顔料、ペリレン系顔料、イソインドリノン系顔料、ジオキサジン系顔料およびインダンスロン系顔料からなる群より選ばれる少なくともいずれかを含む請求項1~5のいずれか一項に記載のハロゲン化有機顔料の製造方法。
- 前記キナクリドン系顔料が、下記式Iで示されるキナクリドン化合物を含む請求項6に記載のハロゲン化有機顔料の製造方法。
- 請求項1~7のいずれか一項に記載のハロゲン化有機顔料の製造方法により得られるハロゲン化有機顔料。
- 請求項8に記載のハロゲン化有機顔料およびビヒクル成分を含む着色組成物。
- 請求項9に記載の着色組成物を含むカラートナー。
- 請求項9に記載の着色組成物を含むインクジェットインキ。
- 請求項9に記載の着色組成物を含むカラーフィルタレジストインキ。
- 請求項10に記載のカラートナーまたは請求項11に記載のインクジェットインキを用いて印刷される印刷物。
- 請求項12に記載のカラーフィルタレジストインキを用いて形成されるフィルタセグメントを具備するカラーフィルタ。
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KR1020217001075A KR102322272B1 (ko) | 2013-08-05 | 2014-03-25 | 할로겐화 유기안료의 제조방법, 그 제조방법에 의해 얻어지는 할로겐화 유기안료 및 이것을 포함하는 착색 조성물 |
CN201480043915.9A CN105452389B (zh) | 2013-08-05 | 2014-03-25 | 卤化有机颜料的制造方法、通过该制造方法获得的卤化有机颜料以及包含该卤化有机颜料的着色组合物 |
US14/910,579 US10155867B2 (en) | 2013-08-05 | 2014-03-25 | Method for producing halogenated organic pigment, halogenated organic pigment obtained by the production method, and colored composition comprising the same |
EP14835310.5A EP3031866B1 (en) | 2013-08-05 | 2014-03-25 | Method for producing halogenated organic pigment, halogenated organic pigment produced by said production method, and colored composition containing said halogenated organic pigment |
KR1020167003072A KR20160039620A (ko) | 2013-08-05 | 2014-03-25 | 할로겐화 유기안료의 제조방법, 그 제조방법에 의해 얻어지는 할로겐화 유기안료 및 이것을 포함하는 착색 조성물 |
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JP2014060231A JP6402464B2 (ja) | 2014-03-24 | 2014-03-24 | ハロゲン化有機顔料の製造方法、その製造方法により得られるハロゲン化有機顔料およびそれを含む着色組成物 |
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KR20180036218A (ko) * | 2016-09-30 | 2018-04-09 | 엘지디스플레이 주식회사 | 착색제, 이를 포함하는 착색 수지 조성물 및 컬러필터 |
US20180314176A1 (en) * | 2017-04-28 | 2018-11-01 | Canon Kabushiki Kaisha | Toner and toner manufacturing method |
US11059983B2 (en) * | 2018-02-09 | 2021-07-13 | Ricoh Company, Ltd. | Ink, ink container, inkjet recording device, and recording method |
WO2020206345A1 (en) * | 2019-04-04 | 2020-10-08 | The Texas A & M University System | Enhancement of polymer mechanical properties using quinacridone additives |
EP3984973A4 (en) * | 2019-06-14 | 2022-07-27 | Sumitomo Electric Industries, Ltd. | COMPOSITION OF RESIN, OPTICAL FIBER AND METHOD FOR MANUFACTURING OPTICAL FIBER |
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CN105452389B (zh) | 2018-03-13 |
KR102322272B1 (ko) | 2021-11-08 |
CN105452389A (zh) | 2016-03-30 |
KR20210008161A (ko) | 2021-01-20 |
US10155867B2 (en) | 2018-12-18 |
EP3031866A1 (en) | 2016-06-15 |
KR20160039620A (ko) | 2016-04-11 |
EP3031866B1 (en) | 2022-05-04 |
EP3031866A4 (en) | 2017-04-05 |
US20160177100A1 (en) | 2016-06-23 |
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