Quinacridone compound

Abstract

To provide a method for producing a coloring composition that contains a bio-based quinacridone compound usable as a bio-red pigment.SOLUTION: A coloring composition production method for producing a coloring composition, which contains a dispersion medium and a quinacridone-based red pigment composition containing a quinacridone compound. The quinacridone compound contains a radioactive carbon atom 14C, has a pMC (percent modern carbon) of 50% or more, and is represented by the formula (B-2) in the figure. The quinacridone compound is synthesized using bio-4-aminobenzoic acid and bio-succinic acid as raw materials.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to quinacridone compounds, compositions containing the compounds, and methods for making the compounds. [Background technology]

[0002] Quinacridone is an important red pigment in our daily lives due to its strong structure and excellent lightfastness and weather resistance, which is why it is widely used in automotive paints, decorative paints, GI coatings, plastics, inks, etc. A method for producing a dichloroquinacridone pigment having a quinacridone structure has been disclosed (see Patent Document 1). In the conventional synthesis of quinacridone, the main raw materials are benzene and butane, which are derived from fossil resources. In recent years, the global trend has shifted toward a focus on sustainable development. Reducing CO2 emissions is an important issue, as is the shift from petroleum-derived raw materials to bio-based raw materials. Furthermore, there is growing emphasis on replacing toxic chemicals with less toxic alternatives. Quinacridone red pigments currently being produced are not satisfactory in view of future demands for environmental issues, and there is a strong demand for bio-derived quinacridone red pigments from the standpoints of clean, green, and carbon neutrality. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-197630 Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention aims to provide a bio-derived quinacridone compound that can be used as a bio-red pigment and that can be obtained through a safe, clean, green, and carbon-neutral approach, and a composition containing the compound. [Means for solving the problem]

[0005] As a result of investigations aimed at solving the above-mentioned problems, the present inventors discovered that a bio-derived quinacridone compound that can be used as a red pigment can be obtained by using bio-4-aminobenzoic acid (4-aminobenzoic acid is also abbreviated as "PABA" in this specification) and biosuccinic acid as raw materials to derive a secondary bio-based raw material or a bio-intermediate, and then subjecting the secondary bio-based raw material or the bio-intermediate to a coupling reaction, dehydration, or ring-closure reaction, thereby completing the present invention.

[0006] That is, the present invention includes the following aspects. [1] Radioactive carbon atoms 14 A quinacridone compound containing C and having a structure represented by the following formula (B): [ka] (In formula (B), X's each independently represent -Cl, -F, -Br, -I, -OH, -NO2, a C1-C12 alkyl group, a C1-C12 alkoxy group, a phenyl group, -COOH, -COO-C1-C12 alkyl, or -CO-NR. Each R independently represents a hydrogen atom, an alkyl group, an alkenyl group, or a phenyl group. Each n's independently represent 1 or 2.) [2] The quinacridone compound according to [1], wherein the quinacridone compound having the structure represented by formula (B) is a quinacridone compound represented by the following formula (B-1) or (B-2): [ka] [ka] (In formula (B-2), T is Cl, CH3, or COOH) [3] A composition containing the quinacridone compound according to [1] or [2]. [4] The composition according to [3], which is used as a pigment composition. [5] The composition according to [3] or [4], wherein the proportion of the quinacridone compound having the structure represented by (B) in the composition is 70 mass % or more. [6] A coloring composition comprising the composition according to [3] or [4] and a dispersion medium. [7] The colored composition according to [6], wherein the proportion of the diketopyrrolopyrrole compound having the structure represented by (B) in the colored composition is 0.5% by mass to 50% by mass. [8] Radioactive carbon atoms 14 A method for producing a quinacridone compound containing C and having a structure represented by the following formula (B), [ka] (In formula (B), X's each independently represent -Cl, -F, -Br, -I, -OH, -NO2, a C1-C12 alkyl group, a C1-C12 alkoxy group, a phenyl group, -COOH, -COO-C1-C12 alkyl, or -CO-NR. Each R independently represents a hydrogen atom, an alkyl group, an alkenyl group, or a phenyl group. Each n's independently represent 1 or 2.) (Bi) 4-aminobenzoic acid is used as a raw material to produce an aniline which may have a substituent; (B-ii) Using succinic acid as a raw material, dimethyl 2,5-dihydroxycyclohexa-1,4-dicarboxylate is produced, However, at least one of the 4-aminobenzoic acid (Bi) and the succinic acid (B-ii) is bio-derived, (B-iii) A method for producing a quinacridone compound, comprising reacting the optionally substituted aniline produced in (Bi) with the dimethyl 2,5-dihydroxycyclohexa-1,4-dicarboxylate produced in (B-ii) to produce a quinacridone compound having a structure represented by formula (B). [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a bio-derived quinacridone compound that can be used as a bio-red pigment and that can be obtained through a safe, clean, green, and carbon-neutral approach, and a composition containing the compound. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a schematic diagram illustrating a process for producing a bio-derived quinacridone compound. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present invention will be described in detail below. Note that the following explanation of the constituent elements is an example for explaining the present invention, and the present invention is not limited to these contents.

[0010] (Radioactive carbon atoms 14 A quinacridone compound containing C and having a structure represented by the following formula (B): The quinacridone compound of the present invention contains a radioactive carbon atom. 14 Contains C. The quinacridone compound of the present invention has a structure represented by the following formula (B).

[0011] [ka]

[0012] In formula (B), X's each independently represent -Cl, -F, -Br, -I, -OH, -NO2, a C1-C12 alkyl group, a C1-C12 alkoxy group, a phenyl group, -COOH, -COO-C1-C12 alkyl, or -CO-NR. Each R independently represents a hydrogen atom, an alkyl group, an alkenyl group, or a phenyl group. Each n's independently represent 1 or 2.

[0013] The quinacridone compound of the present invention can be produced by using bio-derived 4-aminobenzoic acid and bio-derived succinic acid as raw materials, and reacting an optionally substituted aniline produced using the bio-derived 4-aminobenzoic acid with dimethyl 2,5-dihydroxycyclohexa-1,4-dicarboxylate produced using the bio-derived succinic acid. The quinacridone compound of the present invention contains a bio (biomass) component derived from a biomaterial. The fact that the quinacridone compound of the present invention contains a biocomponent can be explained by, for example, the presence of a radioactive carbon atom. 14 This can be confirmed by measuring C.

[0014] For example, compounds and compositions derived from living organisms and those derived from petroleum do not differ in physical properties such as molecular weight, mechanical properties, or thermal properties. To distinguish between them, the biomass ratio is generally used. In this biomass ratio, the carbon in petroleum-derived compounds and compositions has the following characteristics: 14 Since it does not contain C (radioactive carbon 14, half-life 5730 years), 14 By measuring the C concentration using accelerator mass spectrometry, it is possible to determine whether the compounds or compositions produced are petroleum-derived or bio-derived compounds.

[0015] This biomass degree can be measured, for example, by burning a sample to be measured to generate carbon dioxide, which is then purified in a vacuum line and reduced with hydrogen using iron as a catalyst to generate graphite. This graphite was then used in a tandem accelerator-based 14 Attach it to the C-AMS dedicated device (manufactured by NEC) 14Counting C, 13 The concentration of C ( 13 C / 12 C). 14 The concentration of C ( 14 C / 12 C) is measured, and the carbon content of the sample is compared to the standard modern carbon. 14 It can be determined by calculating the percentage of C concentration. For the measurement, oxalic acid (HOxII) provided by the National Institute of Standards (NIST) can be used as a standard sample.

[0016] One index for evaluating the degree of biomass is, for example, percent modern carbon (pMC). Here, pMC (percent modern carbon) can be calculated by measurement according to ASTM-D6866-18, and is the percentage of standard modern carbon. 14 C concentration in the target 14 It represents the percentage of C concentration. 14 If C is not contained, the pMC will be 0%.

[0017] Preferred embodiments of the quinacridone compound having the structure represented by formula (B) include, for example, quinacridone compounds represented by the following formula (B-1) or (B-2).

[0018] [ka]

[0019] [ka] (In formula (B-2), T is Cl, CH3, or COOH)

[0020] The pMC (percent modern carbon) of the quinacridone compound represented by formula (B-1) or the quinacridone compound represented by formula (B-2) is preferably 1% or more, more preferably 20% or more, more preferably 30% or more, more preferably 50% or more, more preferably 75% or more, more preferably 90% or more, and even more preferably 99% or more.

[0021] The quinacridone compound represented by (B-1) is a compound known to constitute the pigment Pigment Violet 19 (PV19), and the quinacridone compound represented by (B-2) is a compound known to constitute the pigment Pigment Red 202 (PR202).

[0022] The quinacridone compound of the present invention having a structure represented by formula (B), or a composition containing the quinacridone compound, is 14 It is used as a quinacridone red pigment containing C, i.e., containing bio-components.

[0023] (Method for producing a quinacridone compound having a structure represented by formula (B)) radioactive carbon atoms 14 The quinacridone compound of the present invention having a structure represented by formula (B) containing C, i.e., containing a biocomponent, is (Bi) 4-aminobenzoic acid is used as a raw material to produce an aniline which may have a substituent; (B-ii) Using succinic acid as a raw material, dimethyl 2,5-dihydroxycyclohexa-1,4-dicarboxylate is produced, However, at least one of the 4-aminobenzoic acid (Bi) and the succinic acid (B-ii) is bio-derived, (B-iii) It can be obtained by reacting the optionally substituted aniline produced in (Bi) with the dimethyl 2,5-dihydroxycyclohexa-1,4-dicarboxylate produced in (B-ii).

[0024] The raw materials, 4-aminobenzoic acid and succinic acid, can be derived from biomass fermentation, plant extraction, or biomass pyrolysis.

[0025] Traditional quinacridone synthesis typically relies on fossil-based benzene and butane, but benzene is toxic to humans and harmful to the environment. Additionally, traditional synthesis methods use petroleum-based feedstocks, which do not contribute to carbon neutral programs. Furthermore, when aniline, which is used in the synthesis of quinacridone, is synthesized from benzene, it is necessary to nitrate benzene with a mixture of concentrated acids (nitric acid and sulfuric acid), and then heat the nitrobenzene to 200 to 300°C to hydrogenate it, which imposes strict manufacturing conditions. On the other hand, the method for synthesizing quinacridone compounds disclosed in the present invention can use plant-derived raw materials as raw materials, and at least one of the raw materials, 4-aminobenzoic acid and succinic acid, is bio-derived bio-4-aminobenzoic acid or bio-succinic acid, thereby contributing to a carbon-neutral approach. In the present invention, 4-aminobenzoic acid and succinic acid are used as raw materials to synthesize quinacridone compounds. Synthesizing quinacridone compounds using 4-aminobenzoic acid and succinic acid as starting materials is a new approach that has not been taken before.

[0026] The quinacridone compound containing the bio-component of the present invention, which is produced using bio-4-aminobenzoic acid or bio-succinic acid as a raw material, has a crystal structure and particle size that are favorable for pigment production.

[0027] A preferred embodiment of the method for producing a quinacridone compound having a structure represented by formula (B) is a method for producing a quinacridone compound, particularly a quinacridone compound represented by formula (B-1) or a quinacridone compound represented by formula (B-2).

[0028] <Method for producing a quinacridone compound having a structure represented by formula (B-1)> First, a method for producing a quinacridone compound represented by formula (B-1) will be described below (in the present specification, when the method for producing each compound is described, reference will also be made to the schematic diagram in FIG. 1). Note that the production method described below will be described in the case where both 4-aminobenzoic acid and succinic acid are bio-derived as raw materials.

[0029] (B-ia) Aniline is produced using bio-derived 4-aminobenzoic acid as a raw material (step (G) below). Aniline can be produced from 4-aminobenzoic acid using, for example, the methods described in JP2013-230913A, JP2016-222575A, etc. For example, it can be produced by the method described in the examples below.

[0030] [ka] In the above step (G), aniline is produced from 4-aminobenzoic acid. In step (G), the reaction may be carried out in a nitrogen atmosphere or in the ambient environment, i.e., in an air atmosphere, but a nitrogen atmosphere is preferred to prevent oxidation of the product. The heating temperature is preferably 170 to 250°C, more preferably 180 to 230°C, and even more preferably 190 to 210°C.

[0031] (B-iia) Bio-derived succinic acid is used as a raw material to obtain dimethyl succinate (also abbreviated as "DMS" in this specification) (Step (J) below), and then dimethyl 2,5-dihydroxycyclohexa-1,4-dicarboxylate (also abbreviated as "DMSS" in this specification) is produced (Step (K) below). Dimethyl 2,5-dihydroxycyclohexa-1,4-dicarboxylate can be produced from succinic acid using methods described in Chemistry-A European Journal (2020), 26 (65), 14963-14968, Journal of Polymer Science, Part A: Polymer Chemistry (2017), 55 (14), 2365-2372, CN102050738A, etc. For example, it can be produced by the method described in the examples below.

[0032] [ka] In the above step (J), dimethyl succinate is produced from succinic acid. Examples of the catalytic acid that can be used in step (J) include hydrochloric acid, sulfuric acid, formic acid, acetic acid, methanesulfonic acid, p-toluenesulfonic acid, etc. Among these, hydrochloric acid and sulfuric acid are preferred from the viewpoint of cost. In the above step (K), dimethyl 2,5-dihydroxycyclohexa-1,4-dicarboxylate (DMSS) is produced from dimethyl succinate. In step (K), the dimerization temperature of dimethyl succinate is preferably 100 to 150° C., more preferably 120 to 130° C. Examples of dimerization reagents include sodium methoxide, potassium methoxide, sodium tert-butoxide, potassium tert-butoxide, sodium hydride, potassium hydride, etc. Among these, sodium methoxide is preferred from the viewpoint of cost and ease of handling.

[0033] (B-iiia) The aniline produced in (B-ia) above is reacted with the dimethyl 2,5-dihydroxycyclohexa-1,4-dicarboxylate produced in (B-iia) above to produce a quinacridone compound represented by formula (B-1) (step (O) below). The reaction method for reacting aniline with dimethyl 2,5-dihydroxycyclohexa-1,4-dicarboxylate is not particularly limited, and can be produced using the methods described in US20190177547A1, WO2005085364A1, etc. For example, it can be produced by the method described in the examples below.

[0034] [ka] In the above step (O), aniline is reacted with dimethyl 2,5-dihydroxycyclohexa-1,4-dicarboxylate to produce a quinacridone compound (PV19 pigment) represented by formula (B-1). In step (O), examples of acids required for synthesis include hydrochloric acid, sulfuric acid, formic acid, acetic acid, methanesulfonic acid, and p-toluenesulfonic acid. Examples of solvents include methanol, ethanol, isopropyl alcohol, butanol, and dodecyl alcohol. These alcohols can be used singly or in combination of two or more, but it is more preferable to use a combination of two or more alcohols. The mixing ratio of the solvents is preferably in the range of 1:0 to 0:1, more preferably 5:1 to 1:5, and even more preferably 2:1 to 1:2. The reaction time is preferably 1 to 12 hours, more preferably 2 to 10 hours, and even more preferably 3 to 8 hours. In the oxidation process, hydrochloric acid, sulfuric acid, formic acid, acetic acid, methanesulfonic acid, and p-toluenesulfonic acid are used. The reaction time is preferably 1 to 12 hours, more preferably 2 to 10 hours, and even more preferably 3 to 8 hours. In the cyclization process (condensation cyclization reaction), the reaction temperature is preferably 100 to 200°C, more preferably 110 to 180°C, and even more preferably 120 to 150°C. The reaction time is preferably 1 to 8 hours, more preferably 2 to 6 hours, and even more preferably 3 to 5 hours. The concentration of polyphosphoric acid used in the cyclization process is preferably 100% or more, more preferably 105% or more, and even more preferably 115% or more.

[0035] <Method for producing a quinacridone compound having a structure represented by formula (B-2)> Next, a method for producing the quinacridone compound represented by formula (B-2) will be described below (see also the schematic diagram in FIG. 1). In the following, an example where T in (B-2) is Cl will be described.

[0036] (B-ib) Bio-derived 4-aminobenzoic acid is used as a raw material to obtain 4-chlorobenzoic acid (Step (C) below), which is then converted to 4-chlorobenzamide (Step (E) below), from which 4-chloroaniline is produced (Step (F) below). 4-Chloroaniline can be produced from 4-aminobenzoic acid by, for example, the method described in the Examples below.

[0037] [ka] In the above step (C), the Sandmeyer reaction is used to produce, for example, 4-chlorobenzoic acid from 4-aminobenzoic acid. Examples of acids used in step (C) include hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid, and methanesulfonic acid. Among these, hydrochloric acid, sulfuric acid, and acetic acid are more preferred from the standpoint of cost. Usable solvents include water, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylformamide, toluene, xylene, and alkylbenzene. Sodium hydroxide is used to increase the dissolution rate of p-aminobenzoic acid, but the reaction can be carried out without sodium hydroxide. The diazotization reaction time is preferably 5 minutes to 4 hours, more preferably 20 minutes to 3 hours, and even more preferably 30 minutes to 2 hours. To exchange the azo group for a chloro group in the final stage, examples of chloro sources include potassium chloride, lithium chloride, cuprous chloride, cupric chloride, tetraethylammonium trichloride, tetrabutylammonium trichloride, N-chlorosuccinimide, and trimethylsilyl chloride. Among these, potassium chloride, lithium chloride, cuprous chloride, cupric chloride, and N-chlorosuccinimide are preferred from the standpoint of ease of handling. In the above step (E), 4-chlorobenzamide is produced from 4-chlorobenzoic acid. In step (E), ammonia sources include ammonia gas, aqueous ammonia, and urea. Among these, urea is preferred for its ease of handling. Molybdenum is used as a catalyst to increase the reaction rate, but the reaction is possible without molybdenum. A high-boiling point solvent such as alkylbenzene can be used for the synthesis, but the reaction will proceed even without a solvent. The reaction temperature is preferably 100 to 180°C, more preferably 130 to 150°C, and even more preferably 120 to 160°C. The appropriate heating time is preferably 1 to 6 hours, more preferably 2 to 4 hours. In the above step (F), a Hofmann elimination reaction is used to produce, for example, 4-chloroaniline from 4-chlorobenzamide. In step (F), the reaction solvent is a mixture of water and acetonitrile, and the proportion of acetonitrile is preferably greater than 0 and less than 100%, more preferably 20 to 80%, and even more preferably 30 to 70%. Reagents that induce the Hoffmann reaction include trichloroisocyanuric acid, tribromoisocyanuric acid, and triiodoisocyanuric acid. Among these, trichloroisocyanuric acid and tribromoisocyanuric acid are preferred due to their ease of availability. The reaction time for the Hoffmann reaction is preferably 30 minutes to 3 hours, more preferably 1 to 2 hours. The heating time required for decomposing the carbamic acid is preferably 5 minutes to 3 hours, more preferably 10 minutes to 2 hours, and even more preferably 30 minutes to 1 hour.

[0038] As another embodiment of the above (B-ib), for example, 4-Chloroaniline may also be obtained by using bio-derived 4-aminobenzoic acid as a raw material to obtain aniline (step (G) below), and then producing 4-chloroaniline (step (H) below).

[0039] [ka] The above step (G) is as explained for step (G) in the section <Method for producing a quinacridone compound having a structure represented by formula (B-1)> above. In the above step (H), 4-chloroaniline is produced from aniline. In step (H), the copper chloride and lithium chloride may be anhydrous or may contain one or two crystal waters. Examples of the solvent include methanol, ethanol, isopropyl alcohol, and butanol. The reaction time is preferably 3 to 24 hours, more preferably 5 to 20 hours, even more preferably 8 to 15 hours, and particularly preferably 10 to 12 hours.

[0040] (B-iib) Bio-derived succinic acid is used as a raw material to obtain dimethyl succinate (step (J) below), and then dimethyl 2,5-dihydroxycyclohexa-1,4-dicarboxylate (DMSS) is produced (step (K) below). Dimethyl 2,5-dihydroxycyclohexa-1,4-dicarboxylate (DMSS) can be produced from succinic acid using the same method as described in (B-iia) above, or by the method described in the Examples below.

[0041] [ka]

[0042] (B-iiib) The 4-chloroaniline produced in (B-ib) above is reacted with the dimethyl 2,5-dihydroxycyclohexa-1,4-dicarboxylate produced in (B-iib) above to produce a quinacridone compound represented by formula (B-2) (step (N) below). The reaction method for reacting 4-chloroaniline with dimethyl 2,5-dihydroxycyclohexa-1,4-dicarboxylate can be the same as that described in (B-iiia) above, for example, by the method described in the Examples below.

[0043] [ka] In the above step (N), 4-chloroaniline and dimethyl 2,5-dihydroxycyclohexa-1,4-dicarboxylate are reacted using a method similar to that described in the above (B-iiia) to produce a quinacridone compound (PR202 pigment) represented by formula (B-2) in which T is Cl.

[0044] As described above, the 4-aminobenzoic acid used as a raw material is preferably derived from biomass, and the succinic acid used as a raw material is also preferably derived from biomass, as described above. It is more preferable that both the 4-aminobenzoic acid and the succinic acid are derived from biomass.

[0045] The biomass content of the raw materials used in the above manufacturing method is preferably 1% or more, more preferably 50% or more, more preferably 75% or more, more preferably 90% or more, and even more preferably 99% or more. Furthermore, if biomass raw materials are available using the mass balance method or the book and claim method, it is easier to achieve a biomass content of 1% or more up to 100%. This patent covers biomass contents including biomass raw materials using the mass balance method and the book and claim method.

[0046] (Quinacridone Compound-Containing Composition) The present invention may be a composition containing the quinacridone compound of the present invention having a structure represented by formula (B). The composition is preferably used as a pigment composition, particularly as a quinacridone red pigment. The composition of the present invention may contain, for example, one or more quinacridone compounds having a structure represented by formula (B). A more preferred embodiment of the composition of the present invention is, for example, a composition containing a quinacridone compound represented by the above formula (B-1) or a quinacridone compound represented by the above formula (B-2).

[0047] When the composition is a pigment composition, the proportion of the quinacridone compound having the structure represented by formula (B) above (more preferably the proportion of the quinacridone compound represented by formula (B-1) or (B-2) above) in the composition is, for example, preferably 70 mass% or more, more preferably 80 mass% or more, and even more preferably 90 mass% or more.

[0048] The BET value of the composition of the present invention is 20 to 100 m 2 / g is preferred, and 30 to 95m 2 / g is preferred, and 40 to 90m 2 / g is preferred, and 50 to 85m 2 / g is preferred. In particular, for ink applications, 20 to 80 is preferred, for paint applications, 40 to 90 is preferred, for resin applications, 50 to 90 is preferred, and for color filters, 50 to 100 is preferred. The BET value can be measured by weighing 0.1 g of pigment into a measurement cell and setting it in a specific surface area meter (Macsorb 1208).

[0049] (Application of the quinacridone compound of the present invention) A radioactive carbon atom having a structure represented by formula (B) obtained by the above method. 14 The quinacridone compound of the present invention containing C and the composition containing the quinacridone compound constitute quinacridone red pigments such as PV19 and PR202. The quinacridone compound of the present invention contains carbon derived from biomass and is carbon neutral, thereby contributing to reducing the environmental load. The quinacridone compound of the present invention and the quinacridone red pigment comprising a composition containing the quinacridone compound can be used as a coloring composition, a molding composition, or the like. Furthermore, the quinacridone compound of the present invention and the quinacridone red pigment comprising a composition containing the quinacridone compound are mixed with other resins, rubbers, additives, solvents, pigments, dyes, etc., as necessary, and adjusted for use in coating materials for cosmetics, pharmaceuticals, or agricultural chemicals, or printing markers, stationery, writing implements, printing inks, inkjet inks, metal inks, paints, plastic colorants, toners (color toners), color filters, etc.

[0050] <Coloring composition> The coloring composition of the present invention preferably contains a quinacridone red pigment composition comprising the quinacridone compound of the present invention and a composition containing the quinacridone compound, and a dispersion medium. The coloring composition of the present invention preferably contains 0.5% by mass to 50% by mass, more preferably 2.5% by mass to 35% by mass, and even more preferably 5% by mass to 20% by mass of the quinacridone compound having the structure represented by formula (B) above.

[0051] <<Dispersion medium>> Examples of the dispersion medium include resins and solvents. Examples of the resin include resin-type dispersants and binder resins. Examples of the solvent include water and organic solvents. If necessary, a low-molecular-weight dispersant such as a surfactant can be used.

[0052] Examples of types of resins in resin-type dispersants include styrene-(meth)acrylic acid copolymers, (meth)acrylic acid-(meth)acrylic acid alkyl ester copolymers, styrene-(meth)acrylic acid-(meth)acrylic acid alkyl ester copolymers, styrene-α-methylstyrene-(meth)acrylic acid copolymers, styrene-α-methylstyrene-(meth)acrylic acid-(meth)acrylic acid alkyl ester copolymers, poly(meth)acrylic acid, vinylnaphthalene-(meth)acrylic acid copolymers, styrene-maleic acid copolymers, maleic acid-maleic anhydride copolymers, α-olefin-maleic acid (anhydride) copolymers, α-olefin-maleic acid (anhydride)-polyalkylene glycol allyl ether copolymer vinylnaphthalene-maleic acid copolymers, polyester-modified (meth)acrylic acid polymers, and salts thereof. The form of the resin in the resin-type dispersant may be, for example, a water-soluble resin or an emulsion (water-insoluble resin).

[0053] The binder resin may be, for example, a polyolefin resin, a polyester resin, a styrene copolymer, an acrylic resin, or a modified resin thereof. Specific examples include polyolefin resins such as polyethylenes, such as high-density polyethylene (HDPE), linear low-density polyethylene (L-LDPE), and low-density polyethylene (LDPE), and polypropylene; polyester resins, such as polyethylene terephthalate; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene, and the like. styrene copolymers such as styrene-isoprene copolymer and styrene-acrylonitrile-indene copolymer; acrylic resins such as acrylic resin and methacrylic resin; polyvinyl chloride, phenolic resin, naturally modified phenolic resin, natural resin modified maleic acid resin, polyvinyl acetate, silicone resin, polyurethane resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, nitrocellulose resin, polyamide resin, epoxy resin, xylene resin, polyvinyl butyral resin, polyvinyl acetal resin, cellulose ester resin, alkyd resin, rosin resin, ketone resin, cyclized rubber, chlorinated polyolefin resin, terpene resin, coumarone-indene resin, alkyd resin, amino resin, petroleum resin, and modified resins thereof.

[0054] Organic solvents can be classified into water-soluble solvents and water-insoluble solvents. Examples of water-soluble solvents include ethanol, n-propanol, isopropanol, isobutanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and glycerin. Examples of water-insoluble solvents include toluene, xylene, butyl acetate, methyl acetate, methyl ethyl ketone, methyl isobutyl ketone, butyl alcohol, and aliphatic hydrocarbons.

[0055] Each material constituting the coloring composition can be used alone or in combination of two or more kinds.

[0056] <Molding composition> The molding composition contains a coloring composition (pigment composition, resin). The molding composition preferably contains a thermoplastic resin in the resin. The molding composition containing a thermoplastic resin is preferably melted and kneaded, and molded into a desired shape to produce a molded product.

[0057] Examples of thermoplastic resins include homopolymers or copolymers using ethylene, propylene, butylene, styrene, or the like as monomer components. More specifically, examples include polyethylenes such as high-density polyethylene (HDPE), linear low-density polyethylene (L-LDPE), and low-density polyethylene (LDPE), as well as polyolefin resins such as polypropylene and polybutylene. Specific examples of other useful resins include polyester resins such as polyethylene terephthalate, polyamide resins such as nylon 6 and nylon 66, polystyrene resins, and thermoplastic ionomer resins. Among these, polyolefin resins and polyester resins are preferred. The number-average molecular weight of the thermoplastic resin is preferably greater than 30,000 and not greater than 200,000.

[0058] The molding composition may contain wax. Waxes are made of low-molecular-weight polyolefins. These are polymers of olefin monomers such as ethylene, propylene, and butylene, and may be block or random copolymers or terpolymers. Specifically, they are polymers of α-olefins such as low-density polyethylene (LDPE), high-density polyethylene (HDPE), and polypropylene (PP). The number average molecular weight of the wax is preferably 1,000 to 30,000, more preferably 2,000 to 25,000. Within this range, the wax migrates appropriately to the surface of the molded article, resulting in an excellent balance between sliding properties and bleed-out suppression. The melting point of the wax is preferably 60 to 150° C., more preferably 70 to 140° C. If the melting point is within this range, the processability when melt-kneading the thermoplastic resin and wax will be good.

[0059] The molding composition may contain other additives, which are materials commonly used in the technical field of molded articles, such as antioxidants, light stabilizers, dispersants, metal soaps, antistatic agents, flame retardants, lubricants, fillers, and colorants other than the quinacridone compound of the present invention.

[0060] The molding composition can be produced, for example, as a masterbatch containing a high concentration of the quinacridone compound. The masterbatch is preferably prepared by, for example, melt-kneading a thermoplastic resin and a pigment composition, and then molding the mixture into any desired shape for easy use in the next step. The masterbatch is then melt-kneaded with a diluting resin (e.g., the thermoplastic resin used in the masterbatch) to form a molded product of the desired shape. Examples of the masterbatch shape include pellets, powder, and plates. To prevent aggregation of the pigment composition, it is preferable to first melt-knead the pigment composition and wax to produce a dispersion, and then melt-knead this dispersion with the thermoplastic resin to produce the masterbatch. The device used for the dispersion is preferably, for example, a blend mixer or a three-roll mill.

[0061] The molding composition can be used for, for example, plastic molded articles, sheets, films, and the like.

[0062] <Toner> The toner contains a coloring composition (pigment composition, resin). The resin in the toner is called a binder resin, and is preferably a thermoplastic resin. The toner may be a dry toner or a wet toner. For example, a dry toner can be produced by melting and kneading the pigment composition and binder resin, cooling the mixture, and then pulverizing and classifying the mixture. This is followed by a post-processing step in which additives are blended and mixed.

[0063] Examples of binder resins include styrene-p-chlorostyrene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, styrene-(meth)acrylate copolymers, styrene-α-chloromethyl methacrylate copolymers, styrene-acrylonitrile copolymers, styrene-vinyl methyl ether copolymers, styrene-vinyl ethyl ether copolymers, styrene-vinyl methyl ketone copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-acrylonitrile-indene copolymers, polyvinyl chloride, phenolic resins, naturally modified phenolic resins, naturally resin-modified maleic acid resins, (meth)acrylic resins, polyvinyl acetate, silicone resins, polyester resins, polyurethanes, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, coumarone-indene resins, and petroleum-based resins.

[0064] Among these, polyester resins and styrene copolymers are preferred, and polyester resins are more preferred. The pigment composition has particularly excellent compatibility with polyester resins, allowing the quinacridone compound to be uniformly and finely dispersed in the toner, thereby producing a high-quality toner.

[0065] The weight average molecular weight (Mw) of the polyester resin is preferably 5,000 or more, more preferably 10,000 to 1,000,000, and even more preferably 20,000 to 100,000. When a polyester resin with an appropriate Mw is used, a toner having good offset resistance and low-temperature fixability can be obtained. The acid value of the polyester resin is preferably 10 to 60 mgKOH / g, more preferably 15 to 55 mgKOH / g. When a polyester resin with an appropriate acid value is used, the release agent is easily prevented from being released, and a decrease in image density in a high-humidity environment is unlikely to occur.

[0066] The toner may further contain a charge control agent. The use of a charge control agent makes it easier to obtain a toner with a stable charge amount. The charge control agent may be selected appropriately from positive and negative charge control agents.

[0067] The toner may contain a release agent, such as hydrocarbon waxes such as polypropylene wax, polyethylene wax, and Fischer-Tropsch wax, synthetic ester waxes, and natural ester waxes such as carnauba wax and rice wax.

[0068] If necessary, lubricants, fluidizing agents, abrasives, conductivity-imparting agents, image peeling prevention agents, etc. may be added to the toner.

[0069] The toner can be used as a one-component developer or a two-component developer. The two-component developer can further contain a carrier. Examples of the carrier include magnetic powders such as iron powder, ferrite powder, and nickel powder, as well as those whose surfaces are coated with resin, etc. Examples of the resin that coats the carrier surface include styrene-(meth)acrylic acid ester copolymers, (meth)acrylic acid ester copolymers, fluorine-containing resins, silicone-containing resins, polyamide resins, ionomer resins, and polyphenylene sulfide resins.

[0070] <Paint> The paint contains a coloring composition (pigment composition, resin, solvent). Examples of the resin include thermosetting resins and thermoplastic resins. The thermosetting resin preferably has a glass transition temperature of 10°C or higher. Examples of the thermosetting resin include acrylic resin, polyester, and polyurethane. The thermosetting resin preferably has a functional group that can react with a curing agent. Examples of the functional group include a carboxyl group and a hydroxyl group. Examples of the curing agent include an isocyanate curing agent, an epoxy curing agent, an aziridine curing agent, and an amine curing agent. The thermoplastic resin is preferably a resin having a glass transition temperature of 30°C or higher. Examples of the thermoplastic resin include nitrocellulose and polyester. The thermosetting resin and the thermoplastic resin can be used in combination.

[0071] Among the solvents, examples of water-insoluble solvents include toluene, xylene, butyl acetate, methyl acetate, methyl ethyl ketone, methyl isobutyl ketone, butyl alcohol, and aliphatic hydrocarbons. Among solvents, examples of water-soluble solvents include water, monohydric alcohols, dihydric alcohols, and glycols. Examples of water-soluble solvents include ethanol, n-propanol, isopropanol, isobutanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and glycerin. Also included are water-dilutable monoethers derived from polyhydric alcohols. Specific examples include methoxypropanol and methoxybutanol. Also included are water-dilutable glycol ethers such as butyl glycol and butyl diglycol. When a paint contains water as a solvent, it is called an aqueous paint.

[0072] The coating material may further contain known additives.

[0073] Examples of uses of the paint include paint for metals and paint for plastics.

[0074] <Printing ink> Printing ink contains a coloring composition (pigment composition, resin, solvent). Printing ink is ink other than inkjet ink, and examples include offset printing ink, flexographic printing ink, gravure printing ink, silk screen printing ink, and color filter ink. When the solvent contains water, it is called aqueous printing ink.

[0075] Examples of the resin include rosin resin, rosin-modified phenolic resin, polyurethane, nitrocellulose, acrylic resin, styrene-acrylic resin, and petroleum resin.

[0076] Examples of the water-insoluble solvents include toluene, xylene, butyl acetate, methyl acetate, methyl ethyl ketone, methyl isobutyl ketone, butyl alcohol, and aliphatic hydrocarbons.

[0077] Examples of water-soluble solvents include ethanol, n-propanol, isopropanol, isobutanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and glycerin. Other examples include water-dilutable monoethers derived from polyhydric alcohols, such as methoxypropanol and methoxybutanol. Other examples include water-dilutable glycol ethers such as butyl glycol and butyl diglycol.

[0078] The printing ink may further contain a lustrous material. The lustrous material is a particle having an average thickness of 0.5 to 10 μm and an average particle diameter of 5 to 50 μm, and examples thereof include metal flakes, mica, and coated glass flakes. Examples of metal flakes include aluminum flakes and gold powder. Examples of mica include ordinary mica and coated mica. Examples of coated glass flakes include glass flakes coated with a metal oxide such as titanium oxide.

[0079] The printing ink may further contain known additives.

[0080] <Inkjet ink> Inkjet inks contain a pigment composition and a resin, and preferably further contain a solvent. Inkjet inks can be broadly classified into (solvent-based) inkjet inks, aqueous inkjet inks, and solvent-free inkjet inks depending on whether or not they contain a solvent and the type of solvent. The following description will focus on aqueous inkjet inks.

[0081] The resin used in aqueous inkjet ink is important for ensuring the ink adheres well to the substrate. Examples of resin types include acrylic resins, styrene-acrylic resins, polyester resins, polyamide resins, and polyurethane resins. Resin forms include water-soluble resins and emulsion particles. Among these, emulsion particles are preferred. Emulsion particles include single-component particles and core-shell particles, and any type can be selected and used. The use of emulsion particles facilitates the reduction of the viscosity of aqueous inkjet inks, making it easy to obtain recorded materials with excellent water resistance. The acidic functional groups of the resin can be neutralized, if necessary, with a pH adjuster such as ammonia, various amines, or various inorganic alkalis.

[0082] Examples of solvents include water-insoluble solvents, water, and water-soluble solvents. Examples of water-soluble solvents include glycol ethers and diols. These solvents penetrate substrates very quickly, even into low-absorbency or non-absorbent substrates such as coated paper, art paper, vinyl chloride sheets, films, and fabrics. This allows for fast drying during printing, resulting in accurate printing. Furthermore, due to their high boiling points, they also function as wetting agents.

[0083] The water-soluble solvent is important for preventing drying and solidification at the nozzle portion of the printer head of the aqueous inkjet ink and for achieving ink ejection stability. Examples of the water-soluble solvent include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, ketone alcohol, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, 1,2-hexanediol, N-methyl-2-pyrrolidone, substituted pyrrolidone, 2,4,6-hexanetriol, tetrafurfuryl alcohol, and 4-methoxy-4-methylpentanone.

[0084] The inkjet ink may further contain additives such as a drying accelerator, a penetrant, a preservative, a chelating agent, and a pH adjuster.

[0085] Inkjet ink is prepared by blending and mixing the various materials. Mixing can be performed using a blade stirrer, various dispersers, emulsifiers, etc. The order in which the materials are added and the mixing method are optional.

[0086] After mixing, the inkjet ink is preferably filtered or centrifuged to remove coarse particles, which improves the ejection properties from the inkjet printer. Filtration and centrifugation can be performed by known methods. Inkjet ink can be used in various inkjet systems, including, for example, charge control systems, continuous jet systems such as spray systems, piezo systems, thermal systems, and electrostatic suction systems. [Example]

[0087] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following examples, "%" in the compositions means "% by mass."

[0088] (composition analysis) The composition of the dye obtained in the examples was analyzed by FD-MS (Field Desorption-Mass Spectroscopy). 5 mg of the dye was dispersed in THF and analyzed using a JMS-T100GC (manufactured by Jeol).

[0089] (Accelerator mass spectrometry (AMS method)) Tandem accelerator-based 14 Using a dedicated C-AMS device (manufactured by NEC), 14 Counting C, 13 C concentration ( 13 C / 12 C). 14 C concentration ( 14 C / 12 C) was measured. For the measurements, oxalic acid (HOxII) provided by the National Institute of Standards (NIST) was used as the standard sample. Measurements of this standard sample and a background sample were also carried out simultaneously. pMC (percent Modern Carbon) is the ratio of sample carbon to standard modern carbon. 14 C concentration ratio.

[0090] (C) Synthesis of 4-chlorobenzoic acid from 4-aminobenzoic acid To a flask immersed in an ice bath containing 4-aminobenzoic acid (10 g) dissolved in 73 mL of 1 M aqueous NaOH, 37% hydrochloric acid (25 g) was added dropwise. Next, 6.04 g of sodium nitrite was added, and the solution mixture was stirred in the ice bath for 30 minutes. 15.7 g of CuCl2 was added, and the reaction mixture was heated at 60 °C until no further nitrogen evolution was observed. After the reaction mixture was cooled to room temperature, cold water was added and the mixture was extracted with ethyl acetate (3 × 100 mL). The combined ethyl acetate was washed with brine, dried over anhydrous sodium sulfate, and filtered. The solid obtained after solvent evaporation was dried in an oven overnight to yield 9.8 g of solid.

[0091] (E) Synthesis of 4-chlorobenzamide 4-Chlorobenzoic acid (10 g) was mixed with 5.4 g of urea and 0.06 g of molybdenum catalyst in 50 mL of alkylbenzene. The reaction mixture was heated at 150°C for 2 hours. After cooling to room temperature, the solid was filtered and washed thoroughly with water. The solid was dried in an oven overnight, yielding 8.9 g of solid.

[0092] (F) Synthesis of 4-chloroaniline from 4-chlorobenzamide A solution of 4-chlorobenzamide (10 g) and NaOH (8.7 g) in water (48 mL) and acetonitrile (80 mL) was poured into a cold suspension of trichloroisocyanuric acid (82 g) in water (32 mL). The mixture was stirred at 0 °C for 1 hour and then heated under reflux for 30 minutes. After the reaction mixture was cooled to room temperature, the solid was filtered and the filtrate was extracted with ethyl acetate (3 × 100 mL). The combined ethyl acetate was washed with brine, dried over anhydrous sodium sulfate, and filtered. The solid obtained after solvent evaporation was dried in an oven overnight to give 7.9 g of solid.

[0093] (G) Synthesis of aniline from 4-aminobenzoic acid 4-Aminobenzoic acid (10 g) was added to a flask equipped with a distillation apparatus, the internal atmosphere was replaced with nitrogen, and the reaction mixture was stirred and heated at 200° C. for 0.5 hours. 5.4 g of liquid was collected in the distillation apparatus.

[0094] (H) Synthesis of 4-chloroaniline from aniline Aniline (10 g), CuCl2·2H2O (54.9 g), LiCl·H2O (6.5 g), and ethanol (200 mL) were added to a flask. The resulting reaction mixture was refluxed for 10 hours. After the reaction was completed, the ethanol was removed under reduced pressure. Then, 28% aqueous ammonium hydroxide (194 mL) and water (500 mL) were added, and the aqueous phase was extracted with ethyl acetate (100 mL x 3). The combined ethyl acetate was washed with brine, dried over anhydrous sodium sulfate, and filtered. The solid obtained after solvent evaporation was dried in an oven overnight to give 11.4 g of solid.

[0095] (J) Synthesis of dimethyl succinate A solution of bio-derived succinic acid (10 g) in methanol (150 mL) and 98% H2SO4 (0.42 g) was stirred under reflux for 15 hours. The solvent was removed under reduced pressure. The product was dissolved in dichloromethane (40 mL), and the organic solution was washed with water (50 mL x 3). The solution was then dried over magnesium sulfate, and the solvent was evaporated to give 11.8 g of a liquid.

[0096] (K) Synthesis of dimethyl 2,5-dihydroxycyclohexyl 1,4-dicarboxylate (DMSS) Dimethyl succinate (10 g) was added to a flask equipped with a distillation apparatus and heated to 120°C under nitrogen. 28% sodium methoxide (NaOMe) (2.9 g) was added over 1 hour while distilling off methanol. After completion of the distillation, the reaction mixture was maintained at 120°C for 30 minutes. Next, 15% H2SO4 (5.0 g) was slowly added dropwise over 30 minutes while maintaining the reaction mixture at 10-20°C. Water (1.5 g) was added and stirred for 30 minutes. The solid was filtered and thoroughly washed with water. The filtered solid was dried in an oven overnight to yield 12.8 g of solid.

[0097] (O) Synthesis of PV19 To a flask containing dimethyl 2,5-dihydroxycyclohexyl-1,4-dicarboxylate (DMSS) (10 g), aniline (8.6 g), isopropyl alcohol (29.7 g), and methanol (14.9 g) was added 37% hydrochloric acid (0.4 g). The reaction mixture was refluxed for 5 hours. Next, nitrobenzene (4.2 g), 48% NaOH (15.1 g), and water (5.0 g) were added and refluxed for 4 hours. After slight cooling, 37% hydrochloric acid (18.0 g) was added. The solid was filtered and washed thoroughly with water. The solid was dried overnight and stirred in 115% polyphosphoric acid (70.2 g) at 120°C for 3 hours. Upon completion, the reaction mixture was poured into ice water, and the solid was filtered, washed thoroughly with water, and dried overnight in an oven to yield 9.0 g of solid. This results in the radioactive carbon atom 14 A quinacridone compound represented by the above formula (B-1) containing C and having a pMC of 34% was obtained.

[0098] Synthesis of PR122 To a flask containing dimethyl 2,5-dihydroxycyclohexyl-1,4-dicarboxylate (DMSS) (10 g), p-toluidine (9.9 g), isopropyl alcohol (29.7 g), and methanol (14.9 g) was added 37% hydrochloric acid (0.4 g). The reaction mixture was refluxed for 5 hours. Next, nitrobenzene (4.2 g), 48% NaOH (15.1 g), and water (5.0 g) were added and refluxed for 4 hours. After slight cooling, 37% hydrochloric acid (18.0 g) was added. The solid was filtered and washed thoroughly with water. The solid was dried overnight and stirred in 115% polyphosphoric acid (70.2 g) at 120°C for 3 hours. Upon completion, the reaction mixture was poured into ice water, and the solid was filtered, washed thoroughly with water, and dried overnight in an oven to yield 11.0 g of solid. This results in the radioactive carbon atom 14 A quinacridone compound containing C and having a pMC of 31%, in which T in the above (B-2) is represented by CH3, was obtained.

[0099] Synthesis of (N)PR202 To a flask containing dimethyl 2,5-dihydroxycyclohexyl-1,4-dicarboxylate (DMSS) (10 g), 4-chloroaniline (11.8 g), isopropyl alcohol (29.7 g), and methanol (14.9 g) was added 37% hydrochloric acid (0.4 g). The reaction mixture was refluxed for 5 hours. Next, nitrobenzene (4.2 g), 48% NaOH (15.1 g), and water (5.0 g) were added and refluxed for 4 hours. After slight cooling, 37% hydrochloric acid (18.0 g) was added. The solid was filtered and washed thoroughly with water. The solid was dried overnight and stirred in 115% polyphosphoric acid (98.7 g) at 120°C for 3 hours. Upon completion, the reaction mixture was cooled to room temperature, poured into water, and the solid was filtered, washed thoroughly with water, and dried in an oven overnight to yield 10.5 g of solid. This results in the radioactive carbon atom 14 A quinacridone compound containing C and having a pMC of 34%, in which T in the above (B-2) is represented by Cl, was obtained.

[0100] The quinacridone compound represented by the above formula (B-1) was obtained in the same manner as described above, except that petroleum-derived succinic acid was used instead of dimethyl succinate. 14 C was below the detection limit and could not be measured, and pMC was also 0%.

Claims

1. radioactive carbon atoms １４ A method for producing a coloring composition comprising a quinacridone red pigment composition containing C, having a pMC (percent modern carbon) of 50% or more, and containing at least a quinacridone compound represented by the following formula (B-2), and a dispersion medium, 【Chemical 1】 (In formula (B-2), T is Cl or CH ３ is) a step of producing the quinacridone compound by a production method including the following steps (Bi) to (B-iii): a step of obtaining the colored composition by incorporating the quinacridone red pigment composition containing the quinacridone compound produced by a production method including the following steps (Bi) to (B-iii) into the dispersion medium; A method for producing a coloring composition comprising the steps of: (Bi) A process for producing aniline having a substituent at the para position by using 4-aminobenzoic acid as a raw material, obtaining benzoic acid having a substituent at the para position from the 4-aminobenzoic acid by Sandmeyer reaction, then reacting the benzoic acid with urea to obtain benzamide having a substituent at the para position, and then subjecting the benzamide to a Hoffmann elimination reaction. (B-ii) A step of using succinic acid as a raw material, reacting the succinic acid with methanol to obtain dimethyl succinate, and then dimerizing the dimethyl succinate to produce dimethyl 2,5-dihydroxycyclohexadiene-1,4-dicarboxylate. However, of the 4-aminobenzoic acid (Bi) and the succinic acid (B-ii), at least the 4-aminobenzoic acid (Bi) is bio-derived, (B-iii) A step of reacting the aniline having a substituent at the para position produced in (B-i) with dimethyl 2,5-dihydroxycyclohexadiene-1,4-dicarboxylate produced in (B-ii).

2. 2. The method for producing a colored composition according to claim 1, wherein the quinacridone compound represented by formula (B-2) accounts for 70% by mass or more of the quinacridone red pigment composition.

3. 2. The method for producing a colored composition according to claim 1, wherein the quinacridone compound represented by formula (B-2) accounts for 0.5% by mass to 50% by mass in the colored composition.

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