Quinacridone compounds

Abstract

The present invention provides a quinacridone compound of biological origin, which can be used as a biological red pigment and is obtained through a safe, clean, green and carbon neutralization pathway, and a composition containing the compound. A quinacridone compound which contains a radioactive carbon atom 14C and has a structure represented by formula (B). (In formula (B), X each independently represents-Cl,-F,-Br,-I,-OH,-NO2, a C1-C12 alkyl group, a C1-C12 alkoxy group, a phenyl group,-COOH, a-COO-C1-C12 alkyl group, or-CO-NR. R each independently represents a hydrogen atom, an alkyl group, an alkenyl group, or a phenyl group. And n independently represent 1 or 2. > # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a quinacridone compound, a composition containing the compound and a method for producing the compound. Background Art

[0002] Quinacridone is an important red pigment in our daily life due to its strong structure and excellent light and weather resistance. Therefore, it is widely used in automotive coatings, decorative coatings, GI coatings, plastics, inks, etc.

[0003] Regarding a dichloroquinacridone pigment having a quinacridone structure, a method for producing the same is disclosed (see Patent Document 1).

[0004] In conventional synthesis methods of quinacridone, benzene and butane derived from fossil resources are the main raw materials.

[0005] However, in recent years, the world trend has shifted to emphasize sustainable development. Reducing CO2 emissions is an important issue, as is switching from petroleum-based raw materials to bio-based raw materials. Furthermore, replacing toxic chemicals with less toxic alternatives is also emphasized.

[0006] Quinacridone red pigments currently produced are not satisfactory in view of future demands for environmental issues, and from the viewpoints of cleanliness, greenness, and carbon neutrality, there is a strong demand for providing bio-derived quinacridone red pigments.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Publication No. 2007-197630 Summary of the invention

[0010] Problems to be solved by the invention

[0011] The object of the present invention is to provide a bio-derived quinacridone compound that can be used as a bio-red pigment and is obtained through a safe, clean, green and carbon-neutral route, and a composition containing the compound.

[0012] Means for solving problems

[0013] The present inventors conducted research to solve the above-mentioned problems and found that by using bio-4-aminobenzoic acid (4-aminobenzoic acid is also abbreviated as "PABA" in this specification) and bio-succinic acid as raw materials, deriving secondary bio-raw materials and bio-intermediates, and then subjecting the secondary bio-raw materials or the bio-intermediates to coupling reactions, dehydration or ring-closure reactions, a bio-derived quinacridone compound that can be used as a red pigment can be obtained, thereby completing the present invention.

[0014] That is, the present invention includes the following aspects.

[0015] [1] A quinacridone compound comprising a radioactive carbon atom 14 C, and has a structure represented by the following formula (B).

[0016] [Chemistry 1]

[0017]

[0018] (In formula (B), X independently represents -Cl, -F, -Br, -I, -OH, -NO2, C1-C12 alkyl, C1-C12 alkoxy, phenyl, -COOH, -COO-C1-C12 alkyl or -CO-NR. R independently represents a hydrogen atom, an alkyl, an alkenyl or a phenyl. n independently represents 1 or 2.)

[0019] [2] The quinacridone compound according to [1], wherein the quinacridone compound having a structure represented by the aforementioned formula (B) is a quinacridone compound represented by the following formula (B-1) or the following formula (B-2).

[0020] [Chemistry 2]

[0021]

[0022] [Chemistry 3]

[0023]

[0024] (In formula (B-2), T is Cl, CH3 or COOH.)

[0025] [3] A composition comprising the quinacridone compound according to [1] or [2].

[0026] [4] The composition according to [3], which is used as a pigment composition.

[0027] [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% by mass or more.

[0028] [6] A coloring composition comprising the composition according to [3] or [4] and a dispersion medium.

[0029] [7] The colored composition according to [6], wherein the ratio of the diketopyrrolopyrrole compound having the structure represented by (B) in the colored composition is 0.5% by mass to 50% by mass.

[0030] [8] A method for producing a quinacridone compound containing radioactive carbon atoms 14 C, and a quinacridone compound having a structure represented by the following formula (B),

[0031] [Chemistry 4]

[0032]

[0033] (In formula (B), X independently represents -Cl, -F, -Br, -I, -OH, -NO2, C1-C12 alkyl, C1-C12 alkoxy, phenyl, -COOH, -COO-C1-C12 alkyl or -CO-NR. R independently represents a hydrogen atom, an alkyl, an alkenyl or a phenyl. n independently represents 1 or 2.)

[0034] In the aforementioned method for producing a quinacridone compound,

[0035] (Bi) using 4-aminobenzoic acid as a raw material to produce aniline which may have a substituent,

[0036] (B-ii) using succinic acid as a raw material to produce dimethyl 2,5-dihydroxycyclohexane-1,4-dicarboxylate,

[0037] wherein at least one of the 4-aminobenzoic acid (Bi) and the succinic acid (B-ii) is a bio-derived substance,

[0038] (B-iii) The aniline which may have a substituent produced in (Bi) is reacted with dimethyl 2,5-dihydroxycyclohexane-1,4-dicarboxylate produced in (B-ii) to produce a quinacridone compound having a structure represented by the formula (B).

[0039] Effects of the Invention

[0040] According to the present invention, a bio-derived quinacridone compound that can be used as a bio-red pigment and is obtained through a safe, clean, green and carbon-neutral route, and a composition containing the compound can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] [ Figure 1] is a schematic diagram for illustrating the process for producing a bio-derived quinacridone compound. DETAILED DESCRIPTION

[0042] Hereinafter, the present invention will be described in detail. In addition, the description of the constituent elements described below is an example for explaining the present invention, and the present invention is not limited to these contents.

[0043] (Contains radioactive carbon atoms 14 C, and a quinacridone compound having a structure represented by the following formula (B)

[0044] The quinacridone compounds of the present invention contain a radioactive carbon atom 14 C.

[0045] The quinacridone compound of the present invention has a structure represented by the following formula (B).

[0046] [Chemistry 5]

[0047]

[0048] In formula (B), X independently represents -Cl, -F, -Br, -I, -OH, -NO2, C1-C12 alkyl, C1-C12 alkoxy, phenyl, -COOH, -COO-C1-C12 alkyl or -CO-NR. R independently represents a hydrogen atom, an alkyl, an alkenyl or a phenyl. n independently represents 1 or 2.

[0049] 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 aniline which may have a substituted group produced using bio-derived 4-aminobenzoic acid with dimethyl 2,5-dihydroxycyclohexane-1,4-dicarboxylate produced using bio-derived succinic acid.

[0050] The quinacridone compounds of the present invention contain biological (biomass) components derived from biological raw materials. The quinacridone compounds of the present invention contain biological components, for example, by measuring radioactive carbon atoms. 14 C to confirm.

[0051] For example, there is no difference in the molecular weight, mechanical properties, and thermal properties of compounds and compositions derived from biological sources and petroleum sources. In order to distinguish between them, the biomass degree is generally used. 14 C (radiocarbon 14, half-life 5730 years), so the accelerator mass spectrometry was used to determine the 14 By measuring the concentration of C, it is possible to confirm whether the generated compound or composition is a petroleum-derived compound or a bio-derived compound.

[0052] In the measurement of the biomass degree, for example, a sample to be measured is burned to generate carbon dioxide, and the carbon dioxide purified in a vacuum line is reduced with hydrogen using iron as a catalyst to generate graphite.

[0053] The graphene is then mounted on a tandem accelerator-based 14 C-AMS dedicated device (manufactured by NEC Corporation) 14 The count of C, 13 The concentration of C 13 C / 12 C) 14 The concentration of C 14 C / 12 C) and calculate the carbon content of the sample from the measured value 14 The ratio of the C concentration to the standard modern carbon can be obtained from this. In addition, in the measurement, oxalic acid (HOx II) provided by the National Institute of Standards and Technology (NIST) of the United States can be used as a standard sample.

[0054] As an index for evaluating the biomass content, for example, pMC (percent modern carbon) can be cited.

[0055] Here, pMC (modern carbon percentage) can be calculated by measurement according to ASTM-D6866-18 and indicates the percentage of carbon in the object. 14 C concentration relative to that in standard modern carbon 14 In addition, the object does not contain radioactive carbon atoms. 14 In the case of C, pMC is 0%.

[0056] Preferred embodiments of the quinacridone compound having a structure represented by formula (B) include, for example, quinacridone compounds represented by the following formula (B-1) or the following formula (B-2).

[0057] [Chemistry 6]

[0058]

[0059] [Chemistry 7]

[0060]

[0061] (In formula (B-2), T is Cl, CH3 or COOH.)

[0062] The pMC (modern carbon percentage) in the quinacridone compound represented by formula (B-1) and 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 further preferably 99% or more.

[0063] The quinacridone compound represented by (B-1) is a known compound as a pigment constituting Pigment Violet 19 (PV19), and the quinacridone compound represented by (B-2) is a known compound as a pigment constituting Pigment Red 202 (PR202).

[0064] The quinacridone compound of the present invention having a structure represented by formula (B) or a composition containing the quinacridone compound is used as a radioactive carbon atom-containing 14 C, that is, a quinacridone red pigment containing biological components.

[0065] (Method for producing quinacridone compound having a structure represented by formula (B))

[0066] Contains radioactive carbon atoms 14 C. The quinacridone compound of the present invention having a structure represented by formula (B) and containing a biological component can be obtained by the following method:

[0067] (Bi) using 4-aminobenzoic acid as a raw material to produce aniline which may have a substituent;

[0068] (B-ii) using succinic acid as a raw material to produce dimethyl 2,5-dihydroxycyclohexane-1,4-dicarboxylate;

[0069] wherein at least one of the 4-aminobenzoic acid in (Bi) and the succinic acid in (B-ii) is a biologically derived substance;

[0070] (B-iii) reacting the aniline which may have a substituent produced in the above (Bi) with dimethyl 2,5-dihydroxycyclohexane-1,4-dicarboxylate produced in the above (B-ii).

[0071] As the raw materials, 4-aminobenzoic acid and succinic acid may be those obtained from biomass fermentation, plant extraction or thermal decomposition of biomass.

[0072] In the past, the synthesis of quinacridone was typically done through a synthetic route using fossil-based benzene and butane, but benzene is toxic to humans and harmful to the environment. In addition, the previous synthesis method did not contribute to the carbon neutrality plan because it used petroleum-based raw materials.

[0073] Furthermore, if one wishes to synthesize aniline used in the synthesis of quinacridone from benzene, for example, benzene needs to be nitrated with a mixed solution of concentrated acids (nitric acid and sulfuric acid), and further, subsequent heating at 200 to 300° C. is required to hydrogenate nitrobenzene, thus requiring strict production conditions.

[0074] On the other hand, the synthesis method of the quinacridone compound 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 uses biological 4-aminobenzoic acid or biological succinic acid, thereby contributing to the carbon neutralization pathway.

[0075] In the present invention, 4-aminobenzoic acid and succinic acid are used as raw materials to synthesize quinacridone compounds. However, the synthesis of quinacridone compounds using 4-aminobenzoic acid and succinic acid as starting materials is a new route that has not been carried out before.

[0076] The bio-component-containing quinacridone compound of the present invention produced using bio-4-aminobenzoic acid and bio-succinic acid as raw materials has a crystal structure and a particle size that are preferred for pigmentation.

[0077] Preferred embodiments of the method for producing a quinacridone compound having a structure represented by formula (B) include a method for producing a quinacridone compound, particularly a quinacridone compound represented by (B-1) or a quinacridone compound represented by (B-2).

[0078] <Method for producing quinacridone compound having a structure represented by formula (B-1)>

[0079] First, the following is a description of the method for producing the quinacridone compound represented by formula (B-1) (In this specification, when describing the method for producing each compound, reference is also made to Figure 1 It should be noted that the production method described below is described in the case where both 4-aminobenzoic acid and succinic acid use biologically derived substances as raw materials.

[0080] (B-ia) Aniline is produced using biologically derived 4-aminobenzoic acid as a raw material (the following step (G)).

[0081] As a method for producing aniline from 4-aminobenzoic acid, for example, it can be produced by the method described in JP2013-230913A, JP2016-222575A, etc. For example, it can be produced by the method described in the Examples described below.

[0082] [Chemistry 8]

[0083]

[0084] In the above step (G), aniline is produced from 4-aminobenzoic acid.

[0085] In step (G), the reaction may be carried out in a nitrogen atmosphere or in an ambient environment, so-called 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.

[0086] (B-iia) Using bio-derived succinic acid as a raw material, dimethyl succinate (also referred to as "DMS" in this specification) is obtained (step (J) below), and then 2,5-dihydroxycyclohexane-1,4-dicarboxylic acid dimethyl ester (also referred to as "DMSS" in this specification) is produced (step (K) below).

[0087] As a method for producing 2,5-dihydroxycyclohexane-1,4-dicarboxylic acid dimethyl ester from succinic acid, it can be produced by the method 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 described below.

[0088] [Chemistry 9]

[0089]

[0090] In the above step (J), dimethyl succinate is produced from succinic acid.

[0091] In step (J), examples of the catalytic acid that can be used include hydrochloric acid, sulfuric acid, formic acid, acetic acid, methanesulfonic acid, p-toluenesulfonic acid, etc. Among them, hydrochloric acid and sulfuric acid are preferred from the viewpoint of cost.

[0092] In the above step (K), dimethyl 2,5-dihydroxycyclohexane-1,4-dicarboxylate (DMSS) is produced from dimethyl succinate.

[0093] In step (K), the dimerization temperature of dimethyl succinate is preferably 100 to 150° C., more preferably 120 to 130° C. Examples of the dimerization agent include sodium methoxide, potassium methoxide, sodium tert-butoxide, potassium tert-butoxide, sodium hydride, potassium hydride, etc. Among them, sodium methoxide is preferred from the perspective of cost and ease of handling.

[0094] (B-iiia) A quinacridone compound represented by the formula (B-1) is produced by reacting the aniline produced in the above (B-ia) with dimethyl 2,5-dihydroxycyclohexane-1,4-dicarboxylate produced in the above (B-iia) (the following step (O)).

[0095] There is no particular limitation on the reaction method for reacting aniline with dimethyl 2,5-dihydroxycyclohexane-1,4-dicarboxylate, and the aniline can be produced by the method described in US20190177547A1, WO2005085364A1, etc. For example, the aniline can be produced by the method described in the examples described below.

[0096] [Chemistry 10]

[0097]

[0098] In the above step (O), aniline is reacted with dimethyl 2,5-dihydroxycyclohexane-1,4-dicarboxylate to produce a quinacridone compound (PV19 pigment) represented by the formula (B-1).

[0099] In step (O), as the acid required for synthesis, hydrochloric acid, sulfuric acid, formic acid, acetic acid, methanesulfonic acid, p-toluenesulfonic acid, etc. can be mentioned. As the solvent, methanol, ethanol, isopropanol, butanol, dodecanol, etc. can be mentioned. These alcohols can be used alone or in combination of two or more, and more preferably in combination of two or more alcohols. As the mixing ratio of the solvent, it is preferably in the range of 1:0 to 0:1, more preferably 5:1 to 1:5, and more preferably 2:1 to 1:2. The reaction time is preferably 1 to 12 hours, more preferably 2 to 10 hours, and more preferably 3 to 8 hours. In the oxidation process, hydrochloric acid, sulfuric acid, formic acid, acetic acid, methanesulfonic acid, p-toluenesulfonic acid, etc. are used. The reaction time is preferably 1 to 12 hours, more preferably 2 to 10 hours, and 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 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 the polyphosphoric acid used in the cyclization process is preferably 100% or more, more preferably 105% or more, and even more preferably 115% or more.

[0100] <Method for producing quinacridone compound having a structure represented by formula (B-2)>

[0101] Next, the method for producing the quinacridone compound represented by formula (B-2) is described below (see Figure 1 Schematic diagram of ).

[0102] In addition, the following description will be given by taking the case where T in (B-2) is Cl as an example.

[0103] (B-ib) Using biologically derived 4-aminobenzoic acid as a raw material, 4-chlorobenzoic acid is obtained (the following step (C)), and then 4-chlorobenzamide is obtained (the following step (E)), thereby producing 4-chloroaniline (the following step (F)).

[0104] 4-Chloroaniline can be produced from 4-aminobenzoic acid by, for example, the method described in Examples below.

[0105] [Chemistry 11]

[0106]

[0107] In the above step (C), 4-chlorobenzoic acid is produced from 4-aminobenzoic acid using the Sandmeyer reaction, for example.

[0108] In step (C), as the acid used, hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid, methanesulfonic acid, etc. can be cited. Among them, from the perspective of cost, hydrochloric acid, sulfuric acid, and acetic acid are more preferred. As solvents that can be used, water, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylformamide, toluene, xylene, alkylbenzenes, etc. can be cited. Sodium hydroxide is used to increase the dissolution rate of p-aminobenzoic acid, but the reaction can be carried out even without sodium hydroxide. The reaction time of diazotization is preferably 5 minutes to 4 hours, more preferably 20 minutes to 3 hours, and further preferably 30 minutes to 2 hours. In order to exchange the azo group with a chlorine group in the final stage, as a chlorine source, potassium chloride, lithium chloride, cuprous chloride, cupric chloride, tetraethylammonium trichloride, tetrabutylammonium trichloride, N-chlorosuccinimide, trimethylchlorosilane, etc. can be cited. Among them, from the perspective of ease of operation, potassium chloride, lithium chloride, cuprous chloride, cupric chloride, and N-chlorosuccinimide are preferred.

[0109] In the above step (E), 4-chlorobenzamide is produced from 4-chlorobenzoic acid.

[0110] In step (E), as the supply source of ammonia, ammonia gas, ammonia water, and urea can be cited. Among them, urea is preferred from the aspect of ease of operation. As a catalyst for increasing the reaction rate, molybdenum is used, but the reaction can be carried out even without molybdenum. A high boiling point solvent such as alkylbenzene can be used in 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 further preferably 120 to 160°C. The appropriate heating time is preferably 1 to 6 hours, more preferably 2 to 4 hours.

[0111] In step (F), 4-chloroaniline is produced from 4-chlorobenzamide, for example, by using a Hofmann elimination reaction.

[0112] In step (F), acetonitrile is mixed in water as a reaction solvent, and the proportion of acetonitrile is preferably greater than 0 and less than 100%, more preferably 20 to 80%, and further preferably 30 to 70%. As reagents for inducing the Hofmann reaction, trichloroisocyanuric acid, tribromoisocyanuric acid, or triiodoisocyanuric acid can be cited. Among them, trichloroisocyanuric acid and tribromoisocyanuric acid are preferred based on the ease of obtaining the reagent. As the reaction time of the Hofmann reaction, it is preferably 30 minutes to 3 hours, and more preferably 1 to 2 hours. The heating time required for the decomposition of carbamic acid is preferably 5 minutes to 3 hours, more preferably 10 minutes to 2 hours, and further preferably 30 minutes to 1 hour.

[0113] As another embodiment of the above (B-ib), for example, 4-chloroaniline can be obtained by using biologically derived 4-aminobenzoic acid as a raw material to obtain aniline (the following step (G)), and then producing 4-chloroaniline (the following step (H)).

[0114] [Chemistry 12]

[0115]

[0116] The step (G) is as described in the description of the step (G) in the above section <Method for producing a quinacridone compound having a structure represented by formula (B-1)>.

[0117] In the above step (H), 4-chloroaniline is produced from aniline.

[0118] In step (H), copper chloride and lithium chloride may be anhydrous or may contain 1 to 2 crystal waters. As solvents, methanol, ethanol, isopropanol or butanol may be mentioned. The reaction time is preferably 3 to 24 hours, more preferably 5 to 20 hours, more preferably 8 to 15 hours, and particularly preferably 10 to 12 hours.

[0119] (B-iib) Using biologically derived succinic acid as a raw material, dimethyl succinate is obtained (the following step (J)), and then dimethyl 2,5-dihydroxycyclohexane-1,4-dicarboxylate (DMSS) is produced (the following step (K)).

[0120] As a method for producing dimethyl 2,5-dihydroxycyclohexane-1,4-dicarboxylate (DMSS) from succinic acid, the same method as described in the above-mentioned (B-iia) can be used. It can also be produced by the method described in the Examples described later.

[0121] [Chemistry 13]

[0122]

[0123] (B-iiib) A quinacridone compound represented by the formula (B-2) is produced by reacting the 4-chloroaniline produced in the above (B-ib) with dimethyl 2,5-dihydroxycyclohexane-1,4-dicarboxylate produced in the above (B-iib) (step (N) below).

[0124] As a reaction method for reacting 4-chloroaniline with dimethyl 2,5-dihydroxycyclohexane-1,4-dicarboxylate, the same method as described in the above (B-iiia) can be used for production. For example, it can be produced by the method described in the Examples described later.

[0125] [Chemistry 14]

[0126]

[0127] In the step (N), 4-chloroaniline is reacted with dimethyl 2,5-dihydroxycyclohexane-1,4-dicarboxylate by the same method as described in the step (B-iiia) to produce a quinacridone compound (PR202 pigment) in which T is represented by Cl in the formula (B-2).

[0128] As described above, the 4-aminobenzoic acid used as a raw material is preferably derived from biomass, and as described above, the succinic acid used as a raw material is also preferably derived from biomass.

[0129] More preferably, both the 4-aminobenzoic acid and the succinic acid are derived from biomass.

[0130] The biomass degree of the raw material used in the above-mentioned 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, when a biomass raw material based on a mass balance method or a certificate trading system (Book & Claim) is available, it is easier to achieve a biomass degree of 1% or more and 100% or less. In this patent, the biomass degree of biomass raw materials based on a mass balance method or a certificate trading system is the object.

[0131] (Composition containing quinacridone compound)

[0132] The present invention may be a composition comprising the quinacridone compound of the present invention having a structure represented by formula (B).

[0133] The composition is preferably used as a pigment composition, and is particularly preferably used as a quinacridone-based red pigment.

[0134] The composition of the present invention may contain, for example, one or two or more quinacridone compounds having a structure represented by formula (B).

[0135] As a more preferred embodiment of the composition of the present invention, 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) can be mentioned.

[0136] The proportion of the quinacridone compound having a structure represented by the above formula (B) in the composition (more preferably the proportion of the quinacridone compound represented by the above formula (B-1) or the above formula (B-2)) is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more, when the composition is a pigment composition.

[0137] The BET value of the composition of the present invention is preferably 20 to 100 m 2 / g, preferably 30 to 95 m 2 / g, preferably 40 to 90 m 2 / g, preferably 50 to 85 m 2 / g. In particular, 20 to 80 is preferred for ink applications, 40 to 90 is preferred for coating applications, 50 to 90 is preferred for resin applications, and 50 to 100 is preferred for color filter applications. It should be noted that the BET value can be measured by weighing 0.1 g of the pigment in a measuring unit and setting it in a specific surface area meter (Macsorb 1208).

[0138] (Application of the Quinacridone Compound of the Present Invention)

[0139] The radioactive carbon atom-containing compound having a structure represented by formula (B) obtained by the above method 14 The quinacridone compound of the present invention of C and a composition containing the quinacridone compound constitute a quinacridone red pigment such as PV19 and PR202.

[0140] The quinacridone compound of the present invention contains biomass-derived carbon and contributes to reducing environmental load through carbon neutralization.

[0141] The quinacridone red pigment comprising the quinacridone compound of the present invention and a composition comprising the quinacridone compound can be used as a coloring composition, a molding composition, and the like.

[0142] In addition, the quinacridone red pigment containing the quinacridone compound of the present invention and the composition containing the quinacridone compound can be mixed with other resins, rubbers, additives, solvents, pigments, dyes, etc. as needed, and adjusted to be used as a coating material or printed mark for cosmetics, pharmaceuticals or pesticides, stationery, writing tools, printing inks, inkjet inks, metallic inks, coatings, plastic colorants, toners (color toners), color filters, etc.

[0143] <Coloring Composition>

[0144] The coloring composition of the present invention preferably comprises: a quinacridone-based red pigment composition comprising the quinacridone compound of the present invention and a composition having the quinacridone compound; and a dispersion medium.

[0145] The colored composition of the present invention preferably contains 0.5 to 50% by mass of the quinacridone compound having a structure represented by the above formula (B), more preferably 2.5 to 35% by mass, and even more preferably 5 to 20% by mass.

[0146] <<Dispersion Medium>>

[0147] 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. In addition, low molecular weight dispersants such as surfactants may be used as needed.

[0148] Examples of the type of resin in the resin-type dispersant include styrene-(meth)acrylic acid copolymers, (meth)acrylic acid-alkyl (meth)acrylic acid ester copolymers, styrene-(meth)acrylic acid-alkyl (meth)acrylic acid ester copolymers, styrene-α-methylstyrene-(meth)acrylic acid copolymers, styrene-α-methylstyrene-(meth)acrylic acid-alkyl (meth)acrylic acid 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 copolymers, vinylnaphthalene-maleic acid copolymers, polyester-modified (meth)acrylic acid polymers, and salts thereof.

[0149] Examples of the form of the resin in the resin-type dispersant include a water-soluble resin and an emulsion (water-insoluble resin).

[0150] The binder resin may be, for example, a polyolefin resin, a polyester resin, a styrene copolymer, an acrylic resin, and modified resins thereof. Specifically, polyolefin resins 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 copolymers, styrene-vinyl toluene copolymers, styrene-vinyl naphthalene copolymers, styrene-acrylate copolymers, styrene-methacrylate 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 ethylene copolymers, styrene copolymers such as styrene-acrylonitrile-indene copolymers; acrylic resins such as acrylic resins and methacrylic resins; polyvinyl chloride, phenolic resins, natural modified phenolic resins, natural resin modified maleic acid resins, polyvinyl acetate, silicone resins, polyurethane resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, nitrocellulose resins, polyamide resins, epoxy resins, xylene resins, polyvinyl butyral resins, polyvinyl acetal resins, cellulose ester resins, alkyd resins, rosin resins, ketone resins, cyclized rubber, chlorinated polyolefin resins, terpene resins, coumarone-indene resins, alkyd resins, amino resins, petroleum resins, and modified resins thereof, etc.

[0151] Organic solvents can be classified into water-soluble solvents and water-insoluble solvents.

[0152] Examples of water-soluble solvents include ethanol, n-propanol, isopropanol, isobutanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and glycerol. Examples of water-insoluble solvents include toluene, xylene, butyl acetate, methyl acetate, methyl ethyl ketone, methyl isobutyl ketone, butanol, and aliphatic hydrocarbons.

[0153] Each material constituting the coloring composition may be used alone or in combination of two or more.

[0154] <Molding Composition>

[0155] 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 the thermoplastic resin is preferably melted, kneaded, and molded into a desired shape to produce a molded body.

[0156] Examples of thermoplastic resins include homopolymers or copolymers using ethylene, propylene, butylene, styrene, etc. as monomer components. More specifically, polyolefin resins such as polyethylene such as high-density polyethylene (HDPE), linear low-density polyethylene (L-LDPE), and low-density polyethylene (LDPE), polypropylene, and polybutene can be cited. 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 them, polyolefin resins and polyester resins are preferred. It should be noted that the number average molecular weight of the thermoplastic resin is preferably greater than 30,000 and less than 200,000.

[0157] The molding composition may contain wax. Wax includes low molecular weight polyolefins. They are polymers of olefin monomers such as ethylene, propylene, butene, etc., and may be block, random copolymers or terpolymers. Specifically, they are polymers of α-olefins such as low density polyethylene (LDPE), high density polyethylene (HDPE), and polypropylene (PP).

[0158] 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 is appropriately transferred to the surface of the molded article, so that the balance between the sliding property and the suppression of bleeding is excellent.

[0159] The melting point of the wax is preferably 60 to 150° C., more preferably 70 to 140° C. Within this range, processability is improved when the thermoplastic resin and the wax are melt-kneaded.

[0160] The molding composition may contain other additives. Other additives are materials commonly used in the technical field of molded bodies, and examples thereof include antioxidants, light stabilizers, dispersants, metal soaps, antistatic agents, flame retardants, lubricants, fillers, and colorants other than the quinacridone compound of the present invention.

[0161] The molding composition can be produced, for example, as a masterbatch containing a quinacridone compound at a high concentration.

[0162] The masterbatch is preferably prepared by melt-kneading a thermoplastic resin and a pigment composition, and then molded into an arbitrary shape in a manner that is easy to use in the next step. Then, the masterbatch and a diluent resin (such as a thermoplastic resin used in the masterbatch) are melt-kneaded to form a molded body of a desired shape. The shape of the masterbatch can be granular, powdery, plate-like, etc. It should be noted that in order to prevent the agglomeration of the pigment composition, it is preferably prepared in advance by melt-kneading a dispersion formed by melt-kneading a pigment composition and wax, and then melt-kneading with a thermoplastic resin to manufacture a masterbatch. The device used in the dispersion is preferably a blending mixer, a three-roll mill, etc.

[0163] Examples of uses of the molding composition include plastic molded products, sheets, and films.

[0164] <Toner>

[0165] The toner contains a coloring composition (pigment composition, resin). In the toner, the resin is preferably a thermoplastic resin called a binder resin. The toner can be a dry toner or a wet toner. For example, in the case of a dry toner, the pigment composition and the binder resin are melt-kneaded, and after cooling, a crushing and classification process is performed. Then, a post-treatment process of mixing with additives can be performed to produce the toner.

[0166] Examples of the binder resin include styrene-p-chlorostyrene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, styrene-(meth)acrylate copolymers, styrene-α-chloromethylacrylate 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, natural modified phenolic resins, natural 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, petroleum resins, and the like.

[0167] Among these, polyester resins and styrene copolymers are preferred, and polyester resins are more preferred. Since the pigment composition has particularly excellent compatibility with the polyester resin, the quinacridone compound is uniformly and finely dispersed in the toner, and thus a high-quality toner can be obtained.

[0168] 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 further preferably 20,000 to 100,000. When a polyester resin having an appropriate Mw is used, a toner having good offset resistance and low-temperature fixing property can be obtained.

[0169] 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 having an appropriate acid value is used, the release agent is easily suppressed from being liberated, and the image density is less likely to decrease under a high humidity environment.

[0170] The toner may further contain a charge control agent. When a charge control agent is used, a toner having a stable charge amount can be easily obtained. The charge control agent may be a positive or negative charge control agent selected appropriately for use.

[0171] The toner may contain a release agent. Examples of the release agent include 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 bran wax.

[0172] The toner may contain a lubricant, a fluidizing agent, a grinding agent, a conductivity imparting agent, an image peeling preventing agent, and the like, as necessary.

[0173] In addition, the toner may be used as a one-component developer or a two-component developer. The two-component developer may further contain a carrier.

[0174] Examples of the carrier include magnetic powders such as iron powder, ferrite powder, and nickel powder, and products obtained by coating the surfaces of these powders with resins, etc. Examples of the resin used to coat the surface of the carrier include styrene-(meth)acrylate copolymers, (meth)acrylate copolymers, fluorine-containing resins, silicon-containing resins, polyamide resins, ionomer resins, and polyphenylene sulfide resins.

[0175] <Paint>

[0176] The coating material contains a coloring composition (a pigment composition, a resin, and a solvent).

[0177] The resin may be a thermosetting resin or a thermoplastic resin. The thermosetting resin preferably has a glass transition temperature of 10°C or higher. Examples of the thermosetting resin include acrylic resin, polyester, polyurethane, etc. In addition, the thermosetting resin preferably has a functional group that can react with a curing agent. Examples of the functional group include carboxyl, hydroxyl, etc. Examples of the curing agent include isocyanate curing agents, epoxy curing agents, aziridine curing agents, amine curing agents, etc.

[0178] 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. In addition, a thermosetting resin and a thermoplastic resin may be used in combination.

[0179] Among the solvents, examples of the water-insoluble solvent include toluene, xylene, butyl acetate, methyl acetate, methyl ethyl ketone, methyl isobutyl ketone, butanol, and aliphatic hydrocarbons.

[0180] Among the solvents, water-soluble solvents include, for example, water, monohydric alcohols, dihydric alcohols, and glycols. As water-soluble solvents, for example, ethanol, n-propanol, isopropanol, isobutyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and glycerol can be mentioned. In addition, water-dilutable monoethers derived from polyhydric alcohols can also be mentioned. Specific examples thereof include methoxypropanol and methoxybutanol. In addition, water-dilutable glycol ethers such as butyl glycol and butyl diglycol can also be mentioned. In addition, when the solvent contains water, the coating is called a water-based coating.

[0181] The coating material may further contain known additives.

[0182] Examples of uses of the coating include coatings for metals and coatings for plastics.

[0183] <Printing ink>

[0184] Printing ink contains a coloring composition (pigment composition, resin, solvent). Printing ink is an ink other than inkjet ink, for example, offset printing ink, flexographic printing ink, gravure printing ink, screen printing ink, color filter ink, etc. In addition, when the solvent contains water, it is called water-based printing ink.

[0185] Examples of the resin include rosin resin, rosin-modified phenolic resin, polyurethane, nitrocellulose, acrylic resin, styrene-acrylic resin, and petroleum resin.

[0186] Among the solvents, examples of the water-insoluble solvent include toluene, xylene, butyl acetate, methyl acetate, methyl ethyl ketone, methyl isobutyl ketone, butanol, and aliphatic hydrocarbons.

[0187] Among the solvents, water-soluble solvents include ethanol, n-propanol, isopropanol, isobutanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and glycerol. In addition, water-dilutable monoethers derived from polyhydric alcohols may be mentioned. For example, methoxypropanol or methoxybutanol may be mentioned. In addition, water-dilutable glycol ethers such as butyl glycol and butyl diglycol may be mentioned.

[0188] The printing ink may further contain a luster material. The luster material is a particle having an average thickness of 0.5 to 10 μm and an average particle size 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 metal oxides such as titanium oxide.

[0189] The printing ink may further contain known additives.

[0190] <Inkjet Ink>

[0191] The inkjet ink contains a pigment composition and a resin, and preferably further contains a solvent. The inkjet ink can be roughly divided into (solvent-based) inkjet ink, water-based inkjet ink, and solvent-free inkjet ink, depending on the presence or absence of a solvent and the type of solvent.

[0192] The following description will focus on aqueous inkjet inks.

[0193] The resin used in the aqueous inkjet ink is important for obtaining the fixability of the ink to the printed material (substrate).

[0194] Examples of the types of resin include acrylic resins, styrene-acrylic resins, polyester resins, polyamide resins, polyurethane resins, and the like. In addition, examples of the forms of the resin include water-soluble resins, emulsion particles, and the like. Among them, emulsion particles are preferred. Emulsion particles include single-component particles, core-shell particles, and the like, which can be selected and used arbitrarily. When emulsion particles are used, it is easy to reduce the viscosity of aqueous inkjet inks, and it is easy to obtain records with excellent water resistance. The resin can be used by neutralizing the acidic functional groups using pH adjusters such as ammonia, various amines, and various inorganic bases as needed.

[0195] Examples of the solvent include non-water-soluble solvents, water, and water-soluble solvents. Examples of the water-soluble solvent include glycol ethers and glycols. These solvents penetrate into the substrate very quickly, and also penetrate quickly into low-liquid-absorbing and non-liquid-absorbing substrates such as coated paper, coated paper, vinyl chloride sheets, films, and cloth. Therefore, the drying is fast during printing, and accurate printing can be achieved. In addition, due to the high boiling point, it also acts as a wetting agent.

[0196] The water-soluble solvent is important for preventing the aqueous inkjet ink from drying and solidifying in the nozzle part of the print head and obtaining the ejection stability of the ink. Examples of the water-soluble solvent include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, polyethylene glycol, glycerol, tetraethylene glycol, dipropylene glycol, ketone alcohols, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, 1,2-hexanediol, N-methyl-2-pyrrolidone, substituted pyrrolidones, 2,4,6-hexanetriol, tetrafurfuryl alcohol, 4-methoxy-4-methylpentanone, and the like.

[0197] The inkjet ink may further contain additives, such as drying accelerators, penetrants, preservatives, chelating agents, and pH adjusters.

[0198] Inkjet ink is produced by mixing various materials. Mixing can be carried out by a stirrer using blades, various dispersers, emulsifiers, etc. The order of adding the materials and the mixing method are arbitrary.

[0199] The inkjet ink is preferably filtered or centrifuged after mixing to remove coarse particles. This improves the ejection properties from the inkjet printer. Filtration and centrifugation can be performed using known methods.

[0200] Various inkjet methods can be used for the inkjet ink, and examples of the inkjet method include charge control type, continuous jet type such as spray type, piezoelectric method, thermal method, electrostatic attraction method, and the like.

[0201] Example

[0202] Hereinafter, the present invention will be described in further detail with reference to Examples, but the present invention is not limited to these Examples. In addition, "%" in the compositions of the following Examples means "mass %".

[0203] (Composition Analysis)

[0204] The composition of the dye obtained in the example was analyzed by FD-MS (Field Desorption-Mass Spectroscopy): 5 mg of the dye was dispersed in THF and analyzed using JMS-T100GC (manufactured by Jeol).

[0205] (Accelerator Mass Spectrometry (AMS))

[0206] Using a tandem accelerator-based 14 C-AMS dedicated device (manufactured by NEC Corporation) 14 The count of C, 13 C concentration ( 13 C / 12 C) 14 C concentration ( 14 C / 12 C) determination.

[0207] In the measurement, oxalic acid (HOx II) provided by the National Institute of Standards and Technology (NIST) was used as the standard sample. The standard sample and the background sample were measured simultaneously. pMC (percent modern carbon) is the percentage of sample carbon relative to the standard modern carbon. 14 The ratio of C concentration.

[0208] (C) Synthesis of 4-chlorobenzoic acid from 4-aminobenzoic acid

[0209] In a flask immersed in an ice bath and containing 4-aminobenzoic acid (10 g) dissolved in 73 mL of 1 M NaOH aqueous solution, 37% hydrochloric acid (25 g) was added dropwise. Next, 6.04 g of sodium nitrate was added, and the solution mixture was stirred in an ice bath for 30 minutes. 15.7 g of CuCl2 was added, and then the reaction mixture was heated at 60°C until no nitrogen generation was observed. After the reaction mixture was cooled to room temperature, cold water was added and 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 evaporation of the solvent was dried in an oven overnight to obtain 9.8 g of solid.

[0210] (E) Synthesis of 4-chlorobenzamide

[0211] 4-Chlorobenzoic acid (10 g) was mixed with 5.4 g urea and 0.06 g platinum catalyst in 50 mL 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 to obtain 8.9 g of solid.

[0212] (F) Synthesis of 4-chloroaniline from 4-chlorobenzamide

[0213] A solution of 4-chlorobenzamide (10 g) and NaOH (8.7 g) in water (48 mL) and acetonitrile (80 mL) were 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 evaporation of the solvent was dried in an oven overnight to obtain 7.9 g of solid.

[0214] (G) Synthesis of aniline from 4-aminobenzoic acid

[0215] 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.

[0216] (H) Synthesis of 4-chloroaniline from aniline

[0217] 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 a 28% aqueous solution of ammonium hydroxide (194 mL) and water (500 mL) were added, and the aqueous phase was extracted with ethyl acetate (100 mL×3). The combined ethyl acetate was washed with brine, dried over anhydrous sodium sulfate, and filtered. The solid obtained after evaporation of the solvent was dried in an oven overnight to obtain 11.4 g of solid.

[0218] (J) Synthesis of dimethyl succinate

[0219] 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 obtain 11.8 g of liquid.

[0220] (K) Synthesis of 2,5-dihydroxycyclohexane-1,4-dicarboxylic acid dimethyl ester (DMSS)

[0221] Add dimethyl succinate (10 g) to a flask equipped with a distillation apparatus, heat to 120°C under nitrogen, remove methanol while distilling, and add 28% sodium methoxide (NaOMe) (2.9 g) over 1 hour. After completion, maintain the reaction mixture at 120°C for 30 minutes. Next, slowly add 15% H2SO4 (5.0 g) dropwise over 30 minutes while maintaining the reaction mixture at 10-20°C. Add water (1.5 g) and stir for 30 minutes. Filter the solid and wash it thoroughly with water. Dry the filtered solid in an oven overnight to obtain 12.8 g of solid.

[0222] (O) Synthesis of PV19

[0223] 37% hydrochloric acid (0.4 g) was added to a flask containing dimethyl 2,5-dihydroxycyclohexane-1,4-dicarboxylate (DMSS) (10 g), aniline (8.6 g), isopropanol (29.7 g) and methanol (14.9 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 cooling slightly, 37% hydrochloric acid (18.0 g) was added. The solid was filtered and washed thoroughly with water. The solid dried overnight was stirred in 115% polyphosphoric acid (70.2 g) at 120°C for 3 hours. After completion, the reaction mixture was poured into ice water, the solid was filtered, washed thoroughly with water, and dried in an oven overnight to obtain 9.0 g of solid.

[0224] Thus, we can get the radioactive carbon atoms 14 C. The quinacridone compound represented by the above (B-1) having a pMC of 34%.

[0225] Synthesis of PR122

[0226] 37% hydrochloric acid (0.4 g) was added to a flask containing dimethyl 2,5-dihydroxycyclohexane-1,4-dicarboxylate (DMSS) (10 g), p-toluidine (9.9 g), isopropanol (29.7 g) and methanol (14.9 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 cooling slightly, 37% hydrochloric acid (18.0 g) was added. The solid was filtered and washed thoroughly with water. The solid dried overnight was stirred in 115% polyphosphoric acid (70.2 g) at 120°C for 3 hours. After completion, the reaction mixture was poured into ice water, the solid was filtered, washed thoroughly with water, and dried in an oven overnight to obtain 11.0 g of solid.

[0227] Thus, we can get the radioactive carbon atoms 14C. A quinacridone compound of the above (B-2) wherein T is represented by CH3, with a pMC of 31%.

[0228] Synthesis of (N)PR202

[0229] 37% hydrochloric acid (0.4 g) was added to a flask containing 2,5-dihydroxycyclohexane-1,4-dicarboxylic acid dimethyl ester (DMSS) (10 g), 4-chloroaniline (11.8 g), isopropanol (29.7 g) and methanol (14.9 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 cooling slightly, 37% hydrochloric acid (18.0 g) was added. The solid was filtered and washed thoroughly with water. The solid dried overnight was stirred in 115% polyphosphoric acid (98.7 g) at 120°C for 3 hours. After completion, the reaction mixture was cooled to room temperature, poured into water, the solid was filtered, washed thoroughly with water, and dried in an oven overnight to obtain 10.5 g of solid.

[0230] Thus, we can get the radioactive carbon atoms 14 C. A quinacridone compound in which T is represented by Cl in the above (B-2) and whose pMC is 34%.

[0231] It should be noted that the quinacridone compound represented by the above (B-1) was obtained by the same method as the above method except that succinic acid derived from petroleum was used instead of dimethyl succinate in the synthesis of dimethyl succinate. As a result, the radioactive carbon atom of the quinacridone compound was 14 C was below the detection limit and could not be measured, and pMC was also 0%.

Claims

1. A quinacridone compound comprising a radioactive carbon atom 14 C, and has a structure represented by the following formula (B), [Chemistry 1] In formula (B), X independently represents -Cl, -F, -Br, -I, -OH, -NO2, C1~C12 alkyl, C1~C12 alkoxy, phenyl, -COOH, -COO-C1~C12 alkyl or -CO-NR, R independently represents a hydrogen atom, an alkyl, an alkenyl or a phenyl, and n independently represents 1 or 2.

2. The quinacridone compound according to claim 1, wherein The quinacridone compound having a structure represented by the formula (B) is a quinacridone compound represented by the following formula (B-1) or the following formula (B-2), [Chemistry 2] [Chemistry 3] In formula (B-2), T is Cl, CH3 or COOH.

3. A composition comprising the quinacridone compound according to claim 1.

4. The composition according to claim 3, which is used as a composition for pigments.

5. The composition according to claim 3, wherein The ratio of the quinacridone compound having the structure represented by (B) in the composition is 70% by mass or more. 6 . A coloring composition comprising the composition according to claim 3 and a dispersion medium.

7. The coloring composition according to claim 6, wherein The ratio of the quinacridone compound having the structure represented by (B) in the coloring composition is 0.5% by mass to 50% by mass.

8. A method for producing a quinacridone compound comprising producing a quinacridone compound comprising a radioactive carbon atom 14 C, and a quinacridone compound having a structure represented by the following formula (B), [Chemistry 4] In formula (B), X independently represents -Cl, -F, -Br, -I, -OH, -NO2, C1-C12 alkyl, C1-C12 alkoxy, phenyl, -COOH, -COO-C1-C12 alkyl or -CO-NR, R independently represents a hydrogen atom, an alkyl, an alkenyl or a phenyl, and n independently represents 1 or 2, In the method for producing the quinacridone compound, (Bi) using 4-aminobenzoic acid as a raw material to produce aniline which may have a substituent, (B-ii) using succinic acid as a raw material to produce dimethyl 2,5-dihydroxycyclohexane-1,4-dicarboxylate, in, At least one of the 4-aminobenzoic acid (Bi) and the succinic acid (B-ii) is a substance of biological origin, (B-iii) reacting the aniline which may have a substituent produced in (Bi) with dimethyl 2,5-dihydroxycyclohexane-1,4-dicarboxylate produced in (B-ii) to produce a quinacridone compound having a structure represented by the formula (B).

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