Diketopyrrolopyrrole compounds

Abstract

The present invention provides a biogenic diketopyrrolopyrrole compound which can be used as a biogenic red pigment and is obtained by a safe, clean, green and carbon neutralization pathway, and a composition containing the compound. A diketopyrrolopyrrole compound which contains a radioactive carbon atom 14C and has a structure represented by formula (A). (In formula (A), 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 diketopyrrolopyrrole compound, a composition containing the compound, and a method for producing the compound. Background Art

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

[0003] Regarding Pigment Red 254 (PR254) (3,6-bis(4-chlorophenyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione) having a diketopyrrolopyrrole structure, a method for producing the same is disclosed (see Patent Document 1).

[0004] In the existing synthesis method of diketopyrrolopyrrole, benzene and butane derived from fossil resources are the main raw materials.

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

[0006] At present, in view of the requirements for future environmental issues, the diketopyrrolopyrrole red pigments produced are not satisfactory, and from the viewpoints of cleanliness, greenness, and carbon neutrality, there is a strong demand for providing a bio-derived diketopyrrolopyrrole red pigment.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent No. 4214493 Summary of the invention

[0010] Problems to be solved by the invention

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

[0012] Means for solving problems

[0013] The present inventors have conducted research to solve the above-mentioned problems and have found that by using bio-4-aminobenzoic acid (4-aminobenzoic acid is also referred to 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 pyrrolopyrrole diketo 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 diketopyrrolopyrrole compound containing a radioactive carbon atom 14 C, and has a structure represented by the following formula (A),

[0016] [Chemistry 1]

[0017]

[0018] (In formula (A), 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 diketopyrrolopyrrole compound according to [1], wherein the diketopyrrolopyrrole compound having a structure represented by the formula (A) is a diketopyrrolopyrrole compound represented by the following formula (A-1) or the following formula (A-2).

[0020] [Chemistry 2]

[0021]

[0022] [Chemistry 3]

[0023]

[0024] [3] A composition comprising the diketopyrrolopyrrole compound according to [1] or [2].

[0025] [4] The composition according to [3], which is used as a pigment composition.

[0026] [5] The composition according to [3] or [4], wherein the ratio of the diketopyrrolopyrrole compound having the structure represented by (A) in the composition is 70% by mass or more.

[0027] [6] A coloring composition comprising the composition according to [3] or [4] and a dispersion medium.

[0028] [7] The colored composition according to [6], wherein the ratio of the diketopyrrolopyrrole compound having the structure represented by (A) in the colored composition is 0.5% by mass to 50% by mass.

[0029] [8] A method for producing a diketopyrrolopyrrole compound containing radioactive carbon atoms 14 C and a diketopyrrolopyrrole compound having a structure represented by the following formula (A),

[0030] [Chemistry 4]

[0031]

[0032] (In formula (A), 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.)

[0033] The preparation method of the diketopyrrolopyrrole compound is:

[0034] (Ai) using 4-aminobenzoic acid as a raw material to produce benzonitrile which may have a substituent,

[0035] (A-ii) using succinic acid as a raw material to produce diisopropyl succinate,

[0036] wherein at least one of the 4-aminobenzoic acid (Ai) and the succinic acid (A-ii) is a substance of biological origin,

[0037] (A-iii) The benzonitrile which may have a substituent produced in (Ai) is reacted with the diisopropyl succinate produced in (A-ii) to produce a diketopyrrolopyrrole compound having a structure represented by the formula (A).

[0038] Effects of the Invention

[0039] According to the present invention, a bio-derived diketopyrrolopyrrole 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

[0040] Figure 1Schematic diagram for explaining the process for producing a bio-derived diketopyrrolopyrrole compound. DETAILED DESCRIPTION

[0041] Hereinafter, the present invention will be described in detail. It should be noted that 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.

[0042] (Contains radioactive carbon atoms 14 C and having a diketopyrrolopyrrole compound represented by the following formula (A)

[0043] The diketopyrrolopyrrole compounds of the present invention contain radioactive carbon atoms. 14 C.

[0044] The diketopyrrolopyrrole compound of the present invention has a structure represented by the following formula (A).

[0045] [Chemistry 5]

[0046]

[0047] In formula (A), 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.

[0048] The diketopyrrolopyrrole 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 benzonitrile which may have a substituted group produced using bio-derived 4-aminobenzoic acid with diisopropyl succinate (also referred to as "DIPS" in this specification) produced using bio-derived succinic acid.

[0049] The diketopyrrolopyrrole compound of the present invention contains a biological (biomass) component derived from a biological raw material. The diketopyrrolopyrrole compound of the present invention contains a biological component, for example, by measuring the radioactive carbon atoms. 14 C to confirm.

[0050] For example, there is no difference in physical properties such as molecular weight, mechanical properties, and thermal properties between compounds and compositions derived from biomass and petroleum. To distinguish between them, the biobased content is usually used. In this biobased content, the carbon content of compounds and compositions derived from petroleum does not contain 14 C (radiocarbon 14, half-life 5730 years), so the accelerator mass spectrometry was used to determine the 14By 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.

[0051] The bio-based content is measured by, for example, burning a sample to be measured to generate carbon dioxide, and reducing the carbon dioxide purified in a vacuum line with hydrogen using iron as a catalyst to generate graphite.

[0052] 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 (HOxII) provided by the National Institute of Standards and Technology (NIST) of the United States can be used as a standard sample.

[0053] As an indicator for evaluating the biobased content, for example, pMC (percent modern carbon) can be cited.

[0054] Here, pMC (modern carbon percentage) can be calculated by measuring according to ASTM-D6866-18, which 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%.

[0055] Preferred embodiments of the diketopyrrolopyrrole compound having a structure represented by formula (A) include, for example, diketopyrrolopyrrole compounds represented by the following formula (A-1) or the following formula (A-2).

[0056] [Chemistry 6]

[0057]

[0058] [Chemistry 7]

[0059]

[0060] The pMC (modern carbon percentage) in the pyrrolopyrrole diketo compound represented by formula (A-1) and the pyrrolopyrrole diketo compound represented by formula (A-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.

[0061] The diketopyrrolopyrrole compound represented by (A-1) is a known compound as a pigment constituting Pigment Red 255 (PR255), and the diketopyrrolopyrrole compound represented by (A-2) is a known compound as a pigment constituting PR254.

[0062] The diketopyrrolopyrrole compound of the present invention having a structure represented by formula (A) or a composition containing the diketopyrrolopyrrole compound is used as a radioactive carbon atom-containing 14 C. A diketopyrrolopyrrole red pigment containing a biological component is used.

[0063] (Method for producing diketopyrrolopyrrole compound having a structure represented by formula (A))

[0064] Contains radioactive carbon atoms 14 C, i.e., the diketopyrrolopyrrole compound of the present invention having a structure represented by formula (A) and containing a biological component, can be obtained by the following method:

[0065] (Ai) using 4-aminobenzoic acid as a raw material to produce benzonitrile which may have a substituent,

[0066] (A-ii) using succinic acid as a raw material to produce diisopropyl succinate,

[0067] wherein at least one of the 4-aminobenzoic acid (Ai) and the succinic acid (A-ii) is a substance of biological origin,

[0068] (A-iii) reacting the benzonitrile which may have a substituent produced in (Ai) with the diisopropyl succinate produced in (A-ii).

[0069] As the raw materials, 4-aminobenzoic acid and succinic acid may be biologically derived substances obtained by fermentation of biomass, plant extraction, or thermal decomposition of biomass.

[0070] In the past, the synthesis of diketopyrrolopyrrole was typically done from fossil-based benzene and butane, but benzene is toxic to humans and harmful to the environment. In addition, the previous synthesis method used petroleum-based raw materials, which is not conducive to carbon neutrality plans.

[0071] In addition to using benzene, there are methods for synthesizing benzonitrile such as ammoxidation of toluene, but this method requires heating at 400 to 450° C. On the other hand, halogenated benzenes can also be used, but in this case, since metal cyanide is used, there is a possibility that highly toxic hydrogen cyanide will be generated.

[0072] On the other hand, the synthesis method of the diketopyrrolopyrrole compound disclosed in the present invention can use plant-derived raw materials as raw materials. Since at least one of the raw materials 4-aminobenzoic acid and succinic acid uses biological 4-aminobenzoic acid or biological succinic acid, it contributes to the carbon neutralization pathway.

[0073] In the present invention, 4-aminobenzoic acid and succinic acid are used as raw materials to synthesize a diketopyrrolopyrrole compound. However, the synthesis of a diketopyrrolopyrrole compound using 4-aminobenzoic acid and succinic acid as starting materials is a new route that has not been conducted before.

[0074] The bio-component-containing diketopyrrolopyrrole compound of the present invention produced using bio-4-aminobenzoic acid and bio-succinic acid as raw materials has a crystal structure and particle size that are preferred in terms of pigmentation.

[0075] Preferred embodiments of the method for producing a diketopyrrolopyrrole compound having a structure represented by formula (A) include a method for producing a diketopyrrolopyrrole compound, particularly a diketopyrrolopyrrole compound represented by (A-1) or a diketopyrrolopyrrole compound represented by (A-2).

[0076] <Method for producing diketopyrrolopyrrole compound having a structure represented by formula (A-1)>

[0077] First, the following describes a method for producing a diketopyrrolopyrrole compound represented by formula (A-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.

[0078] (A-ia) Using biologically derived 4-aminobenzoic acid as a raw material, benzoic acid is obtained (the following step (A)), and then benzonitrile is produced (the following step (B)).

[0079] As a method for producing benzonitrile from 4-aminobenzoic acid, for example, it can be produced by the method described in Examples described later.

[0080] [Chemistry 8]

[0081]

[0082] In the above step (A), benzoic acid is produced from 4-aminobenzoic acid.

[0083] In step (A), as the acid used, hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid, methanesulfonic acid, etc. can be cited. Among them, hydrochloric acid, sulfuric acid, and acetic acid are more preferred from the cost point of view. As the solvent that can be used, water, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylformamide, toluene, xylene, alkylbenzene, 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 for a proton group in the final stage, tetrahydrofuran, acetonitrile or N,N-dimethylformamide can be used as a proton source.

[0084] In the above step (B), benzonitrile is produced from benzoic acid.

[0085] In step (B), as a source of ammonia, ammonia gas, ammonia water, and urea can be cited. Among them, urea is preferred from the viewpoint 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. High boiling point solvents such as alkylbenzenes can be used in the synthesis, but the reaction will be carried out even without a solvent. The temperature required for the initial heating stage is preferably 100 to 180°C, more preferably 130 to 150°C, and further preferably 120 to 160°C. The appropriate heating time is 1 to 6 hours, preferably 2 to 4 hours. The second stage of heating is preferably 200 to 300°C, more preferably 210 to 280°C, and further preferably 230 to 250°C. The reaction time is preferably 1 to 8 hours, more preferably 2 to 6 hours, and further preferably 3 to 5 hours.

[0086] (A-iia) Using biologically derived succinic acid as a raw material, diisopropyl succinate is produced (the following step (I)).

[0087] As a method for producing diisopropyl succinate from succinic acid, for example, it can be produced by the method described in Otera J., Nishikido J., Esterification: Methods, Reactions, and Applications, 2nd Edition, 25 Nov. 2009, Wiley-VCH Verlag GmbH & Co. KGaA. For example, it can be produced by the method described in the examples described below.

[0088] [Chemistry 9]

[0089]

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

[0091] In the above step (I), the catalyst acid that can be used includes hydrochloric acid, sulfuric acid, formic acid, acetic acid, methanesulfonic acid or p-toluenesulfonic acid. Among them, hydrochloric acid and sulfuric acid are preferred from the perspective of cost.

[0092] (A-iiia) The diketopyrrolopyrrole compound represented by the formula (A-1) is produced by reacting the benzonitrile produced in the above (A-ia) with the diisopropyl succinate produced in the above (A-iia) (the following step (L)).

[0093] The reaction method for reacting benzonitrile with diisopropyl succinate is not particularly limited, and the benzonitrile can be produced by the method described in, for example, Chem. Eur. J. 2021, 27, 5259-5267, J. Phys. Chem. C 2016, 120, 2070-2078, etc. For example, the benzonitrile can be produced by the method described in the examples described below.

[0094] [Chemistry 10]

[0095]

[0096] In the above step (L), benzonitrile and diisopropyl succinate are reacted to produce a diketopyrrolopyrrole compound (PR255 pigment) represented by formula (A-1).

[0097] In step (L), the base that can be used for the deprotonation of diisopropyl succinate can include sodium methoxide, potassium methoxide, sodium tert-butoxide, potassium tert-butoxide, sodium hydride, potassium hydride, lithium diisopropylamide, metallic sodium or metallic potassium. Among them, when judging from the ease of operation, the ease of acquisition, and the deprotonation ability, sodium methoxide, potassium methoxide, sodium tert-butoxide, potassium tert-butoxide, sodium hydride, potassium hydride, and potassium hydride are preferred, and potassium butoxide is more preferred. As the solvent that can be used, methanol, ethanol, isopropanol, tert-butanol, tert-amyl alcohol, neopentyl alcohol, isopentanol, methyl isopropyl methanol, methyl isopropyl alcohol, dodecanol, etc. can be mentioned. The reaction time is preferably 5 to 24 hours, more preferably 8 to 20 hours, and further preferably 10 to 18 hours.

[0098] <Method for producing diketopyrrolopyrrole compound having a structure represented by formula (A-2)>

[0099] Next, the method for producing the diketopyrrolopyrrole compound represented by formula (A-2) is described below (see also Figure 1 Schematic diagram of ).

[0100] (A-ib) Using biologically derived 4-aminobenzoic acid as a raw material, 4-chlorobenzoic acid is obtained (the following step (C)), and then 4-chlorobenzonitrile is produced (the following step (D)).

[0101] As a method for producing 4-chlorobenzonitrile from 4-aminobenzoic acid, it can be produced by the method described in Examples described below, for example.

[0102] [Chemistry 11]

[0103]

[0104] In the above step (C), 4-chlorobenzoic acid is produced from 4-aminobenzoic acid using the Sandmeyer reaction, for example.

[0105] 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, hydrochloric acid, sulfuric acid, and acetic acid are preferred from the perspective of cost. As solvents that can be used, water, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylformamide, toluene, xylene, and alkylbenzenes 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 for a chlorine group in the final stage, potassium chloride, lithium chloride, cuprous chloride, cupric chloride, tetraethylammonium trichloride, tetrabutylammonium trichloride, N-chlorosuccinimide, trimethylsilyl chloride, etc. can be cited as chlorine sources. Among them, from the perspective of ease of operation, potassium chloride, lithium chloride, cuprous chloride, cupric chloride, and N-chlorosuccinimide are preferred.

[0106] In the step (D), 4-chlorobenzonitrile is produced by the same method as described in the step (B) with respect to 4-chlorobenzoic acid.

[0107] (A-iib) Diisopropyl succinate is produced using biologically derived succinic acid as a raw material (the following step (I)).

[0108] As a method for producing diisopropyl succinate from succinic acid, the same method as described in the above-mentioned (A-iia) can be used for production. For example, it can be produced by the method described in the Examples described later.

[0109] [Chemistry 12]

[0110]

[0111] (A-iiib) The diketopyrrolopyrrole compound represented by the formula (A-2) is produced by reacting the 4-chlorobenzonitrile produced in the above (A-ib) with the diisopropyl succinate produced in the above (A-iib) (the following step (M)).

[0112] As a reaction method for reacting 4-chlorobenzonitrile with diisopropyl succinate, the same method as described in the above-mentioned (A-iiia) can be used for production. For example, it can be produced by the method described in the Examples described later.

[0113] [Chemistry 13]

[0114]

[0115] In the step (M), benzonitrile and diisopropyl succinate are reacted by the same method as described in the step (A-iiia) to produce a diketopyrrolopyrrole compound (PR254 pigment) represented by the formula (A-2).

[0116] 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.

[0117] More preferably, both the 4-aminobenzoic acid and the succinic acid are derived from biomass.

[0118] The biobased content 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 biomass raw materials based on the mass balance method and the certificate trading system (Book & Claim) are available, it is easier to set the biobased content to 100% or more. In this patent, the biobased content including biomass raw materials based on the mass balance method and the certificate trading system is taken as the object.

[0119] (Composition containing diketopyrrolopyrrole compound)

[0120] The present invention may be a composition containing the diketopyrrolopyrrole compound of the present invention having a structure represented by formula (A).

[0121] The composition is used as a pigment composition, and is particularly preferably used as a diketopyrrolopyrrole red pigment.

[0122] The composition of the present invention may contain, for example, one or two or more diketopyrrolopyrrole compounds having a structure represented by formula (A).

[0123] As a more preferred embodiment of the composition of the present invention, for example, a composition containing a diketopyrrolopyrrole compound represented by the above formula (A-1) or a diketopyrrolopyrrole compound represented by the above formula (A-2) can be mentioned.

[0124] The proportion of the diketopyrrolopyrrole compound having a structure represented by the above formula (A) in the composition (more preferably the proportion of the diketopyrrolopyrrole compound represented by the above formula (A-1) or the above formula (A-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.

[0125] 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, it is preferably 20 to 80 for ink applications, 40 to 90 for coating applications, 50 to 90 for resin applications, and 50 to 100 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 cell and placing it in a specific surface area meter (Macsorb 1208).

[0126] (Application of the diketopyrrolopyrrole compound of the present invention)

[0127] The compound having a structure represented by formula (A) obtained by the above method and containing radioactive carbon atoms 14 The diketopyrrolopyrrole compound of the present invention of C and a composition containing the diketopyrrolopyrrole compound constitute a diketopyrrolopyrrole red pigment such as PR255 and PR254.

[0128] The diketopyrrolopyrrole compound of the present invention contains biomass-derived carbon and contributes to reduction of environmental load by carbon neutralization.

[0129] The diketopyrrolopyrrole compound of the present invention and the diketopyrrolopyrrole red pigment formed from a composition containing the diketopyrrolopyrrole compound can be used as a coloring composition, a molding composition, and the like.

[0130] In addition, the diketopyrrolopyrrole compound of the present invention and the diketopyrrolopyrrole red pigment formed from a composition containing the diketopyrrolopyrrole compound can be mixed with other resins, rubbers, additives, solvents, pigments or dyes as needed to prepare coating materials for cosmetics, pharmaceuticals or pesticides, or printed markings, stationery, writing instruments, printing inks, inkjet inks, metallic inks, coatings, plastic colorants, toners (color toners), color filters, etc. for use.

[0131] <Coloring composition>

[0132] The coloring composition of the present invention preferably contains the diketopyrrolopyrrole compound of the present invention, a diketopyrrolopyrrole red pigment composition formed of a composition containing the diketopyrrolopyrrole compound, and a dispersion medium.

[0133] The colored composition of the present invention preferably contains 0.5 to 50% by mass of the diketopyrrolopyrrole compound having a structure represented by the above formula (A), more preferably 2.5 to 35% by mass, and even more preferably 5 to 20% by mass.

[0134] <<Dispersion medium>>

[0135] 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.

[0136] Examples of the type of resin in the resin-type dispersant 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 copolymers, vinylnaphthalene-maleic acid copolymers, polyester-modified (meth)acrylic acid polymers, and salts thereof.

[0137] Examples of the form of the resin in the resin-type dispersant include a water-soluble resin and an emulsion (water-insoluble resin).

[0138] 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 Styrene copolymers such as diene copolymers and 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 rubbers, chlorinated polyolefin resins, terpene resins, coumarone-indene resins, alkyd resins, amino resins, petroleum resins, and modified resins thereof, etc.

[0139] Organic solvents can be classified into water-soluble solvents and water-insoluble solvents.

[0140] 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.

[0141] Each material constituting the coloring composition may be used alone or in combination of two or more.

[0142] <Molding composition>

[0143] 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.

[0144] Examples of thermoplastic resins include homopolymers or copolymers using ethylene, propylene, butylene, styrene, etc. as monomer components. More specifically, polyolefin resins such as high-density polyethylene (HDPE), linear low-density polyethylene (L-LDPE), low-density polyethylene (LDPE), polypropylene, polybutene, etc. 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.

[0145] The molding composition may contain wax. The wax is composed of low molecular weight polyolefins. They are polymers of olefin monomers such as ethylene, propylene, butene, etc., and may also 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).

[0146] 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.

[0147] 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.

[0148] 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 diketopyrrolopyrrole compound of the present invention.

[0149] The molding composition can be produced, for example, as a masterbatch containing the diketopyrrolopyrrole compound at a high concentration.

[0150] The masterbatch is preferably melt-kneaded by thermoplastic resin and pigment composition, and then, molded into any shape in a manner that is easy to use in the next process. Then, the masterbatch and the diluent resin (for example, the 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 that the dispersion formed by the pigment composition and the wax are melt-kneaded, and then melt-kneaded together with the thermoplastic resin to manufacture the masterbatch. The device used in the dispersion is preferably a blending mixer, a three-roll mill, etc.

[0151] Examples of uses of the molding composition include plastic molded products, sheets, and films.

[0152] <Toner>

[0153] 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, the dry toner is prepared by melting and kneading the pigment composition and the binder resin, and then performing a crushing and classification process after cooling. Then, a post-treatment process of mixing and adding additives can be performed to produce the toner.

[0154] 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, and petroleum-based resins.

[0155] Among them, polyester resins and styrene copolymers are preferred, and polyester resins are more preferred. The pigment composition has particularly excellent compatibility with polyester resins, so the diketopyrrolopyrrole compound can be uniformly and finely dispersed in the toner, thereby obtaining a high-quality toner.

[0156] 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 having an appropriate Mw is used, a toner having good anti-offset properties and low-temperature fixing properties can be obtained.

[0157] 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 and the image density is less likely to decrease in a high humidity environment.

[0158] The toner may further contain a charge control agent. If a charge control agent is used, a toner with a stable charge amount can be easily obtained. The charge control agent may be a positive or negative charge control agent selected appropriately.

[0159] 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.

[0160] 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.

[0161] The toner may be used as a one-component developer or a two-component developer. The two-component developer may further contain a carrier.

[0162] Examples of the carrier include magnetic powders such as iron powder, ferrite powder, and nickel powder, and coated products obtained by coating the surfaces of these powders with resins, etc. Examples of the resin coating 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.

[0163] <Paint>

[0164] The coating material contains a coloring composition (a pigment composition, a resin, and a solvent).

[0165] The resin may 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 resins, polyesters, and polyurethanes. In addition, the thermosetting resin preferably has a functional group that can react with a curing agent. Examples of the functional group include carboxyl groups and hydroxyl groups. Examples of the curing agent include isocyanate curing agents, epoxy curing agents, aziridine curing agents, and amine curing agents.

[0166] 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.

[0167] 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.

[0168] Among the solvents, water-soluble solvents include, for example, water, monohydric alcohols, dihydric alcohols, and glycols. Water-soluble solvents include, for example, 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 also be mentioned. Specific examples thereof include methoxypropanol and methoxybutanol. In addition, water-dilutable glycol ethers such as ethylene glycol butyl ether and diethylene glycol butyl ether may also be mentioned. It should be noted that a coating is called a water-based coating when it contains water in the solvent.

[0169] The coating material may further contain known additives.

[0170] Examples of uses of the coating include coatings for metals and coatings for plastics.

[0171] <Printing ink>

[0172] 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. It should be noted that when the solvent contains water, it is called an aqueous printing ink.

[0173] Examples of the resin include rosin resin, rosin-modified phenolic resin, polyurethane, nitrocellulose, acrylic resin, styrene-acrylic resin, and petroleum resin.

[0174] Examples of the water-insoluble solvent include toluene, xylene, butyl acetate, methyl acetate, methyl ethyl ketone, methyl isobutyl ketone, butanol, and aliphatic hydrocarbons.

[0175] The water-soluble solvents in the solvent 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 ethylene glycol butyl ether and diethylene glycol butyl ether may be mentioned.

[0176] 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.

[0177] The printing ink may further contain known additives.

[0178] <Inkjet ink>

[0179] 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, aqueous inkjet ink, and solvent-free inkjet ink, depending on whether or not there is a solvent.

[0180] The following description will focus on aqueous inkjet inks.

[0181] The resin used in the aqueous inkjet ink is very important for obtaining the fixability of the ink to the printed material (substrate).

[0182] The types of resins include, for example, acrylic resins, styrene-acrylic resins, polyester resins, polyamide resins, polyurethane resins, etc. In addition, the forms of resins include water-soluble resins, emulsion particles, etc. Among them, emulsion particles are preferred. Emulsion particles include single-component particles, core-shell particles, etc., which can be selected and used arbitrarily. If 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 with pH adjusters such as ammonia, various amines, and various inorganic bases as needed.

[0183] Solvents include non-water-soluble solvents, water, and water-soluble solvents. Water-soluble solvents include glycol ethers and glycols. These solvents penetrate the substrate very quickly, and also penetrate quickly into low-liquid-absorbing and non-liquid-absorbing substrates such as coated paper, art 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.

[0184] The water-soluble solvent is very important for preventing the nozzle part in the print head of the aqueous inkjet ink from drying and solidifying 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.

[0185] The inkjet ink may further contain additives, such as drying accelerators, penetrants, preservatives, chelating agents, and pH adjusters.

[0186] Inkjet ink is prepared 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.

[0187] 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.

[0188] Inkjet ink can be produced by various inkjet methods, such as charge control type, continuous jet type such as spray type, piezoelectric type, thermal type, electrostatic attraction type, etc.

[0189] Example

[0190] Hereinafter, the present invention will be described in more 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 %".

[0191] (Composition Analysis)

[0192] 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).

[0193] (Accelerator Mass Spectrometry (AMS))

[0194] Using a serial 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.

[0195] In the measurement, oxalic acid (HOxII) provided by the National Institute of Standards and Technology (NIST) was used as a 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.

[0196] (A) Synthesis of benzoic acid from 4-aminobenzoic acid

[0197] In a flask containing 4-aminobenzoic acid (10 g) dissolved in 73 mL of 1 M NaOH aqueous solution and immersed in an ice bath, 37% hydrochloric acid (25 g) was added dropwise. Then, 6.04 g of sodium nitrate was added, and the solution mixture was stirred in an ice bath for 30 minutes. THF216 g was added, and the reaction mixture was further stirred at 20°C for 3 hours. Then, the reaction mixture was extracted with ethyl acetate (3×100 mL). The organic layer was collected, dried over anhydrous MgSO4, and filtered. The solid obtained after evaporation of the solvent was dried in an oven overnight to obtain 5.3 g of solid.

[0198] (B) Synthesis of benzonitrile

[0199] Benzoic acid (10 g) was mixed with 6.9 g of urea and 0.08 g of platinum in 50 mL of alkylbenzene. The reaction mixture was heated at 150° C. for 2 hours, then raised to 250° C. and maintained for 3 hours. After cooling to room temperature, the solid was filtered, washed thoroughly with water, and dried in an oven overnight. 8.9 g of solid was obtained.

[0200] (C) Synthesis of 4-chlorobenzoic acid from 4-aminobenzoic acid

[0201] In a flask containing 4-aminobenzoic acid (10 g) dissolved in 73 mL of 1 M NaOH aqueous solution and immersed in an ice bath, 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.

[0202] (D) Synthesis of 4-chlorobenzonitrile

[0203] 4-Chlorobenzoic acid (10 g) was mixed with 5.4 g of urea and 0.06 g of platinum in 50 mL of alkylbenzene. The reaction mixture was heated at 150°C for 2 hours, then raised to 250°C and maintained for 3 hours. After cooling to room temperature, the solid was filtered, washed thoroughly with water, and dried in an oven overnight. 5.8 g of solid was obtained.

[0204] (I) Synthesis of diisopropyl succinate

[0205] A solution of bio-derived succinic acid (10 g) in isopropanol (150 mL) and 98% H2SO4 (0.42 g) was stirred at reflux for 15 hours. The solvent was removed under reduced pressure. The resultant was dissolved in DCM (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 16.3 g of liquid.

[0206] Synthesis of (L)R255

[0207] Benzonitrile (10.2 g) was added to a solution of potassium tert-butoxide (11.9 g) in tert-amyl alcohol (171.6 g) under a nitrogen atmosphere. Diisopropyl succinate (10 g) was added dropwise to the mixture, and the reaction mixture was then heated under reflux for 16 hours. After completion, the mixture was injected into a methanol solution (167.6 g) and a concentrated hydrochloric acid solution (29.7 g). The precipitate was filtered, washed with cold methanol, and dried in an oven overnight to obtain 11.1 g of a solid.

[0208] Thus, it is possible to obtain 14 C is the diketopyrrolopyrrole compound represented by the above (A-1).

[0209] Synthesis of (M)R254

[0210] 4-Chlorobenzonitrile (13.6 g) was added to a solution of potassium tert-butoxide (11.9 g) in tert-amyl alcohol (171.6 g) under a nitrogen atmosphere. Diisopropyl succinate (10 g) was added dropwise to the mixture, and the reaction mixture was then heated under reflux for 16 hours. After completion, a methanol solution (167.6 g) and a concentrated hydrochloric acid solution (29.7 g) were injected. The precipitate was filtered, washed with cold methanol, and dried in an oven overnight to obtain 13.8 g of a solid.

[0211] Thus, it is possible to obtain 14 C. The diketopyrrolopyrrole compound represented by the above (A-2) having a pMC of 22%.

[0212] It should be noted that, when synthesizing diisopropyl succinate, the diketopyrrolopyrrole compound represented by (A-2) was obtained by the same method as the above method except that succinic acid derived from petroleum was used instead. As a result, the radioactive carbon atom of the diketopyrrolopyrrole compound was 14 C was below the detection limit and could not be measured, and pMC was also 0%.

Claims

1. A diketopyrrolopyrrole compound containing a radioactive carbon atom 14 C, and has a structure represented by the following formula (A), [Chemistry 1] In formula (A), 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.

2. The diketopyrrolopyrrole compound according to claim 1, wherein The diketopyrrolopyrrole compound having a structure represented by the formula (A) is a diketopyrrolopyrrole compound represented by the following formula (A-1) or the following formula (A-2), [Chemistry 2] [Chemistry 3] 3 . A composition comprising the diketopyrrolopyrrole 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 diketopyrrolopyrrole compound having the structure represented by (A) 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 diketopyrrolopyrrole compound having the structure represented by (A) in the colored composition is 0.5% by mass to 50% by mass.

8. A method for producing a diketopyrrolopyrrole compound, wherein the method comprises producing a diketopyrrolopyrrole compound containing a radioactive carbon atom 14 C and a diketopyrrolopyrrole compound having a structure represented by the following formula (A), [Chemistry 4] In formula (A), 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, The preparation method of the diketopyrrolopyrrole compound is: (Ai) using 4-aminobenzoic acid as a raw material to produce benzonitrile which may have a substituent, (A-ii) using succinic acid as a raw material to produce diisopropyl succinate, in, At least one of the 4-aminobenzoic acid (Ai) and the succinic acid (A-ii) is a substance of biological origin, (A-iii) The benzonitrile which may have a substituent produced in (Ai) is reacted with the diisopropyl succinate produced in (A-ii) to produce a diketopyrrolopyrrole compound having a structure represented by the formula (A).

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