Isoindoline compounds

Abstract

Provided are: a biologically-derived isoindoline compound which can be used as an isoindoline-based yellow pigment and which is obtained by means of a safe, clean, green and carbon neutralization pathway; and a composition containing the isoindoline compound. An isoindoline compound which contains a radioactive carbon atom 14C and has a group represented by formula (A). In formula (A), R1-R4 each independently represent a hydrogen atom, a linear or branched alkyl group having 1-12 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a phenyl group which may be substituted by an alkyl group. In addition, R2 and R3 may be closed-loop to form a 5-to 8-membered ring. R7-R8 independently represent a hydrogen atom, a linear or branched alkyl group having 1-12 carbon atoms, or a phenyl group which may be substituted by an alkyl group. And * represents a binding bond. # imgabs0 #

Description

Technical Field

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

[0002] The molecules of isoindoline yellow pigments are not as large as azo dimers, and they are relatively fast to light and heat even though they do not contain halogens. Therefore, they have high potential for various applications such as automotive coatings, decorative coatings, GI coatings, plastics, inks, and special applications.

[0003] Commercially available isoindoline yellow pigments are produced by coupling a specific building block with DII (1,3-diimidoisoindole). This DII is mainly synthesized using phthalonitrile as a starting material (for example, see Non-Patent Document 1), and in addition, substances using phthalic anhydride as a starting material (for example, see Patent Document 1) have also been reported.

[0004] However, phthalonitrile is harmful to the human body and has an adverse effect on the environment. In addition, the supply source of phthalonitrile is usually only petroleum resources.

[0005] In recent years, from the perspectives of sustainable development, reduction of carbon dioxide emissions, and safety, there has been an active movement to switch raw materials from petroleum to raw materials from organisms (biomass), and to replace harmful chemical substances with less toxic substances.

[0006] Currently produced isoindoline yellow pigments are likely to fail to meet future environmental requirements, and from the viewpoints of cleanliness, greenness, and carbon neutrality, it is desired to provide isoindoline yellow pigments derived from biological sources.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Laid-Open No. 7-330729

[0010] Non-patent literature

[0011] Non-patent document 1: Chem. Lett. 1984 8 1423-1426 Summary of the invention

[0012] Problems to be solved by the invention

[0013] An object of the present invention is to provide an isoindoline compound derived from a biological source and obtained by a safe, clean, green and carbon-neutral route, which can be used as an isoindoline yellow pigment, and a composition containing the isoindoline compound.

[0014] Methods for solving problems

[0015] The present inventors have conducted research to solve the above problems and have found that a DA intermediate containing a radioactive carbon atom can be obtained by using bio-derived furan and bio-derived maleic anhydride as raw materials, obtaining a DA intermediate by Diels-Alder (DA) reaction, dehydrating and aromaticizing the DA intermediate, and aminating the DA intermediate with urea. 14 C, and coupling the bio-DII with a building block to obtain an isoindoline compound derived from a bio-source that can be used as an isoindoline-based yellow pigment, thereby completing the present invention.

[0016] That is, the present invention includes the following aspects.

[0017] [1] An isoindoline compound containing a radioactive carbon atom 14 C and having a group represented by the following formula (A),

[0018] [Chemistry 1]

[0019]

[0020] In the formula (A), R 1 ~R 4 independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a phenyl group which may be substituted with an alkyl group; and R 2 and R 3 Can close the ring to form a 5- to 8-membered ring; R 7 ~R 8 Each of the groups independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a phenyl group which may be substituted with an alkyl group; and * represents a bond.

[0021] [2] The isoindoline compound according to [1], wherein the isoindoline compound having a group represented by the formula (A) is an isoindoline compound represented by the following formula (A-1) or the following formula (A-2),

[0022] [Chemistry 2]

[0023]

[0024] [Chemistry 3]

[0025]

[0026] In the formula (A-1) and the formula (A-2), R 1 ~R 4 Indicates that the R1 ~R 4 Same meaning; R 7 ~R 8 Indicates that the R 7 ~R 8 Same meaning; R 9 ~R 10 With the R 7 ~R 8 Likewise, they independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a phenyl group which may be substituted with an alkyl group.

[0027] [3] The isoindoline compound according to [2], wherein the isoindoline compound represented by the formula (A-1) is an isoindoline compound represented by the following formula (A-1-1), or the isoindoline compound represented by the formula (A-2) is an isoindoline compound represented by the following formula (A-2-1),

[0028] [Chemistry 4]

[0029]

[0030] [Chemistry 5]

[0031]

[0032] [4] A composition comprising the isoindoline compound having a group represented by the formula (A) according to [1].

[0033] [5] The composition according to [4], which is used as a pigment composition.

[0034] [6] The composition according to [4], comprising at least two or more isoindoline compounds having a group represented by the formula (A).

[0035] [7] The composition according to [4], comprising an isoindoline compound represented by the following formula (A-1) and an isoindoline compound represented by the following formula (A-3).

[0036] [Chemistry 6]

[0037]

[0038] [Chemistry 7]

[0039]

[0040] In the formula (A-1) and the formula (A-3), R 1 ~R 4independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a phenyl group which may be substituted with an alkyl group; and R 2 and R 3 Can close the ring to form a 5- to 8-membered ring; R 7 ~R 10 Each of them independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a phenyl group which may be substituted with an alkyl group.

[0041] [8] The composition according to [7], wherein the ratio of the isoindoline compound represented by the formula (A-3) in the composition is 0.5 to 10.0% by mass.

[0042] [9] The composition according to [7], wherein the isoindoline compound represented by the formula (A-1) is an isoindoline compound represented by the following formula (A-1-1), and the isoindoline compound represented by the formula (A-3) is an isoindoline compound represented by the following formula (A-3-1),

[0043] [Chemistry 8]

[0044]

[0045] [Chemistry 9]

[0046]

[0047]

[10] A method for producing an isoindoline compound containing a radioactive carbon atom 14 C and having a group represented by the following formula (A) and a method for producing an isoindoline compound,

[0048] [Chemistry 10]

[0049]

[0050] In the formula (A), R 1 ~R 4 independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a phenyl group which may be substituted with an alkyl group; and R 2 and R 3 Can close the ring to form a 5- to 8-membered ring; R 7 ~R 8 independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a phenyl group which may be substituted by an alkyl group; * represents a bond;

[0051] In the method for producing the isoindoline compound, barbituric acid represented by the following formula (B) is reacted with a compound represented by the following formula (I-2) under the condition of not containing an acid solvent or under the condition of containing at least one acid selected from the group consisting of hydrochloric acid, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, acetic acid, trifluoromethanesulfonic acid, phosphoric acid, polyphosphoric acid, pyrophosphoric acid and nitric acid to obtain an isoindoline compound having a group represented by the above formula (A).

[0052] [Chemistry 11]

[0053]

[0054] In the formula (I), R 1 ~R 4 Indicates that the R 1 ~R 4 The same meaning,

[0055] [Chemistry 12]

[0056]

[0057] In the formula (B), R 5 ~R 6 Each of them independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a phenyl group which may be substituted with an alkyl group.

[0058]

[11] The method for producing an isoindoline compound according to

[10] , wherein, for the compound represented by the formula (I-2), a compound represented by the following formula (PA) is obtained from a compound represented by the following formula (DA), and the isoindoline compound represented by the formula (I-2) is obtained from the compound represented by the following formula (PA).

[0059] [Chemistry 13]

[0060]

[0061] In the formula (DA), R 1 ~R 4 Indicates that the R 1 ~R 4 The same meaning,

[0062] [Chemistry 14]

[0063]

[0064] In the formula (PA), R 1 ~R 4 Indicates that the R 1 ~R 4 Same meaning.

[0065]

[12] The method for producing an isoindoline compound according to

[10] , wherein the solvent is any one selected from the group consisting of H2O, dimethylacetamide (DMA), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), MeOH, EtOH, isopropyl alcohol (IPA) and tBuOH.

[0066] Effects of the Invention

[0067] According to the present invention, it is possible to provide an isoindoline compound derived from a biomass and obtained by a safe, clean, green and carbon-neutral route, which can be used as an isoindoline yellow pigment, and a composition containing the isoindoline compound. BRIEF DESCRIPTION OF THE DRAWINGS

[0068] [ Figure 1 ] is a diagram showing the TEM observation results of the pigment of Example 1.

[0069] [ Figure 2 ] is a diagram showing the TEM observation results of the pigment of Comparative Example 1. DETAILED DESCRIPTION

[0070] 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.

[0071] (Contains radioactive carbon atoms 14 C and an isoindoline compound having a group represented by the following formula (A)

[0072] The isoindoline compounds of the present invention contain radioactive carbon atoms 14 C.

[0073] The isoindoline compound of the present invention has a group represented by the following formula (A).

[0074] [Chemistry 15]

[0075]

[0076] In formula (A), R 1 ~R 4 Each of R independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a phenyl group which may be substituted with an alkyl group. 2 and R 3 The ring can be closed to form a 5- to 8-membered ring. 7 ~R 8 Each of the groups independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a phenyl group which may be substituted with an alkyl group. * represents a bond.

[0077] The isoindoline compound of the present invention uses a radioactive carbon atom represented by the following formula (I-2): 14 The isoindoline compound of the present invention is prepared by using a bio-isoindoline compound of C, which is prepared by using furan derived from a bio-source and maleic anhydride derived from a bio-source. Therefore, the isoindoline compound of the present invention contains a biological (biomass) component derived from a biological raw material. The isoindoline compound of the present invention contains a biological component, for example, by measuring the radioactive carbon atoms. 14 C to confirm.

[0078] [Chemistry 16]

[0079]

[0080] In the above formula (I-2), R 1 ~R 4 Represents the same as above R 1 ~R 4 Same meaning.

[0081] For example, there is no difference in physical properties such as molecular weight, mechanical properties, and thermal properties between compounds and compositions derived from organisms and from petroleum. In order to distinguish between them, the biomass degree is usually used. The biomass degree refers to the carbon content of compounds and compositions derived from petroleum that does not contain 14 C (radiocarbon 14, half-life 5730 years), so the accelerator mass analysis 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.

[0082] The biomass degree is measured by, for example, burning a sample to be measured to generate carbon dioxide, and reducing the carbon dioxide purified through a vacuum line with hydrogen using iron as a catalyst to generate graphite.

[0083] 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) is measured, and the carbon content of the sample is calculated based on the measured value 14 The ratio of C concentration to standard modern carbon. It should be noted that 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.

[0084] As an index for evaluating the biomass content, for example, pMC (percent modern carbon) can be cited.

[0085] Here, pMC (modern carbon percentage) can be calculated by measurement according to ASTM-D6866-18 and represents the percentage of carbon in the object. 14 C concentration relative to that in standard modern carbon 14 The ratio of C concentration. It should be noted that the object does not contain radioactive carbon atoms. 14 In the case of C, pMC is 0%.

[0086] In the above formula (I), R 2 and R 3 As described above, a 5- to 8-membered ring can be formed by ring closure. Moreover, the ring structure can be a functional ether, alcohol or carboxyl functional group. Here, the functional functional group refers to a ring structure that can have -OH group, -COOH group, -O- group. For example, it can also be a compound represented by the following formula (v), the following formula (vi), and the following formula (vii).

[0087] [Chemistry 17]

[0088]

[0089] Preferred embodiments of the isoindoline compound having a group represented by the formula (A) include, for example, isoindoline compounds represented by the following (A-1) and isoindoline compounds represented by the following (A-2).

[0090] [Chemistry 18]

[0091]

[0092] [Chemistry 19]

[0093]

[0094] In the above formula (A-1) and the above formula (A-2), R 1 ~R 4 Represents the same as above R 1 ~R 4 Same meaning. 7 ~R 8 Represents the same as above R 7 ~R 8 Same meaning. 9 ~R 10 With the above R 7 ~R 8 Likewise, they independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a phenyl group which may be substituted with an alkyl group.

[0095] The pMC (modern carbon percentage) in the isoindoline compound represented by formula (A-1) and the isoindoline compound represented by formula (A-2) is preferably 1% or more, more preferably 50% or more, more preferably 75% or more, more preferably 90% or more, and further preferably 99% or more.

[0096] Furthermore, as a preferred embodiment of the isoindoline compound represented by formula (A-1), for example, as a preferred embodiment of the isoindoline compound represented by the following (A-1-1), and the isoindoline compound represented by formula (A-2), for example, the isoindoline compound represented by the following (A-2-1) can be cited. It should be noted that the isoindoline compound represented by (A-1-1) is a compound known by the pigment constituting Y139, and the isoindoline compound represented by (A-2-1) is a compound known by the pigment constituting Y185.

[0097] [Chemistry 20]

[0098]

[0099] [Chemistry 21]

[0100]

[0101] The isoindoline compound of the present invention containing a group represented by formula (A) or a composition containing the isoindoline compound as a radioactive carbon atom 14 C. Use isoindoline yellow pigments containing biological components.

[0102] (Method for producing an isoindoline compound containing a group represented by formula (A))

[0103] The isoindoline compounds of the present invention contain radioactive carbon atoms 14 C. That is, it contains a biological component and contains a group represented by formula (A). The isoindoline compound of the present invention can be obtained by the method described below.

[0104] The compound represented by the following formula (I-2) can be reacted with barbituric acid represented by the following formula (B) even in the absence of an acid, more preferably in the presence of an acid in a solvent, to obtain an isoindoline compound having a group represented by the above formula (A).

[0105] [Chemistry 22]

[0106]

[0107] In the above formula (I-2), R 1 ~R 4 Represents the same as above R1 ~R 4 Same meaning.

[0108] [Chemistry 23]

[0109]

[0110] In the above formula (B), R 5 ~R 6 Each of them independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a phenyl group which may be substituted with an alkyl group.

[0111] As a preferred embodiment of the method for producing an isoindoline compound containing a group represented by formula (A), a method for producing an isoindoline compound represented by formula (A-1) is particularly exemplified.

[0112] The isoindoline compound represented by the formula (A-1) can be obtained by the method described below.

[0113] [Chemistry 24]

[0114]

[0115] In the above formula (I-2) and the above formula (A-1), R 1 ~R 10 Represents the same as above R 1 ~R 10 Same meaning.

[0116] <Reaction G>

[0117] The compound represented by the above formula (I-2) will proceed even in the absence of an acid, and more preferably, the barbituric acid represented by the above formula (B) is reacted under conditions containing an acid solvent (more specifically, under conditions containing at least one acid selected from the group consisting of hydrochloric acid, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, acetic acid, trifluoromethanesulfonic acid, phosphoric acid, polyphosphoric acid, pyrophosphoric acid and nitric acid) or under conditions not containing an acid solvent, thereby obtaining the isoindoline compound represented by the above formula (A-1).

[0118] The concentration of the acid used in the reaction G is preferably 0.5 to 30% by mass, more preferably 1 to 10% by mass.

[0119] The solvent used when reacting the barbituric acid represented by the above formula (B) is preferably any one selected from the group consisting of H2O, dimethylacetamide (DMA), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), MeOH, EtOH, isopropyl alcohol (IPA) and tBuOH.

[0120] In the isoindoline compound having a group represented by the above formula (A-1) obtained by reaction G, R 7 and R 8 Corresponding to R in the above formula (B) 5 and R 6 , which can be R 7 For R 5 , R 8 For R 6 , or it can be R 7 For R 6 , R 8 For R 5 In addition, R 9 and R 10 Similarly, they correspond to R in the above formula (B) 5 and R 6 , which can be R 9 For R 5 , R 10 For R 6 , or it can be R 9 For R 6 , R 10 For R 5 .

[0121] It should be noted that the compound represented by the above formula (I-2) can be obtained from the compound represented by the following formula (DA) to obtain the compound represented by the following formula (PA), and the isoindoline compound represented by the above formula (I-2) can be obtained from the compound represented by the above formula (PA).

[0122] [Chemistry 25]

[0123]

[0124] In formula (DA), R 1 ~R 4 Represents the same as above R 1 ~R 4 Same meaning.

[0125] [Chemistry 26]

[0126]

[0127] In formula (PA), R 1 ~R 4 Represents the same as above R 1 ~R 4 Same meaning.

[0128] When the compound represented by the above formula (DA) is used to obtain the compound represented by the above formula (PA), the reaction may be carried out under acidic conditions.

[0129] The acidic conditions may be any conditions as long as they allow the reaction to proceed appropriately, and may be, for example, formed by using any acid selected from the group consisting of hydrochloric acid, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, acetic acid, acetic anhydride, trifluoromethanesulfonic acid, phosphoric acid, phosphoric anhydride, polyphosphoric acid, pyrophosphoric acid, nitric acid, or a mixture of these acids.

[0130] When the isoindoline compound represented by the above formula (I-2) is obtained from the compound represented by the above formula (PA), ammonium molybdate is used as a catalyst and urea or NH 3 is used as an amine source, and an amination reaction is carried out in the presence of these.

[0131] As a preferred embodiment of the method for producing the isoindoline compound represented by formula (I-2), for example, the following production method can be mentioned.

[0132] <Method for producing the isoindoline compound represented by (I-2)>

[0133] The isoindoline compound represented by the formula (I-2) can be obtained from the compound represented by the following formula (DA) via the compound represented by the following formula (PA) or the following formula (I-2 nitrate).

[0134] The specific reaction pathway of this production method is shown below.

[0135] [Chemistry 27]

[0136]

[0137] In the formula, R 1 ~R 4 Represents the same as above R 1 ~R 4 Same meaning.

[0138] <<Reaction A>>

[0139] Compound (PA) can be produced by performing a ring-opening dehydration reaction of compound (DA).

[0140] The reaction solvent may be any solvent as long as the reaction proceeds appropriately, but water, acetonitrile, toluene, xylene, alkylbenzene, or a mixed solvent thereof, or no solvent is preferred.

[0141] The reaction temperature may be any temperature as long as the reaction proceeds appropriately, and is preferably 20 to 150° C., more preferably 30 to 120° C., and further preferably 40 to 100° C. As a lower limit, it is preferably 20° C. or more, preferably 25° C. or more, preferably 30° C. or more, preferably 35° C. or more, and preferably 40° C. or more. As an upper limit, it is preferably 150° C. or less, preferably 140° C. or less, preferably 130° C. or less, preferably 120° C. or less, preferably 110° C. or less, and preferably 100° C. or less.

[0142] The above reaction can be carried out under acidic conditions. The acidic conditions can be any conditions that allow the reaction to proceed appropriately, and can be formed by using any acid selected from the group consisting of hydrochloric acid, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, acetic acid, acetic anhydride, trifluoromethanesulfonic acid, phosphoric acid, phosphoric anhydride, polyphosphoric acid, pyrophosphoric acid, nitric acid, or a mixture of these acids.

[0143] Among them, it is preferred to use an acid containing sulfur or phosphorus. This is because these acids may become δ as shown in the following formula (p). + and δ - Configuration.

[0144] [Chemistry 28]

[0145]

[0146] In formula (p), X represents -OH, -ONa, -OK or methyl. Y represents a sulfur atom or a phosphorus atom, and Z represents a hydrogen atom, -COCH3, -COH or -(PO2). n OH.

[0147] The amount of the acid is preferably 0.1 to 3000 mol%, preferably 0.5 to 2500 mol%, preferably 1 to 2000 mol%, preferably 5 to 1500 mol%, preferably 10 to 1000 mol%, preferably 20 to 500 mol%, preferably 50 to 500 mol%, preferably 70 to 500 mol%, preferably 100 to 500 mol%, preferably 150 to 500 mol%, preferably 200 to 500 mol%, preferably 250 to 500 mol%, preferably 300 to 500 mol%. The lower limit is preferably 0.1 mol% or more, preferably 0.5 mol% or more, preferably 1 mol% or more, preferably 5 mol% or more, preferably 10 mol% or more, preferably 20 mol% or more, preferably 50 mol% or more, preferably 70 mol% or more, preferably 100 mol% or more, preferably 150 mol% or more, preferably 200 mol% or more, preferably 250 mol% or more, preferably 300 mol% or more. The upper limit is preferably 3000 mol% or less, preferably 2500 mol% or less, preferably 2000 mol% or less, preferably 1500 mol% or less, preferably 1000 mol% or less, and preferably 500 mol% or less. These upper limits and lower limits may be used in any combination.

[0148] <<Reaction C>>

[0149] As shown in the above reaction A, after the reaction under acidic conditions, in reaction C, amination can be carried out in the presence of ammonium molybdate as a catalyst and urea or NH3 as an amine source.

[0150] It should be noted that in reaction C, when the oxygen atoms in the compound represented by the above-mentioned compound (PA) are replaced by nitrogen atoms, if the replacement is 1 to 2 oxygen atoms, there is no need to add any special additives, but in order to replace all oxygen atoms with nitrogen atoms as in reaction C, it is preferred to add a compound represented by the following formula (q) to prevent side reactions such as oligomerization and polymerization.

[0151] [Chemistry 29]

[0152] M f+ [NO3] f (q)

[0153] In formula (q), M f+ Indicates NH4 + , Li + 、Na + , K + Mg 2+ , Ca 2+ or Al3+ .

[0154] <<Reaction D>>

[0155] In the above reaction D, by supplying aqueous ammonia and sodium hydroxide to the reactant obtained in reaction C, the isoindoline compound represented by formula (I-2) can be produced.

[0156] When the above production method is used, a composition containing the compound represented by formula (I-2) can be obtained. However, it is also possible to extract only the compound represented by formula (I-2) by purifying it by a known and conventional method.

[0157] The compound represented by the above formula (DA) for producing the isoindoline compound represented by the above formula (I-2) can be obtained by reacting a compound represented by the following formula (FR) with maleic anhydride.

[0158] [Chemistry 30]

[0159]

[0160] In formula (FR), R 1 ~R 4 Represents the same as above R 1 ~R 4 Same meaning.

[0161] The maleic anhydride mentioned above is preferably derived from biomass.

[0162] The compound represented by the above formula (FR) is preferably derived from biomass.

[0163] More preferably, both the maleic anhydride and the compound represented by the formula (FR) are derived from biomass.

[0164] 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, in the case where a biomass raw material based on a mass balance method or a certificate transaction (Book & Claim) method can be obtained, it becomes easier to set the biomass degree to be 1% or more and 100% or less. In this patent, the biomass degree of biomass raw materials based on a mass balance method and a certificate transaction method is the object.

[0165] Maleic anhydride derived from biomass can be obtained, for example, by dehydration cyclization of maleic acid obtained by oxidation of FF and HMF, or can also be obtained by direct oxidation, wherein FF and HMF are obtained by the methods described in Japanese Patent No. 5791838 and Japanese Patent No. 6328990. The compound represented by formula (FR) derived from biomass can be obtained, for example, by decarbonylation reaction, reduction reaction and dehydration reaction of FF and HMF obtained by the methods described in the above Japanese Patent No. 5791838 or the above Japanese Patent No. 6328990.

[0166] The specific reaction pathway of the above-mentioned production method is shown below.

[0167] [Chemistry 31]

[0168]

[0169] <<Reaction a>>

[0170] Compound (DA) can be produced by subjecting compound (FR) and maleic anhydride to a Diels-Alder reaction.

[0171] The above reaction may be carried out with or without a reaction solvent. Any reaction solvent may be used as long as the reaction can proceed appropriately, but chloroform, dioxane, ethyl acetate, alkylbenzene, toluene, xylene, and diethyl ether are preferred.

[0172] The reaction temperature may be any temperature as long as the reaction proceeds appropriately, preferably -10 to 100°C, more preferably 0 to 80°C, further preferably 10 to 70°C, and particularly preferably 15 to 50°C. As the lower limit, it is preferably -10°C or higher, more preferably 0°C or higher, further preferably 10°C or higher, and particularly preferably 15°C or higher. As the upper limit, it is preferably 100°C or lower, more preferably 80°C or lower, further preferably 70°C or lower, and particularly preferably 50°C or lower.

[0173] The reaction pressure may be any pressure as long as it is a pressure at which the reaction is suitably carried out, preferably 0.1 to 5 MPa, more preferably 0.1 to 3 MPa, further preferably 0.1 to 1 MPa, and particularly preferably 0.1 to 0.5 MPa. As a lower limit, it is preferably 0.1 MPa or more, preferably 0.2 MPa or more, preferably 0.3 MPa or more, and preferably 0.4 MPa or more. As an upper limit, it is preferably 5 MPa or less, preferably 3 MPa or less, preferably 1 MPa or less, preferably 0.9 MPa or less, preferably 0.8 MPa or less, preferably 0.7 MPa or less, preferably 0.6 MPa or less, and preferably 0.5 MPa or less.

[0174] (Composition containing isoindoline compound)

[0175] The present invention may be a composition containing the isoindoline compound of the present invention having a group represented by formula (A).

[0176] This composition is preferably used as a pigment composition, particularly as an isoindoline-based yellow pigment.

[0177] The composition of the present invention may contain, for example, one or two or more isoindoline compounds having a group represented by formula (A).

[0178] As a more preferred embodiment of the composition of the present invention, for example, a composition containing an isoindoline compound represented by the following formula (A-1) and / or an isoindoline compound represented by the following formula (A-3) can be mentioned.

[0179] [Chemistry 32]

[0180]

[0181] [Chemistry 33]

[0182]

[0183] In the above formula (A-1) and the above formula (A-3), R 1 ~R 4 Represents the same as above R 1 ~R 4 Same meaning. 7 ~R 10 Represents the same as above R 7 ~R 10 Same meaning.

[0184] The proportion of the isoindoline compound represented by the above formula (A-3) in the composition is preferably 0 to 30% by mass, more preferably 0.001 to 15% by mass, further preferably 0.01 to 10% by mass, further preferably 0.1 to 7% by mass, further preferably 0.5 to 5.0% by mass.

[0185] As described in the column of the above <Method for producing isoindoline compounds represented by (I-2)>, a compound represented by the above formula (DA) is obtained by Diels-Alder (DA) reaction using furan derived from a biological source and maleic anhydride derived from a biological source as raw materials, and the compound represented by the above formula (DA) is dehydrated and aromaticized, and aminated with urea to produce a compound containing a radioactive carbon atom. 14C. In this case, the isoindoline compound represented by the formula (I-2) may also contain the isoindoline compound represented by the following formula (I-1) produced in the production process in the composition containing the isoindoline compound represented by the formula (I-2).

[0186] [Chemistry 34]

[0187]

[0188] In the above formula (I-1), R 1 ~R 4 Represents the same as above R 1 ~R 4 Same meaning.

[0189] In a composition containing an isoindoline compound represented by formula (I-1) in addition to the isoindoline compound represented by formula (I-2), by reacting the barbituric acid represented by formula (B) described in the column of <Reaction G> in the above (method for producing an isoindoline compound containing a group represented by formula (A)), in addition to the isoindoline compound represented by formula (A-1), an isoindoline compound represented by formula (A-3) is produced.

[0190] In the present invention, a composition containing an isoindoline compound represented by the above formula (A-3) in addition to the isoindoline compound represented by the above formula (A-1) can be provided. The pigment composition has excellent color strength and shows pigment performance equal to or better than that of a commercially available non-bio-isoindoline pigment composition. Thus, a Y139 isoindoline yellow pigment composition with excellent color strength can be provided.

[0191] As a more preferred embodiment of the composition of the present invention, a composition containing an isoindoline compound represented by the following formula (A-1-1) and an isoindoline compound represented by the following formula (A-3-1) can be mentioned.

[0192] [Chemistry 35]

[0193]

[0194] [Chemistry 36]

[0195]

[0196] The proportion of the isoindoline compound represented by the above formula (A-3-1) in the composition is preferably 0 to 30% by mass, more preferably 0.001 to 15% by mass, further preferably 0.01 to 10% by mass, further preferably 0.1 to 7% by mass, further preferably 0.5 to 5.0% by mass.

[0197] 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 measurement cell, setting it in a specific surface area meter (Macsorb 1208).

[0198] (Application of the isoindoline compound of the present invention)

[0199] The compound obtained by the above method contains a group represented by formula (A) and contains a radioactive carbon atom 14 The isoindoline compound of the present invention of C and a composition containing the isoindoline compound constitute an isoindoline yellow pigment such as Y139 and Y185.

[0200] The isoindoline compound of the present invention contains carbon derived from biomass and contributes to reduction of environmental load by carbon neutralization.

[0201] Furthermore, since the isoindoline compound of the present invention is obtained by the above-mentioned production method, the number and position of various functional groups can be controlled by changing the type of furan or changing it to another type of diene.

[0202] The isoindoline yellow pigment formed from the isoindoline compound of the present invention and a composition containing the isoindoline compound can be used as a coloring composition, a molding composition, or the like.

[0203] In addition, the isoindoline yellow pigment formed by the isoindoline compound of the present invention and the composition containing the isoindoline compound can be mixed with other resins, rubbers, additives, solvents, pigments, dyes, etc. as needed to prepare a coating material for cosmetics, pharmaceuticals or pesticides or a printed mark, stationery, writing tools, printing inks, inkjet inks, metallic inks, coatings, plastic colorants, toners (color toners), color filters, etc. for use.

[0204] <Coloring Composition>

[0205] The coloring composition preferably contains the isoindoline compound of the present invention, an isoindoline yellow pigment composition containing a composition having the isoindoline compound, and a dispersion medium.

[0206] <<Dispersion Medium>>

[0207] 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. It should be noted that a low molecular weight dispersant such as a surfactant may be used as needed.

[0208] 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.

[0209] In addition, examples of the form of the resin in the resin-type dispersant include a water-soluble resin and an emulsion (water-insoluble resin).

[0210] 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), polypropylene, and 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 Diene 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.

[0211] Organic solvents can be classified into water-soluble solvents and water-insoluble solvents.

[0212] 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.

[0213] Each material constituting the coloring composition may be used alone or in combination of two or more.

[0214] <Molding Composition>

[0215] 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.

[0216] 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, polybutylene, 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. In addition, the number average molecular weight of the thermoplastic resin exceeds 30,000, preferably 200,000 or less.

[0217] The molding composition may contain wax. The wax is composed of low molecular weight polyolefins. These 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).

[0218] 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, thereby achieving an excellent balance between slidability and bleed-out suppression.

[0219] 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.

[0220] 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 isoindoline compound of the present invention.

[0221] The molding composition can be produced, for example, as a masterbatch containing the isoindoline compound at a high concentration.

[0222] 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 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, for example, 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 by the dispersion is, for example, preferably a co-mixing mixer, a three-roll mill, etc.

[0223] Examples of uses of the molding composition include plastic molded products, sheets, and films.

[0224] <Toner>

[0225] The toner contains a coloring composition (pigment composition, resin). The resin in the toner is called a binder resin, preferably a thermoplastic resin. The toner can be a dry toner or a wet toner. For example, in the 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-processing process of mixing and mixing additives can be performed to produce the toner.

[0226] 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.

[0227] 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 isoindoline compound is uniformly and finely dispersed in the toner, and thus a high-quality toner can be obtained.

[0228] 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-smearing properties and low-temperature fixing properties can be obtained.

[0229] 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.

[0230] 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.

[0231] 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.

[0232] 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.

[0233] In addition, the toner can be used as a single-component developer or a two-component developer. The two-component developer may further contain a carrier.

[0234] 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, silicone-containing resins, polyamide resins, ionomer resins, and polyphenylene sulfide resins.

[0235] <Paint>

[0236] The coating material contains a coloring composition (a pigment composition, a resin, and a solvent).

[0237] 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, and polyurethane. In addition, the thermosetting resin preferably has a functional group that can react with a curing agent. Examples of the functional group include carboxyl and hydroxyl groups. Examples of the curing agent include isocyanate curing agents, epoxy curing agents, aziridine curing agents, and amine curing agents.

[0238] 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.

[0239] 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.

[0240] 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 butanediol and butyl diglycol may also be mentioned. It should be noted that when the coating contains water in the solvent, it is called a water-based coating.

[0241] The coating material may further contain known additives.

[0242] Examples of uses of the coating include coatings for metals and coatings for plastics.

[0243] <Printing ink>

[0244] 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.

[0245] Examples of the resin include rosin resin, rosin-modified phenolic resin, polyurethane, nitrocellulose, acrylic resin, styrene-acrylic resin, and petroleum resin.

[0246] Examples of the water-insoluble solvent include toluene, xylene, butyl acetate, methyl acetate, methyl ethyl ketone, methyl isobutyl ketone, butanol, and aliphatic hydrocarbons.

[0247] Examples of 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 butanediol and butyl diglycol may also be mentioned.

[0248] 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.

[0249] The printing ink may further contain known additives.

[0250] <Inkjet Ink>

[0251] The inkjet ink preferably contains a pigment composition and a resin, and 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.

[0252] Hereinafter, the description will be mainly focused on aqueous inkjet ink.

[0253] The resin used in the aqueous inkjet ink is important in order to obtain the fixability of the ink to the printed material (substrate).

[0254] 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.

[0255] Examples of the solvent include non-water-soluble solvents, water, and water-soluble solvents. Examples of the water-soluble solvent include glycol ethers and ethylene 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.

[0256] The water-soluble solvent is important for preventing the nozzle portion in the print head of the aqueous inkjet ink from drying and solidifying and obtaining ink ejection stability. 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.

[0257] The inkjet ink may further contain additives, such as drying accelerators, penetrants, preservatives, chelating agents, and pH adjusters.

[0258] 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.

[0259] 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.

[0260] 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.

[0261] Example

[0262] 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 %".

[0263] (Synthesis Example 1) Synthesis of DA intermediate

[0264] In a nitrogen atmosphere, 12 g of biomass-derived maleic anhydride was dissolved in ether (250 ml) in a reactor equipped with a stirring device, and 10 g of biomass-derived furan was added, and the mixture was reacted at room temperature and 0.25 MPa for 24 hours. Thereafter, the white crude product was filtered with a filter and vacuum dried to obtain 20 g of a DA intermediate.

[0265] (Synthesis Example 1) Bio-DII

[0266] Add 14 g of acetic anhydride to 74 g of methanesulfonic acid, and slowly add 5 g of DA intermediate while cooling in an ice bath. Stir the reaction mixture at room temperature for 2 hours, and then heat it at 80°C for 4 hours. Extract the reaction mixture with toluene (3×50 mL). Wash the combined toluene with brine and sodium bicarbonate, and evaporate under reduced pressure. Mix 13 g of urea, 6 g of ammonium nitrate, and 0.03 g of molybdenum in 10 mL of alkylbenzene in the obtained needle white. After heating the reaction mixture at 165°C for 5 hours, remove the alkylbenzene by vacuum distillation. Add 30 mL of methanol, distill for 15 minutes, cool to room temperature, and filter. Disperse the obtained solid in 10 mL of water, add 3 g of ammonia water and 4.4 mL of 25% caustic soda. Cool the solution in an ice bath, filter the precipitated solid, and wash with water. By vacuum drying the obtained solid, a radioactive carbon C in the molecule is obtained. 14 2.9g of compound.

[0267] (Example 1) Synthesis of Isoindoline Compounds

[0268] In a reaction vessel equipped with a cooling tube, 1.2 g of the bio-DII obtained in Synthesis Example 1, 2.7 g of barbituric acid, 19 mL of water, and 1 mL of acetic acid with a concentration of 5% by mass were added, and heated to 90° C. while stirring. After stirring for 1.5 hours, the mixture was cooled to room temperature, filtered out with a filter, and washed with water, IPA, and water in sequence. The obtained solid was dried once in an oven, thereby obtaining a molecule containing radioactive carbon C 14 2.7g of isoindoline compound.

[0269] (Comparative Example 1)

[0270] Commercially available Y139 (Fanchon Yellow 279-5139) (manufactured by Sun Chemical Co., Ltd.) was purchased and used.

[0271] (Quality Analysis)

[0272] The pigment compositions containing isoindoline compounds obtained in Example 1 and Comparative Example 1 were subjected to mass analysis. As the analysis method, 5 mg of the obtained pigment composition was dissolved in THF and subjected to FD-MS JMS-T100 GC (manufactured by JEOL). The results are shown in the following table.

[0273] [Table 1]

[0274] m / z 183 238 257 280 312 323 334 367 384 568 640 896 Example 1 0.2 0.1 3 - 0.1 - 0.1 96.6 - - - - Comparative Example 1 - - 0.2 0.1 - 0.2 - 98.8 0.1 0.1 0.3 0.2

[0275] From the results in Table 1, it is understood that the pigment composition of Example 1 contains 96.6% of the compound represented by the above formula (A-1-1) and 3.0% of the compound represented by the above formula (A-3-1).

[0276] (TEM observation)

[0277] The pigment compositions containing the isoindoline compound obtained in Example 1 and Comparative Example 1 were observed by TEM to confirm the state of the particles.

[0278] The results of TEM observation of Example 1 are shown in Figure 1 The results of TEM observation of Comparative Example 1 are shown in Figure 2 .

[0279] The specific surface area (BET value) of Example 1 is 74 m 2 / g, and the BET value of Comparative Example 1 is 18m 2 / g.

[0280] (Accelerator Mass Spectrometry (AMS))

[0281] 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.

[0282] 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 carbon in the sample. 14 The ratio of C concentration relative to standard modern carbon.

[0283] The analysis results of Example 1 and Comparative Example 1 by the AMS method are shown in Table 2 below.

[0284] [Table 2]

[0285] Data Name pMC(%) Example 1 51.63±0.21 Comparative Example 1 0.20±0.02

[0286] (Flat plate ink test)

[0287] Using the pigment compositions of Example 1 and Comparative Example 1, 1 part of the pigment composition and 4 parts of MG63 varnish were kneaded with a Hoover grinder, 10 times of FG79 white was added, the discharged ink was spread on paper, and L was measured using a spectrophotometer (Datacolor 650). * a * b * C * h *value and color intensity. * a * b * C * h * The difference between Example 1 and Comparative Example 1 (Example 1-Comparative Example 1) is shown in Table 3 below.

[0288] [Table 3]

[0289] <![CDATA[L * ]]> <![CDATA[a * ]]> <![CDATA[b * ]]> <![CDATA[C * ]]> <![CDATA[h * ]]> The difference between Example 1 and Comparative Example 1 0.53 -5.79 12.18 10.79 11.61

[0290] Regarding color strength, when the pigment composition of Example 1 is 100, the pigment composition of Comparative Example 1 is 66, and the Y139 pigment composition of the present invention shows a value 34% higher than the commercially available Y139 pigment composition in the color strength of the offset ink.

Claims

1. An isoindoline compound containing a radioactive carbon atom 14 C and having a group represented by the following formula (A), [Chemistry 1] In the formula (A), R 1 ~R 4 independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a phenyl group which may be substituted with an alkyl group, and R 2 and R 3 It can close the ring to form a 5- to 8-membered ring, R 7 ~R 8 Each of them independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a phenyl group which may be substituted with an alkyl group, and * represents a bond.

2. The isoindoline compound according to claim 1, wherein The isoindoline compound having a group represented by the formula (A) is an isoindoline compound represented by the following formula (A-1) or the following formula (A-2), [Chemistry 2] [Chemistry 3] In the formula (A-1) and the formula (A-2), R 1 ~R 4 Indicates that the R 1 ~R 4 The same meaning, R 7 ~R 8 Indicates that the R 7 ~R 8 The same meaning, R 9 ~R 10 With the R 7 ~R 8 Likewise, they independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a phenyl group which may be substituted with an alkyl group.

3. The isoindoline compound according to claim 2, wherein The isoindoline compound represented by the formula (A-1) is an isoindoline compound represented by the following formula (A-1-1), or the isoindoline compound represented by the formula (A-2) is an isoindoline compound represented by the following formula (A-2-1), [Chemistry 4] [Chemistry 5] 4 . A composition comprising the isoindoline compound having a group represented by the formula (A) according to claim 1 .

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

6. The composition according to claim 4, wherein Contains at least two or more isoindoline compounds having a group represented by the formula (A).

7. The composition according to claim 4, comprising an isoindoline compound represented by the following formula (A-1) and an isoindoline compound represented by the following formula (A-3), [Chemistry 6] [Chemistry 7] In the formula (A-1) and the formula (A-3), R 1 ~R 4 independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a phenyl group which may be substituted with an alkyl group, and R 2 and R 3 It can close the ring to form a 5- to 8-membered ring, R 7 ~R 10 Each of them independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a phenyl group which may be substituted with an alkyl group.

8. The composition according to claim 7, wherein The ratio of the isoindoline compound represented by the formula (A-3) in the composition is 0.5 to 10.0% by mass.

9. The composition according to claim 7, wherein The isoindoline compound represented by the formula (A-1) is an isoindoline compound represented by the following formula (A-1-1), and the isoindoline compound represented by the formula (A-3) is an isoindoline compound represented by the following formula (A-3-1). [Chemistry 8] [Chemistry 9] 10. A method for producing an isoindoline compound, comprising producing a 14 C and having a group represented by the following formula (A) and a method for producing an isoindoline compound, [Chemistry 10] In the formula (A), R 1 ~R 4 independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a phenyl group which may be substituted with an alkyl group, and R 2 and R 3 It can close the ring to form a 5- to 8-membered ring, R 7 ~R 8 Each of them independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a phenyl group which may be substituted by an alkyl group; * represents a bond; In the method for producing the isoindoline compound, barbituric acid represented by the following formula (B) is reacted with a compound represented by the following formula (I-2) under the condition of not containing an acid solvent or under the condition of containing at least one acid selected from the group consisting of hydrochloric acid, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, acetic acid, trifluoromethanesulfonic acid, phosphoric acid, polyphosphoric acid, pyrophosphoric acid and nitric acid to obtain an isoindoline compound having a group represented by the above formula (A). [Chemistry 11] In the formula (I), R 1 ~R 4 Indicates that the R 1 ~R 4 The same meaning, [Chemistry 12] In the formula (B), R 5 ~R 6 Each of them independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a phenyl group which may be substituted with an alkyl group.

11. The method for producing an isoindoline compound according to claim 10, wherein Regarding the compound represented by the formula (I-2), The compound represented by the following formula (DA) is used to obtain the compound represented by the following formula (PA), and the isoindoline compound represented by the above formula (I-2) is obtained from the compound represented by the above formula (PA). [Chemistry 13] In the formula (DA), R 1 ~R 4 Indicates that the R 1 ~R 4 The same meaning, [Chemistry 14] In the formula (PA), R 1 ~R 4 Indicates that the R 1 ~R 4 Same meaning.

12. The method for producing an isoindoline compound according to claim 10, wherein The solvent is selected from any one of the group consisting of H2O, dimethylacetamide (DMA), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), MeOH, EtOH, isopropyl alcohol (IPA) and tBuOH.

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