WO2022181621A1

WO2022181621A1 - Condensed heterocyclic compound–containing composition and organic material–containing composition

Info

Publication number: WO2022181621A1
Application number: PCT/JP2022/007303
Authority: WO
Inventors: 強青木; ハンズンド
Original assignee: 日本ゼオン株式会社
Priority date: 2021-02-26
Filing date: 2022-02-22
Publication date: 2022-09-01

Abstract

A condensed heterocyclic compound–containing composition comprising: a compound represented by general formula (A); and at least one compound selected from the group consisting of specific condensed heterocyclic compounds, specific aromatic diamine compounds, and specific aromatic disulfide compounds.

Description

Composition containing condensed heterocyclic compound and composition containing organic material

The present invention provides a condensed heterocyclic compound-containing composition that exhibits high dispersibility in organic materials and exhibits an excellent anti-aging effect on organic materials, and such a condensed heterocyclic compound-containing composition and an organic material. It relates to an organic material-containing composition containing and.

Since organic materials such as polymers are susceptible to oxidative deterioration due to heat, etc., various anti-aging agents are added to improve heat resistance according to the purpose.

Also, in recent years, organic materials such as polymers are increasingly being used under severer high temperatures. For example, with regard to rubber materials used around automobile engines, the temperature in the engine room tends to rise due to the development of high-output automobile engines and low-pollution engines. Therefore, the rubber materials used in the surrounding area are required to have better heat resistance. As one measure for achieving the object, an antiaging agent having a phenothiazine skeleton described in Patent Document 1 has been developed as an antiaging agent capable of imparting higher heat resistance.

Japanese Patent No. 5682575

On the other hand, although the antioxidant described in Patent Document 1 can impart high heat resistance, the dispersibility in organic materials such as polymers is not necessarily sufficient, so it is said that it cannot fully exhibit its function as an antioxidant. I had a problem.

An object of the present invention is to provide a condensed heterocyclic compound-containing composition that exhibits high dispersibility in organic materials and exhibits excellent anti-aging action on organic materials.

The inventors of the present invention conducted studies to achieve the above objects, and found that, with respect to a specific condensed heterocyclic compound that exhibits excellent effects as an antioxidant, a specific condensed heterocyclic compound having a structure different from this, The inventors have found that the above object can be achieved by blending at least one compound selected from the group consisting of a specific aromatic diamine compound and a specific aromatic disulfide compound, and have completed the present invention.

That is, according to the present invention, a compound represented by the following general formula (A) and at least one compound selected from the group consisting of compounds represented by the following general formulas (B) to (E): A composition containing a fused heterocyclic compound is provided.

(In general formula (A) above, R ^a and R ^b each independently represent an optionally substituted organic group having 1 to 30 carbon atoms.
Z ^a and Z ^b each independently represent a chemical single bond or —SO ₂ —.
X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, a cyano group, a nitro group, -OR ¹ , -OC( =O)-R ¹ , -C(=O)-OR ¹ , -O-C(=O)-OR ¹ , -NR ² (R ³ ), -NR ² -C(=O)-R ¹ , -C(=O)-NR ² (R ³ ) or -OC(=O)-NR ² (R ³ ). Here, R ¹ , R ² and R ³ each independently represent a hydrogen atom or an optionally substituted organic group having 1 to 20 carbon atoms.
n and m each independently represent an integer of 0 to 2, and one of n and m is not 0;
Also, when n and/or m is 2, two ^Ra 's and two ^Rb 's may be the same or different. )

(In general formula (B) above, Y ¹ represents -S- or -S(=O)-, and R ^a , R ^b , Z ^a , Z ^b , X ¹ , X ² , n and m is synonymous with the above general formula (A).)

(In the above general formula (C), X ³ and X ⁴ are each independently a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, a cyano group, a nitro group, —OR ¹ , -OC(=O)-R ¹ , -C(=O)-OR ¹ , -OC(=O)-OR ¹ , -NR ² (R ³ ), -NR ² -C(= O)-R ¹ , -C(=O)-NR ² (R ³ ), or -O-C(=O)-NR ² (R ³ ), where R ¹ , R ² and R ³ each independently represents a hydrogen atom or an optionally substituted organic group having 1 to 20 carbon atoms, and p and q each independently represents an integer of 0 to 7.)

(In general formula (D) above, X ³ and X ⁴ have the same definitions as in general formula (C) above, and r and s each independently represent an integer of 0 to 4.)

(In general formula (E) above, X ³ and X ⁴ have the same definitions as in general formula (C) above, t and u each independently represent an integer of 0 to 4, and v and w each independently represents an integer from 0 to 5.)

The condensed heterocyclic compound-containing composition of the present invention is synthesized by using a phenothiazine-based compound as a raw material and adding the compounds represented by the general formulas (B) to (E) to a reaction solution containing the compound represented by the general formula (A). It is preferably obtained by adding at least one compound selected from the group consisting of the compounds represented.
The fused heterocyclic compound-containing composition of the present invention comprises at least one selected from the group consisting of the compound represented by the general formula (A) and the compounds represented by the general formulas (B) to (E). It is preferably a co-precipitate obtained by co-precipitating a compound from a solution containing these.
In the condensed heterocyclic compound-containing composition of the present invention, at least selected from the group consisting of compounds represented by the general formulas (B) to (E) with respect to 1 mol of the compound represented by the general formula (A) The content of one kind of compound is preferably 1 mol or less.
In the condensed heterocyclic compound-containing composition of the present invention, the crystallinity of the compound represented by the general formula (A) is preferably 35% or less.
The condensed heterocyclic compound-containing composition of the present invention preferably contains the compound represented by the general formula (A) and the compound represented by the general formula (B).

Further, according to the present invention, there is provided an organic material-containing composition containing (a) an organic material and (b) the above condensed heterocyclic compound-containing composition.
In the organic material-containing composition of the present invention, the (a) organic material is preferably acrylic rubber.

According to the present invention, it is possible to provide a condensed heterocyclic compound-containing composition that exhibits high dispersibility in organic materials and exhibits excellent antiaging action on organic materials.

The condensed heterocyclic compound-containing composition of the present invention is at least selected from the group consisting of a compound represented by the general formula (A) described later and a compound represented by the general formulas (B) to (E) described later. It contains a kind of compound.

<Compound Represented by Formula (A)>
The condensed heterocyclic compound-containing composition of the present invention contains a compound represented by the following general formula (A).

In general formula (A) above, R ^a and R ^b each independently represent an optionally substituted organic group having 1 to 30 carbon atoms.
Organic groups having 1 to 30 carbon atoms constituting R ^a and R ^b include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and t-butyl group. , n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and other alkyl groups having 1 to 30 carbon atoms; cyclopropyl group, cyclopentyl group, cyclohexyl group , cycloheptyl group, cycloalkyl group having 3 to 30 carbon atoms such as cyclooctyl group; aryl group having 6 to 30 carbon atoms such as phenyl group, biphenyl group, naphthyl group, anthranyl group; alkoxy groups having 1 to 30 carbon atoms such as propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group; be done.

Further, the organic groups constituting R ^a and R ^b described above may have a substituent, and the position of the substituent may be any position.

Substituents for the organic group include, when the organic group is an alkyl group, a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; alkoxy group; nitro group; cyano group; phenyl group, which may have a substituent such as phenyl group, 4-methylphenyl group and 2-chlorophenyl group;
When the organic group is a cycloalkyl group and an aryl group, a fluorine atom, a chlorine atom, a halogen atom such as a bromine atom; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, an isopropoxy group; cyano group; alkyl group having 1 to 10 carbon atoms such as methyl group, ethyl group and t-butyl group;
Moreover, when the said organic group is an alkoxy group, halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom; a nitro group; a cyano group;

When the organic groups constituting R ^a and R ^b have a substituent, the number of carbon atoms in the organic group does not include the number of carbon atoms in the substituent. That is, the number of carbon atoms contained in the substituents of the organic groups constituting R ^a and R ^b may be in the range of 1 to 30, excluding carbon atoms. For example, when the organic group constituting R ^a and R ^b is a methoxyethyl group, the organic group has 2 carbon atoms. That is, in this case, since the methoxy group is a substituent, the number of carbon atoms in the organic group is obtained by excluding the number of carbon atoms in the methoxy group, which is the substituent.

In the present invention, each of R ^a and R ^b is independently a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, and A phenyl group and an optionally substituted naphthyl group are preferred, and an optionally substituted linear or branched alkyl group having 2 to 8 carbon atoms and an optionally substituted group are preferred. A phenyl group is more preferred.
Preferable specific examples of organic groups constituting such R ^a and R ^b include α-methylbenzyl group, α,α-dimethylbenzyl group, t-butyl group, phenyl group, 4-methylphenyl group, and the like. Among these, an α,α-dimethylbenzyl group or a 4-methylphenyl group is particularly preferred. Note that these may be independent of each other.

In general formula (A) above, Z ^a and Z ^b are each independently a chemical single bond or —SO ₂ —, preferably a chemical single bond.

In the above general formula (A), X ¹ and X ² are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, a cyano group, a nitro group, - OR ¹ , -OC(=O)-R ¹ , -C(=O)-OR ¹ , -OC(=O)-OR ¹ , -NR ² (R ³ ), -NR ² -C represents (=O)-R ¹ , -C(=O)-NR ² (R ³ ), or -OC(=O)-NR ² (R ³ );

A fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned as ^a halogen atom which ^comprises X1 and X2.
Examples of the alkyl group having 1 to 10 carbon atoms in the alkyl group having 1 to 10 carbon atoms which may have a substituent include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t -butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like.

Examples of substituents for alkyl groups having 1 to 10 carbon atoms include halogen atoms such as fluorine, chlorine and bromine; methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, t-butoxy; alkoxy group such as group; nitro group; cyano group and the like.

R ¹ , R ² and R ³ each independently represent a hydrogen atom or an optionally substituted organic group having 1 to 20 carbon atoms, and all of R ¹ , R ² and R ³ are hydrogen atoms is preferably

Examples of the organic group having 1 to 20 carbon atoms which may have a substituent constituting R ¹ , R ² and R ³ include a methyl group, an ethyl group and an n-propyl group. , isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, etc. 1 to 20 alkyl groups; cycloalkyl groups having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups; 6 to 6 carbon atoms such as phenyl, naphthyl and anthranyl groups 20 aryl groups; methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, t-butoxy, n-pentyloxy, n-hexyloxy, etc. An alkoxy group having 1 to 20 carbon atoms;

Examples of substituents for the organic groups constituting R ¹ , R ² and R ³ include those listed as the substituents for the organic groups constituting R ^a and R ^b described above.

Among these, X ¹ and X ² are both preferably hydrogen atoms from the viewpoint of availability.

In general formula (A) above, n and m each independently represent an integer of 0 to 2, and one of n and m is not 0. n and m are each independently preferably 0 or 1 (one of n and m is not 0), more preferably n and m are 1;
Also, when n and/or m is 2, two ^Ra 's and two ^Rb 's may be the same or different.

The compound represented by the general formula (A) used in the present invention may be any of the compounds represented by the following general formulas (A′), (A″), and (A′″). preferable.

In general formulas (A′), (A″) and (A′″), R ^a , R ^b , Z ^a and Z ^b have the same meanings as in general formula (A) above. Among the compounds represented by the general formulas (A'), (A'') and (A'''), the compound represented by the general formula (A''') is particularly preferred.
In the above general formulas (A′), (A″) and (A′″), —Z ^a —R ^a and —Z ^b —R ^b are each independently an α-methylbenzyl group, α , α-dimethylbenzyl group, t-butyl group, phenylsulfonyl group or 4-methylphenylsulfonyl group is more preferred, and α,α-dimethylbenzyl group is particularly preferred.

The compound represented by the general formula (A) can be synthesized, for example, according to the method described in Japanese Patent No. 5682575. That is, the compound represented by the above general formula (A) is a compound in which the sulfur of the phenothiazine ring is not oxidized (that is, the above A compound in which —S(=O) ₂ — is —S— in the general formula (A)) is obtained, and then the obtained compound is oxidized to give a sulfur of the phenothiazine ring (that is, —S— ) to -S(=O) ₂ -.

In this case, acetic acid-hydrogen peroxide, m _- chloro An organic peroxide such as perbenzoic acid may be used, the temperature of the oxidation reaction should be 60 to 100° C., and the amount of the oxidizing agent used per 1 mol of the compound before oxidation should be 2.0 to 3.0 mol. . By setting the temperature of the oxidation reaction and the amount of the oxidizing agent to be used within the above ranges, since an excessive amount of the oxidizing agent is used, substantially all of the sulfur (that is, -S-) in the phenothiazine ring is reduced to - It will be oxidized to S(=O) ₂ -.

<Compounds Represented by General Formulas (B) to (E)>
The condensed heterocyclic compound-containing composition of the present invention is at least selected from the group consisting of the compound represented by the general formula (A) and the compounds represented by the general formulas (B) to (E) described later. It contains one kind of compound.

The compound represented by general formula (B) has the following structure.

In general formula (B) above, Y ¹ represents -S- or -S(=O)-, preferably -S(=O)-.
In addition, R ^a , R ^b , Z ^a , Z ^b , X ¹ , X ² , n and m have the same meanings as in general formula (A) above, and these examples and suitable groups are also defined in general formula ( It is the same as A).

The compound represented by the general formula (B) is preferably any one of the compounds represented by the following general formulas (B′), (B″), and (B′″).

In general formulas (B′), (B″) and (B′″) above, R ^a , R ^b , Z ^a and Z ^b have the same meanings as in general formula (B) above. Among the compounds represented by the general formulas (B'), (B'') and (B'''), the compound represented by the general formula (B''') is particularly preferred.
In the above general formulas (B′), (B″) and (B′″), —Z ^a —R ^a and —Z ^b —R ^b each independently represents an α-methylbenzyl group, α , α-dimethylbenzyl group, t-butyl group, phenylsulfonyl group or 4-methylphenylsulfonyl group is more preferred, and α,α-dimethylbenzyl group is particularly preferred.

Further, in the present invention, when the compound represented by the general formula (B) is used, the compound represented by the general formula (A) is used from the viewpoint that the dispersibility in organic materials such as polymers can be further improved. and the compound having the same R ^a , R ^b , Z ^a , Z ^b , X ¹ , X ² , n and m, and the substitution positions of -Z ^a -R ^a , -Z ^b -R ^b It is preferred to use compounds that are the same. That is, in the compound represented by the general formula (B), the sulfur atom of the phenothiazine ring is a -S(=O) ₂ - group or a -S(=O)- group. It is preferable to use only one.

The compound represented by the general formula (B) can be synthesized, for example, according to the method described in Japanese Patent No. 5682575. That is, the compound represented by the general formula (B) can be produced by applying a known method for producing phenothiazine-based compounds using phenothiazine as a raw material. Further, among the compounds represented by the above general formula (B), the compound in which Y ¹ is -S(=O)- is a compound in which sulfur in the phenothiazine ring is not oxidized (i.e., the above general formula (B ) in which Y ¹ is -S-), and then by oxidizing the resulting compound, the sulfur of the phenothiazine ring (i.e., -S-) is replaced by -S(=O)- It can be manufactured by

In this case, acetic acid-hydrogen peroxide, m _- chloro An organic peroxide such as perbenzoic acid is used, the temperature of the oxidation reaction is set to 60 to 100° C., and the amount of the oxidizing agent used is set to 1.0 to 1.3 mol per 1 mol of the compound before oxidation, The oxidizing agent may be gradually added to the reaction system. By setting the temperature of the oxidation reaction and the amount of the oxidizing agent used within the above ranges, substantially all of the sulfur in the phenothiazine ring (that is, -S-) is oxidized to -S(=O)-. It is possible to effectively suppress the formation of -S(=O) ₂ - due to further oxidation.

The compound represented by general formula (C) has the following structure.

In general formula (C) above, X ³ and X ⁴ are each independently a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, a cyano group, a nitro group, —OR ¹ , -OC(=O)-R ¹ , -C(=O)-OR ¹ , -OC(=O)-OR ¹ , -NR ² (R ³ ), -NR ² -C(=O )-R ¹ , -C(=O)-NR ² (R ³ ), or -O-C(=O)-NR ² (R ³ ) (R ¹ , R ² and R ³ are each independently represents a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent.), examples and preferred groups thereof are the same as those of the general formula (A).
In addition, p and q each independently represent an integer of 0 to 7, preferably 0 to 2, more preferably 0 or 1, and particularly preferably 0 (that is, a substituent on the naphthalene ring is particularly preferred).

The compound represented by general formula (D) has the following structure.

In general formula (D) above, X ³ and X ⁴ have the same definitions as in general formula (C) above, and examples and preferred groups thereof are also the same as in general formula (C) above.
In addition, r and s each independently represent an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1, particularly preferably 0 (that is, a substituent on the benzene ring is particularly preferred).

The compound represented by general formula (E) has the following structure.

In general formula (E) above, X ³ and X ⁴ have the same definitions as in general formula (C) above, and examples and suitable groups thereof are also the same as in general formula (C) above.
Further, t and u each independently represent an integer of 0-4, and v and w each independently represent an integer of 0-5. t, u, v and w are preferably 0 to 2, more preferably 0 or 1, particularly preferably 0 (that is, those having no substituents on the benzene ring are particularly preferred).

Among the compounds represented by the general formulas (B) to (E), from the viewpoint that the dispersibility in organic materials such as polymers can be further improved, the compounds represented by the general formula (B) and the general A compound represented by the formula (D) is preferred, and a compound represented by the general formula (B) is particularly preferred.

At least one compound selected from the group consisting of the compound represented by the above general formula (A) and the compounds represented by the above general formulas (B) to (E) in the composition containing a condensed heterocyclic compound of the present invention The content ratio with the compound is not particularly limited, but is selected from the group consisting of the compounds represented by the general formulas (B) to (E) with respect to 1 mol of the compound represented by the general formula (A). The content of at least one compound is preferably 1 mol or less, more preferably 0.01 to 0.5 mol, still more preferably 0.01 to 0.15 mol, particularly preferably 0.01 to 0.1 mol. By setting the content within the above range, the anti-aging function of the compound represented by the general formula (A) can be made more sufficient, while the dispersibility in organic materials such as polymers can be made more appropriate. can be done.

<Method for Preparing Composition Containing Condensed Heterocyclic Compound>
The method for preparing the fused heterocyclic compound-containing composition of the present invention is not particularly limited. Examples include a method of mixing with at least one of the compounds in a solid state, a method of mixing in a state of being dissolved or dispersed in a solvent, and a method of removing the solvent.

In the present invention, the degree of crystallinity of the compound represented by the general formula (A) is kept low in the obtained composition containing a condensed heterocyclic compound, thereby further increasing the dispersibility in organic materials such as polymers. From the viewpoint that the above general formula A method of adding at least one of the compounds represented by (B) to (E) is preferred. That is, after synthesizing the compound represented by the general formula (A), the compound represented by the general formula (A) is never recovered as a solid compound, and the reaction obtained by synthesis A preferred method is to use the liquid as it is, add at least one compound among the compounds represented by the general formulas (B) to (E), and mix them.

Hereinafter, as a method for preparing the composition containing a condensed heterocyclic compound of the present invention, the above general formula (B) is added to a reaction solution containing the compound represented by the above general formula (A) synthesized using a phenothiazine-based compound as a raw material. A method of adding at least one compound among the compounds represented by (E) will be described by exemplifying it.

The method of adding and mixing at least one compound among the compounds represented by the general formulas (B) to (E) to the reaction solution containing the compound represented by the general formula (A) is particularly limited. However, it is preferable to use the solvent contained in the reaction solution containing the compound represented by the general formula (A) as a dispersion medium for mixing, and if necessary, add another solvent and good too. The mixing temperature may be a temperature at which the compound represented by the general formula (A) and the compounds represented by the general formulas (B) to (E) do not precipitate, but is preferably 30 to 80°C. , more preferably 35 to 60° C., and the mixing time is preferably 5 minutes to 5 hours, more preferably 15 minutes to 2 hours.

In addition, before adding at least one compound among the compounds represented by the general formulas (B) to (E) to the reaction solution containing the compound represented by the general formula (A), the general formula ( A deactivator such as sodium bisulfite is added to the reaction solution containing the compound represented by A) in order to deactivate the oxidizing agent used in the synthesis of the compound represented by the general formula (A). Also, by adding a deactivator in advance, oxidation of the compounds represented by the general formulas (B) to (E) can be suppressed.

Further, in the present invention, at least one compound among the compounds represented by the general formulas (B) to (E) is added to the reaction solution containing the compound represented by the general formula (A), and mixed. After performing the above, it is preferable to subject the obtained mixed liquid to aging treatment. By performing the aging treatment, the degree of crystallinity of the compound represented by the above general formula (A) in the resulting condensed heterocyclic compound-containing composition can be suppressed to a lower level, whereby an organic material such as a polymer can be used. It is possible to further increase the dispersibility for

As the aging treatment, it is preferable to stir the mixture at a temperature of preferably 30 to 60°C, more preferably 35 to 55°C, for 5 minutes to 5 hours, more preferably 15 minutes to 3 hours.

In addition, from the viewpoint that the degree of crystallinity of the compound represented by the general formula (A) in the resulting condensed heterocyclic compound-containing composition can be further suppressed, the aging treatment is performed by adding seed crystals. The compound represented by the general formula (A) is preferably used as the seed crystal, and the compound represented by the general formula (A) has a crystallinity of 35% or less. is particularly preferred. When the compound represented by the general formula (A) is used as the seed crystal, the condensed heterocyclic compound-containing composition of the present invention may be used as the seed crystal. You may use the compound represented by the said general formula (A) manufactured on such conditions. The amount of seed crystals used is preferably 0.01 to 100 parts by weight in total of the compound represented by the general formula (A) and the compounds represented by the general formulas (B) to (E). 5 parts by weight, more preferably 0.03 to 1 part by weight.

Then, the mixed liquid that has undergone the aging treatment is slowly cooled, preferably to 0 to 25 ° C., so that the mixed liquid contains the compound represented by the general formula (A) and the general formulas (B) to (E ) is co-precipitated with at least one of the compounds represented by ) to form these co-precipitates. The cooling rate during slow cooling is preferably 3 to 20°C/hour, more preferably 5 to 15°C/hour. By performing slow cooling under such conditions, the degree of crystallinity of the compound represented by the general formula (A) in the resulting condensed heterocyclic compound-containing composition can be suppressed to a lower level. Dispersibility in organic materials such as polymers can be further enhanced. The cooling rate during slow cooling may be constant, or may be different between the initial stage of slow cooling and the final stage of slow cooling. In addition, after slow cooling, the mixture after slow cooling is aged by maintaining it at the temperature after cooling, preferably for 15 minutes to 30 hours, more preferably for 30 minutes to 18 hours. may

Then, by performing a recovery operation such as filtration on the coprecipitate precipitated in the mixed solution, the compound represented by the general formula (A) and the compounds represented by the general formulas (B) to (E) Wet crystals containing the compound are obtained.

Then, the obtained wet crystals are subjected to a drying treatment to obtain at least one compound among the compound represented by the general formula (A) and the compounds represented by the general formulas (B) to (E). to obtain a condensed heterocyclic compound-containing composition comprising The condensed heterocyclic compound-containing composition obtained in this manner contains at least one of the compounds represented by the general formula (A) and the compounds represented by the general formulas (B) to (E). Since it has undergone a step of co-precipitating with a compound, it can be said to be a co-precipitate of these.

The drying treatment method is not particularly limited as long as it is a method capable of removing the solvent contained in the wet crystals, and is not particularly limited. The drying temperature may be selected according to the type of solvent, preferably 20 to 100°C, more preferably 50 to 90°C. In addition, as a method of performing heating as necessary under reduced pressure conditions, for example, a method using a vacuum tray dryer and a method using an evaporator can be mentioned. In the method using a vacuum tray dryer, drying is performed. The drying time is preferably 12 to 150 hours, more preferably 24 to 100 hours. In the method using an evaporator, the drying time is preferably 16 to 120 hours, more preferably 24 to 100 hours. In the drying treatment, as the solvent is removed by drying, the formation of crystals proceeds. From the viewpoint of lowering the crystallinity of the compound, it is preferable to appropriately select the drying conditions within the above range.

The crystallinity of the compound represented by the general formula (A) contained in the composition containing a condensed heterocyclic compound of the present invention is preferably 35% or less, more preferably 30% or less, and still more preferably 28% or less. Although the lower limit of crystallinity is not particularly limited, it is preferably 15% or more, more preferably 20% or more. By keeping the crystallinity of the compound represented by the general formula (A) contained in the condensed heterocyclic compound-containing composition low as described above, the dispersibility in organic materials such as polymers can be further enhanced. can. The degree of crystallinity is measured using a differential scanning calorimeter (DSC) for the condensed heterocyclic compound-containing composition, and the exothermic peak and the endothermic peak are obtained from the obtained DSC curve. can be calculated.
Crystallinity (%) = 100 - {(calorie at exothermic peak)/(calorie at endothermic peak) x 100}

Further, in the condensed heterocyclic compound-containing composition of the present invention, selected from the group consisting of the compound represented by the general formula (A) and the compounds represented by the general formulas (B) to (E) The total content with at least one compound is preferably 99.5% by weight or more, more preferably 99.7% by weight or more, even more preferably 99.9% by weight or more, The volatile content is preferably 0.5% by weight or less, more preferably 0.3% by weight or less, and even more preferably 0.1% by weight or less. Examples of the volatile content include the solvent used in the production.

<Composition containing organic material>
The organic material-containing composition of the present invention is a composition containing an organic material as component (a) and the aforementioned condensed heterocyclic compound-containing composition of the present invention as component (b).

The organic material of component (a) used in the present invention is not particularly limited, and may be a natural organic material or a synthetic organic material. Among them, as the organic material of component (a), since the effect of adding the condensed heterocyclic compound-containing composition of the present invention is large, synthetic rubber, polyolefin, polystyrene resin, polyester, polycarbonate, polyamide, etc. Synthetic polymers are preferred, and synthetic rubbers are more preferred, for use in applications requiring

The synthetic rubber that can constitute the organic material-containing composition of the present invention is not particularly limited. nitrile rubber), styrene-butadiene-isoprene copolymer rubber, butadiene-isoprene copolymer rubber, acrylonitrile-styrene-butadiene copolymer rubber containing conjugated diene units; acrylic rubber; hydrin rubber; be done. These synthetic rubbers may have hydroxyl groups, carboxyl groups, alkoxysilyl groups, amino groups, epoxy groups, and the like. These rubbers may also be hydrogenated, such as acrylonitrile-butadiene copolymer rubber hydrogenates (hydrogenated nitrile rubbers). These synthetic rubbers may be used alone or in combination of two or more. Among these, application to acrylic rubber or hydrogenated nitrile rubber, which is particularly required to have high heat resistance, is preferable from the viewpoint of the effect of improving heat resistance, and application to acrylic rubber is more preferable.

The acrylic rubber that can be used in the present invention contains 50 to 100% by weight of (meth)acrylic acid ester monomer units and 10 to 0% by weight of crosslinkable monomer units, and if necessary, these monomer units is a rubber containing 50 to 0% by weight of units of other monomers that can be copolymerized with monomers that form can be adjusted. In the present invention, "(meth)acryl" indicates acryl and/or methacryl.

Acrylic rubber is known for its excellent oil resistance, especially at high temperatures, and as a rubber with good heat resistance. It is in demand for automotive hoses, oil seals, O-rings, and conveyor belts built into equipment and machinery. It is increasing.

The (meth)acrylic acid ester monomer forming the (meth)acrylic acid ester monomer unit, which is the main component of the acrylic rubber, is not particularly limited. monomers, and (meth)acrylic acid alkoxyalkyl ester monomers.

The (meth)acrylic acid alkyl ester monomer is not particularly limited, but an ester of an alkanol having 1 to 8 carbon atoms and (meth)acrylic acid is preferable, and specifically, methyl (meth)acrylate, ( meth)ethyl acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isopropyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, (meth)acrylate 2-ethylhexyl acrylate, cyclohexyl (meth)acrylate and the like. Among these, ethyl (meth)acrylate and n-butyl (meth)acrylate are preferred, and ethyl acrylate and n-butyl acrylate are more preferred. These can be used individually by 1 type or in combination of 2 or more types.

The (meth)acrylic acid alkoxyalkyl ester monomer is not particularly limited, but an ester of an alkoxyalkyl alcohol having 2 to 8 carbon atoms and (meth)acrylic acid is preferable, and specifically, (meth)acrylic acid Methoxymethyl, ethoxymethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-propoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate , 3-methoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, and the like. Among these, 2-ethoxyethyl (meth)acrylate and 2-methoxyethyl (meth)acrylate are preferred, and 2-ethoxyethyl acrylate and 2-methoxyethyl acrylate are particularly preferred. These can be used individually by 1 type or in combination of 2 or more types.

The content of (meth)acrylate monomer units in the acrylic rubber is 50-100% by weight, preferably 60-99.5% by weight, more preferably 70-99.5% by weight. If the content of the (meth)acrylic acid ester monomer units is too low, the obtained crosslinked rubber may have poor weather resistance, heat resistance and oil resistance.

The breakdown of the (meth)acrylic acid ester monomer units is 30 to 100% by weight of (meth)acrylic acid alkyl ester monomer units and 70 to 0% by weight of (meth)acrylic acid alkoxyalkyl ester monomer units. is preferred.

The crosslinkable monomer forming the crosslinkable monomer unit is not particularly limited, but α,β-ethylenically unsaturated carboxylic acid monomer; monomer having a halogen atom or epoxy group; diene monomer body; and the like.

Although the α,β-ethylenically unsaturated carboxylic acid monomer is not particularly limited, examples include α,β-ethylenically unsaturated monocarboxylic acids having 3 to 12 carbon atoms, α,β- Examples thereof include ethylenically unsaturated dicarboxylic acids, and monoesters of α,β-ethylenically unsaturated dicarboxylic acids having 4 to 12 carbon atoms and alkanols having 1 to 8 carbon atoms. Examples of α,β-ethylenically unsaturated monocarboxylic acids having 3 to 12 carbon atoms include acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid and cinnamic acid. The α,β-ethylenically unsaturated dicarboxylic acids having 4 to 12 carbon atoms include butenedioic acid such as fumaric acid or maleic acid, itaconic acid, citraconic acid, chloromaleic acid and the like. Monoesters of α,β-ethylenically unsaturated dicarboxylic acids having 4 to 12 carbon atoms and alkanols having 1 to 8 carbon atoms include monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monomethyl maleate, and monoethyl maleate. , butenedionic acid mono-chain alkyl esters such as monobutyl maleate; Itaconic acid monoesters such as monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, and monocyclohexyl itaconate; and the like. Among these, butenedioic acid monochain alkyl esters or butenedioic acid monoesters having an alicyclic structure are preferred, and monobutyl fumarate, monobutyl maleate, monocyclohexyl fumarate and monocyclohexyl maleate are more preferred. These α,β-ethylenically unsaturated carboxylic acid monomers can be used alone or in combination of two or more. Among the above monomers, the dicarboxylic acid may be copolymerized as an anhydride, as long as it hydrolyzes to form a carboxyl group during crosslinking.

The monomer having a halogen atom is not particularly limited, but examples include unsaturated alcohol esters of halogen-containing saturated carboxylic acids, (meth)acrylic acid haloalkyl esters, (meth)acrylic acid haloacyloxyalkyl esters, (meth)acryl acid (haloacetylcarbamoyloxy) alkyl esters, halogen-containing unsaturated ethers, halogen-containing unsaturated ketones, halomethyl group-containing aromatic vinyl compounds, halogen-containing unsaturated amides, haloacetyl group-containing unsaturated monomers, and the like. Examples of unsaturated alcohol esters of halogen-containing saturated carboxylic acids include vinyl chloroacetate, vinyl 2-chloropropionate, and allyl chloroacetate. (Meth)acrylic acid haloalkyl esters include chloromethyl (meth)acrylate, 1-chloroethyl (meth)acrylate, 2-chloroethyl (meth)acrylate, 1,2-dichloroethyl (meth)acrylate, (meth)acrylic acid ) 2-chloropropyl acrylate, 3-chloropropyl (meth)acrylate, 2,3-dichloropropyl (meth)acrylate and the like. Examples of haloacyloxyalkyl (meth)acrylates include 2-(chloroacetoxy)ethyl (meth)acrylate, 2-(chloroacetoxy)propyl (meth)acrylate, and 3-(chloroacetoxy)propyl (meth)acrylate. , 3-(hydroxychloroacetoxy)propyl (meth)acrylate, and the like. Examples of (haloacetylcarbamoyloxy)alkyl (meth)acrylates include 2-(chloroacetylcarbamoyloxy)ethyl (meth)acrylate and 3-(chloroacetylcarbamoyloxy)propyl (meth)acrylate. Halogen-containing unsaturated ethers include chloromethyl vinyl ether, 2-chloroethyl vinyl ether, 3-chloropropyl vinyl ether, 2-chloroethyl allyl ether, 3-chloropropyl allyl ether, and the like. Halogen-containing unsaturated ketones include 2-chloroethyl vinyl ketone, 3-chloropropyl vinyl ketone, 2-chloroethyl allyl ketone, and the like. Examples of halomethyl group-containing aromatic vinyl compounds include p-chloromethylstyrene and p-chloromethyl-α-methylstyrene. Halogen-containing unsaturated amides include N-chloromethyl(meth)acrylamide. Haloacetyl group-containing unsaturated monomers include 3-(hydroxychloroacetoxy)propyl allyl ether, p-vinylbenzyl chloroacetate and the like.

The monomer having an epoxy group is not particularly limited, but examples include epoxy group-containing (meth)acrylic acid esters and epoxy group-containing ethers. Examples of epoxy group-containing (meth)acrylic acid esters include glycidyl (meth)acrylate, and examples of epoxy group-containing ethers include allyl glycidyl ether.

Diene monomers include conjugated diene monomers and non-conjugated diene monomers. Conjugated diene monomers include 1,3-butadiene, isoprene, and piperylene. Examples of non-conjugated diene monomers include ethylidenenorbornene, dicyclopentadiene, dicyclopentadienyl (meth)acrylate, and 2-dicyclopentadienylethyl (meth)acrylate.

These crosslinkable monomers can be used singly or in combination of two or more. The content of the crosslinkable monomer units in the acrylic rubber is 0 to 10% by weight, preferably 0.5 to 7% by weight, more preferably 0.5 to 5% by weight. If the content of the crosslinkable monomer units is too high, the resulting crosslinked rubber may have reduced elongation or increased compression set.

Other monomers that can be copolymerized with each of the above monomers are not particularly limited. Examples include monomers having one or more, olefinic monomers, and vinyl ether compounds.

　Styrene, α-methylstyrene, divinylbenzene and the like are examples of aromatic vinyl monomers. Examples of α,β-ethylenically unsaturated nitrile monomers include acrylonitrile and methacrylonitrile. Examples of polyfunctional (meth)acrylic monomers include (meth)acrylic acid diesters of ethylene glycol and (meth)acrylic acid diesters of propylene glycol. Examples of olefinic monomers include ethylene, propylene, 1-butene and 1-octene. Vinyl ether compounds include vinyl acetate, ethyl vinyl ether, butyl vinyl ether and the like. Among these, styrene, acrylonitrile and methacrylonitrile are preferred, and acrylonitrile and methacrylonitrile are more preferred.

These other copolymerizable monomers can be used singly or in combination of two or more. The content of other monomer units in the acrylic rubber is 0 to 50% by weight, preferably 0 to 39.5% by weight, more preferably 0 to 29.5% by weight.

The acrylic rubber used in the present invention can be obtained by polymerizing the above monomers. As the form of polymerization reaction, any of emulsion polymerization method, suspension polymerization method, bulk polymerization method and solution polymerization method can be used. It is preferable to use an emulsion polymerization method under normal pressure, which is generally used as a method.

Emulsion polymerization may be batch, semi-batch or continuous. The polymerization is usually carried out in the temperature range of 0-70°C, preferably 5-50°C.

Mooney viscosity [ML1+4, 100°C] (polymer Mooney) of the acrylic rubber produced in this manner and used in the present invention is preferably 10 to 80, more preferably 20 to 70, and particularly preferably 25 to 60. .

Moreover, the organic material-containing composition of the present invention may further contain other additives in addition to the components (a) and (b) described above.
Other additives include additives commonly used in fields using synthetic polymer materials and the like. For example, reinforcing fillers such as carbon black and silica; non-reinforcing fillers such as calcium carbonate and clay; light stabilizers; scorch inhibitors; plasticizers; anti-mold agent; antistatic agent; colorant; silane coupling agent; cross-linking agent; cross-linking accelerator;
The amount of these additives to be blended is not particularly limited as long as it does not impair the purpose and effect of the present invention, and the amount can be appropriately blended according to the purpose of blending.

The organic material-containing composition of the present invention is prepared by mixing and kneading predetermined amounts of component (a), component (b), and optionally other additives in a Banbury mixer, kneader, or the like, and then using kneading rolls to further It can be prepared by kneading.
The order in which each component is mixed is not particularly limited, but after thoroughly mixing the components that are difficult to react or decompose with heat, add the cross-linking agent, which is a component that easily reacts or decompose with heat, at a temperature where no reaction or decomposition occurs. Mixing for hours is preferred.

For example, when rubber such as acrylic rubber is used as the organic material that constitutes the organic material-containing composition, and a cross-linking agent is included, a cross-linked rubber product can be obtained by cross-linking the rubber. The cross-linked rubber product is obtained by molding with a molding machine corresponding to the desired shape, such as an extruder, injection molding machine, compressor, roll, etc., and fixing the shape of the cross-linked rubber product through a cross-linking reaction. can be done. In that case, the cross-linking may be performed after pre-molding, or the cross-linking may be performed at the same time as the molding. The molding temperature is usually 10-200°C, preferably 25-120°C. The cross-linking temperature is generally 130-220° C., preferably 150-190° C., and the cross-linking time is generally 2 minutes to 10 hours, preferably 3 minutes to 6 hours. As the heating method, a method used for cross-linking rubber, such as press heating, steam heating, oven heating, and hot air heating, may be appropriately selected.

In addition, depending on the shape and size of the crosslinked rubber product, even if the surface is crosslinked, the interior may not be sufficiently crosslinked, so secondary crosslinking may be performed by further heating. The secondary cross-linking time varies depending on the heating method, cross-linking temperature, shape, etc., but is preferably 1 to 48 hours. A heating method and a heating temperature may be appropriately selected.

The organic material-containing composition of the present invention is obtained by blending the above-described condensed heterocyclic compound-containing composition of the present invention, and the condensed heterocyclic compound-containing composition of the present invention has excellent dispersibility in organic materials. Therefore, it can impart excellent heat resistance to organic materials. Therefore, the organic material-containing composition of the present invention and the rubber cross-linked product obtained using the same have excellent heat resistance.

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples.
Various physical properties were evaluated according to the following methods.

<Content of various compounds>
The content of each compound in the wet crystals obtained in Examples and Comparative Examples was measured according to the following method.
That is, the wet crystals are measured using HPLC (high performance liquid chromatography) to obtain the amount of the compound (A-1) described later, and from the results, the amount of the compound (A-1) described later, The amounts of compound (B-1), compound (C-1), compound (D-1) and compound (E-1), which will be described later, were calculated as percentages of the two components. In the HPLC measurement, as a calibration curve, high-purity compounds of 99.0% or more were used to prepare solutions with three different concentrations as standard samples. Based on the results of constant amount analysis of these three types of standard samples with different concentrations using an autosampler, a calibration curve was created with the horizontal axis representing the HPLC peak area and the vertical axis representing the concentration, and quantification was carried out.
Specific conditions for HPLC measurement are shown below.
Measuring device: Agilent LC1260 type Column: XDB-C18 diameter 4.6 mm × length 250 mm (Agilent 990967-902)
Column temperature: 40°C
Mobile phase: acetonitrile/distilled water = 90/10 (volume ratio) (0 to 10 minutes), acetonitrile/distilled water = 95/5 (volume ratio) (10 to 25 minutes) (that is, analysis for a total of 25 minutes rice field.)

<Measurement of crystallinity>
The crystallinity of compound (A-1), which will be described later, in the composition containing the condensed heterocyclic compound was measured according to the method described below.
A sample container was prepared by weighing 10 mg of the compositions or compounds obtained in Examples and Comparative Examples in an aluminum pan, putting an aluminum pan cover on top of this, and sealing with a sample sealer. As a control sample, an aluminum pan cover was placed on an empty aluminum pan and sealed with a sample sealer to obtain a reference container.
Then, with respect to the sample container and the reference container, using a differential scanning calorimeter (DSC), the temperature of the reference and the sample is measured while increasing the temperature at a constant rate to measure the heat quantity accompanying the state change of the sample, From the measured DSC curve, the amount of heat associated with crystallization and melting (melting point) was obtained, and the degree of crystallinity was calculated from the values of these two amounts of heat.
For the measurement, a DSC apparatus (DSC7000 series manufactured by Hitachi High-Tech Science Co., Ltd.) was used, and the temperature was raised in the range of 0 to 250°C at a rate of 10°C/min. From the DSC curve, the heat quantity of an exothermic peak (crystallization peak) having an apex at 125 to 140°C was calculated and defined as an "exothermic peak". Also, the calorific value of an endothermic peak (melting point peak) having a peak at 180 to 220° C. was calculated and defined as an "endothermic peak". Then, the degree of crystallinity (%) was obtained according to the following formula.
Crystallinity (%) = 100 - {(calorie at exothermic peak)/(calorie at endothermic peak) x 100}

<Dispersibility in acrylic rubber>
100 parts by weight of acrylic rubber (Nipol AR22, manufactured by Nippon Zeon Co., Ltd.), 60 parts by weight of carbon black (manufactured by Tokai Carbon Co., Ltd., Siest SO), 2 parts by weight of stearic acid, and as an anti-aging agent obtained in the examples Add 1 part by weight of the condensed heterocyclic compound-containing composition or 1 part by weight of the compound (A-1) obtained in Comparative Example, start kneading at 50 ° C. using a Brabender, and knead for 5 minutes. After that, the temperature was raised to 100° C. and kneaded. Then, the particulate matter derived from the anti-aging agent in the kneaded product during kneading and after kneading was visually counted and evaluated according to the following criteria.
A: After kneading at 100°C for 10 minutes, no anti-aging agent particulate matter was observed.
B: After kneading at 100°C for 10 minutes, a very small amount of anti-aging agent granules was observed, but after kneading at 100°C for 20 minutes, no anti-aging agent granules were observed. rice field.
C: Even after kneading at 100°C for 20 minutes, anti-aging agent granules were confirmed. , 1 or more and 5 or less.
D: Even after kneading at 100°C for 20 minutes, granules of the anti-aging agent were confirmed, and after kneading at 100°C for 20 minutes, the granules of the rubber cross section (8 cm x 0.5 cm) were measured. , was 6 or more.

(Synthesis Example 1) Preparation of Reaction Solution of Compound (A-1) Compound (A-1) represented by the above formula (A-1) was synthesized according to the following method.

First, 80.0 g (401.47 mmol) of phenothiazine and 200 g of o-xylene were added to a three-necked reactor equipped with a thermometer in a nitrogen stream. Then, 94.89 g (802.94 mmol) of α-methylstyrene and 3.82 g (20.07 mmol) of p-toluenesulfonic acid monohydrate were added thereto and reacted at 80° C. for 1 hour. After that, 80 g of acetic acid, 400 g of o-xylene, and 102.57 g (905.03 mmol) of 30% by weight hydrogen peroxide were added to the reaction solution, and the mixture was further reacted at 80° C. for 2 hours. 52.22 g (200.74 mmol) of a 10% by weight sodium hydrogen sulfite aqueous solution was added to the reaction solution, and the mixture was heated at 85° C. for 1 hour. After removing the aqueous layer, 180 g of methanol was added to the organic layer to prepare a reaction solution of compound (A-1).

Then, a part of the reaction solution of compound (A-1) is taken out and cooled to 20° C. to precipitate crystals. The precipitated crystals are filtered and rinsed with methanol to obtain wet crystals containing methanol. Dry white crystals were obtained by vacuum-drying the wet crystals. The yield at this time was 66%. The dry white crystals thus obtained were subjected to ¹ H-NMR measurement and identified as the compound (A-1) represented by the above formula (A-1).

¹ H-NMR (500 MHz, DMSO-d6, TMS, δ ppm): 1.67 (s, 12H), 7.15-7.32 (m , 12H), 7.43 (dd, 2H, J=9. 0, 2.0 Hz), 7.68 (d, 2H, J = 1.5 Hz), 10.84 (s, 1H).

(Synthesis Example 2) Synthesis of compound (B-1) A compound (B-1) represented by the following formula (B-1) was synthesized according to the following method.

First, 80.0 g (401.47 mmol) of phenothiazine and 200 g of o-xylene were added to a three-necked reactor equipped with a thermometer in a nitrogen stream. Then, 94.89 g (802.94 mmol) of α-methylstyrene and 3.82 g (20.07 mmol) of p-toluenesulfonic acid monohydrate were added thereto and reacted at 80° C. for 1 hour. After cooling the reaction solution to 50°C, 60 g of acetic acid and 400 g of o-xylene were added, and 49.88 g (440.12 mmol) of 30% by weight hydrogen peroxide was slowly added dropwise over 30 minutes. reacted over time. 52.22 g (200.74 mmol) of a 10% by weight sodium hydrogen sulfite aqueous solution was added to the reaction solution, and the mixture was heated at 85° C. for 1 hour. After removing the aqueous layer, 180 g of methanol was added to the organic layer.

Thereafter, the reaction solution was cooled to 20° C., and the precipitated crystals were filtered and rinsed with 240 g of methanol to obtain 136.29 g of compound (B-1) as white crystals at a yield of 66%. The structure was identified by ¹ H-NMR.

¹ H-NMR (500 MHz, DMSO-d6, TMS, δppm): 1.68 (s, 6H), 1.70 (s, 6H), 7.15-7.32 (m, 12H), 7.38 (dd, 2H, J = 9.0, 2.0 Hz), 7.70 (d, 2H, J = 1.5 Hz), 10.85 (s, 1H).

(Example 1) Preparation of condensed heterocyclic compound-containing composition (α-1) containing compound (A-1) and compound (B-1) according to the following method, compound (A-1) and compound (B) A condensed heterocyclic compound-containing composition (α-1) containing -1) was prepared.
That is, first, 129.43 g of the reaction solution of compound (A-1) prepared in Synthesis Example 1 above (the amount of compound (A-1), 23.18 g), and 28.90 g of methanol were added. To this solution, 0.10 g of the compound (B-1) synthesized in Synthesis Example 2 was added, and the mixture was dissolved by heating under reflux on a hot bath at 70° C. for 1 hour. After refluxing for 1 hour, the mixture was cooled to 40°C, 12.9 mg of compound (A-1) seed crystals (crystallinity: 35% or less) were added, and the reaction solution was heated at 40°C for 1 After stirring for 2 hours, the reaction solution was cooled to 20°C over 2 hours and then held at 20°C for 1 hour. Coprecipitate precipitated by cooling was filtered and rinsed with 38.8 g of methanol to obtain 24.30 g of wet crystals containing compound (A-1) and compound (B-1). As a result of measuring the loss on drying of the wet crystals, it was 14.78% by weight. Further, as a result of analyzing this wet crystal using HPLC, the area ratio of compound (A-1) to compound (B-1) was 98.91:1.09. It was confirmed that the wet crystals contained compound (A-1) and compound (B-1) in the above molar ratio (the same applies to each example and comparative example described later).

Then, the wet crystals obtained above are air-dried overnight at room temperature, the air-dried crystals are transferred to an aluminum weighing dish, and dried for 168 hours using a vacuum tray dryer at 70 ° C. A condensed heterocyclic compound-containing composition (α-1) was obtained and evaluated for crystallinity and dispersibility in acrylic rubber according to the methods described above. The results are shown in Table 1 together with residual methanol content (ie, volatile content). The pressure in the vacuum tray dryer was reduced using an oil rotary vacuum pump, and the degree of pressure reduction was 1 mmHg or less.

(Example 2) Preparation of condensed heterocyclic compound-containing composition (α-2) containing compound (A-1) and compound (B-1) The amount of compound (B-1) added was 0.29 g. Except for this, the same operation as in Example 1 was carried out to obtain 24.19 g of wet crystals containing compound (A-1) and compound (B-1). As a result of measuring the loss on drying of the wet crystals, it was 14.88% by weight. As a result of analyzing this wet crystal using HPLC, the area ratio of compound (A-1) to compound (B-1) was 98.17:1.83.
Then, the wet crystals obtained above were dried in the same manner as in Example 1 to obtain a condensed heterocyclic compound-containing composition (α-2), which was evaluated in the same manner. Table 1 shows the results.

(Example 3) Preparation of condensed heterocyclic compound-containing composition (α-3) containing compound (A-1) and compound (B-1) The amount of compound (B-1) added was 0.45 g. Except for this, the same operation as in Example 1 was carried out to obtain 24.36 g of wet crystals containing compound (A-1) and compound (B-1). The loss on drying of the wet crystals was measured and found to be 14.99% by weight. As a result of analyzing this wet crystal using HPLC, the area ratio of compound (A-1) to compound (B-1) was 97.32:2.68.
Then, the wet crystals obtained above were dried in the same manner as in Example 1 to obtain a condensed heterocyclic compound-containing composition (α-3), which was evaluated in the same manner. Table 1 shows the results.

(Example 4) Preparation of condensed heterocyclic compound-containing composition (α-4) containing compound (A-1) and compound (B-1) The amount of compound (B-1) added was 0.88 g. Except for this, the same operation as in Example 1 was carried out to obtain 24.41 g of wet crystals containing compound (A-1) and compound (B-1). As a result of measuring the loss on drying of the wet crystals, it was 15.54% by weight. As a result of analyzing this wet crystal using HPLC, the area ratio of compound (A-1) to compound (B-1) was 94.94:5.06.
Then, the wet crystals obtained above were dried in the same manner as in Example 1 to obtain a condensed heterocyclic compound-containing composition (α-4), which was evaluated in the same manner. Table 1 shows the results.

(Example 5) Preparation of condensed heterocyclic compound-containing composition (α-5) containing compound (A-1) and compound (B-1) The amount of compound (B-1) added was 1.58 g. Except for this, the same operation as in Example 1 was carried out to obtain 25.23 g of wet crystals containing compound (A-1) and compound (B-1). As a result of measuring the loss on drying of the wet crystals, it was 15.21% by weight. As a result of analyzing this wet crystal using HPLC, the area ratio of compound (A-1) to compound (B-1) was 91.40:8.60.
Then, the wet crystals obtained above were dried in the same manner as in Example 1 to obtain a condensed heterocyclic compound-containing composition (α-5), which was evaluated in the same manner. Table 1 shows the results.

(Example 6) Preparation of condensed heterocyclic compound-containing composition (α-6) containing compound (A-1) and compound (B-1) After obtaining wet crystals in the same manner as in Example 4, The resulting wet crystals are placed in an eggplant-shaped flask and dried using an evaporator for 48 hours to obtain a condensed heterocyclic compound-containing composition (α-6), and the resulting condensed heterocyclic compound-containing composition ( Evaluation was performed in the same manner as in Example 1 using α-6). Table 1 shows the results. The drying operation was carried out by heating the eggplant-shaped flask on a hot water bath at 70° C. and rotating it at a speed of 10 to 30 times per minute, using a diaphragm vacuum pump at a reduced pressure of 10 mmHg.

(Example 7) Preparation of condensed heterocyclic compound-containing composition (α-7) containing compound (A-1) and compound (B-1) except that the drying time in drying using an evaporator was 80 hours A condensed heterocyclic compound-containing composition (α-7) was obtained in the same manner as in Example 6 and evaluated in the same manner. Table 1 shows the results.

(Example 8) Preparation of condensed heterocyclic compound-containing composition (α-8) containing compound (A-1) and compound (C-1) Instead of compound (B-1), the following formula (C- 1) Compound (C-1: Nocrac White (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.)) 1.20 g was added, but the same operation as in Example 1 was performed to obtain compound (A-1) and compound ( 22.16 g of wet crystals containing C-1) were obtained. As a result of measuring the loss on drying of the wet crystals, it was 7.94% by weight. As a result of analyzing this wet crystal using HPLC, the area ratio of compound (A-1) to compound (C-1) was 99.28:0.72.
Then, the wet crystals obtained above were dried in the same manner as in Example 1 to obtain a condensed heterocyclic compound-containing composition (α-8), which was evaluated in the same manner. Table 1 shows the results.

(Example 9) Preparation of condensed heterocyclic compound-containing composition (α-9) containing compound (A-1) and compound (D-1) Instead of compound (B-1), the following formula (D- 1) Compound (A-1) and compound (A-1) and 22.02 g of wet crystals containing compound (D-1) were obtained. As a result of measuring the loss on drying of the wet crystals, it was 9.28% by weight. As a result of analyzing this wet crystal using HPLC, the area ratio of compound (A-1) to compound (D-1) was 96.34:3.66.
Then, the wet crystals obtained above were dried in the same manner as in Example 1 to obtain a condensed heterocyclic compound-containing composition (α-9), which was evaluated in the same manner. Table 1 shows the results.

(Example 10) Preparation of Condensed Heterocyclic Compound-Containing Composition (α-10) Containing Compound (A-1) and Compound (E-1) 1) Compound (E-1: Noctider SS (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.)) was added in the same manner as in Example 1, except that 1.20 g of the compound (A-1) and compound ( 20.26 g of wet crystals containing E-1) were obtained. As a result of measuring the loss on drying of the wet crystals, it was 5.73% by weight. As a result of analyzing this wet crystal using HPLC, the area ratio of compound (A-1) to compound (E-1) was 98.57:1.43.
Then, the wet crystals obtained above were dried in the same manner as in Example 1 to obtain a condensed heterocyclic compound-containing composition (α-10), which was evaluated in the same manner. Table 1 shows the results.

(Example 11) Preparation of condensed heterocyclic compound-containing composition (α-11) containing compound (A-1) and compound (C-1) After obtaining wet crystals in the same manner as in Example 8, A condensed heterocyclic compound-containing composition (α-11) was obtained in the same manner as in Example 8 except that the obtained wet crystals were dried for 80 hours using an evaporator in the same manner as in Example 7. made an evaluation. Table 1 shows the results.

(Example 12) Preparation of condensed heterocyclic compound-containing composition (α-12) containing compound (A-1) and compound (D-1) After obtaining wet crystals in the same manner as in Example 9, A condensed heterocyclic compound-containing composition (α-12) was obtained in the same manner as in Example 9, except that the obtained wet crystals were dried for 80 hours using an evaporator in the same manner as in Example 7. made an evaluation. Table 1 shows the results.

(Example 13) Preparation of condensed heterocyclic compound-containing composition (α-13) containing compound (A-1) and compound (E-1) After obtaining wet crystals in the same manner as in Example 10, A condensed heterocyclic compound-containing composition (α-13) was obtained in the same manner as in Example 10, except that the obtained wet crystals were dried for 80 hours using an evaporator in the same manner as in Example 7. made an evaluation. Table 1 shows the results.

(Example 14) Preparation of condensed heterocyclic compound-containing composition (α-14) containing compound (A-1) and compound (B-1) In Synthesis Example 1, except that o-xylene was changed to toluene. , Compound (A-1) is synthesized in the same manner as in Synthesis Example 1 to obtain a reaction solution (toluene solution) of compound (A-1), and a reaction solution (toluene solution) of compound (A-1) is prepared. 24.41 g of wet crystals containing compound (A-1) and compound (B-1) were obtained in the same manner as in Example 4 except that they were used. Next, a condensed heterocyclic compound-containing composition (α-14) was obtained in the same manner as in Example 4, except that the obtained wet crystals were dried for 80 hours using an evaporator in the same manner as in Example 7. Evaluation was performed in the same manner. Table 1 shows the results.
At this time, the loss on drying of the wet crystals was measured and found to be 12.14% by weight. As a result of analyzing this wet crystal using HPLC, the area ratio of compound (A-1) to compound (B-1) was 95.48:4.52.

(Comparative Example 1) Preparation of compound (A-1) in dry state The same operation as in Example 1 was performed except that compound (B-1) was not added, and wet crystals containing compound (A-1) were prepared. 24.58 g was obtained. As a result of measuring the loss on drying of the wet crystals, it was 18.27% by weight. Further, as a result of analyzing the wet crystals using HPLC, components other than the compound (A-1) (specifically, the compound (B-1), the compound (C-1), the compound (D-1) and compound (E-1)) were not detected.
Then, the wet crystals obtained above were dried in the same manner as in Example 1 to obtain a dry compound (A-1), which was evaluated in the same manner. Table 1 shows the results.

(Comparative Example 2) Preparation of dry state compound (A-1) After obtaining wet crystals in the same manner as in Comparative Example 1, the obtained wet crystals were dried using an evaporator in the same manner as in Example 6. By doing so, a dry compound (A-1) was obtained and evaluated in the same manner. Table 1 shows the results.

(Comparative Example 3) Preparation of compound (A-1) in dry state In the same manner as in Comparative Example 2, except that the drying time in the drying using an evaporator was 80 hours, Compound (A-1) in dry state was prepared. obtained and evaluated in the same way. Table 1 shows the results.

(Comparative Example 4) Preparation of compound (A-1) in dry state synthesized in toluene solvent A dried compound (A-1) was obtained and evaluated in the same manner. Table 1 shows the results.

As shown in Table 1, in addition to compound (A-1), one of compound (B-1), compound (C-1), compound (D-1), and compound (E-1) According to the condensed heterocyclic compound-containing compositions of Examples 1 to 14, the crystallinity is lower than that of Comparative Examples 1 to 4, which consist only of the compound (A-1) and do not contain these compounds. it was suppressed.
Further, as shown in Table 1, in addition to compound (A-1), compound (B-1), compound (C-1), compound (D-1), and compound (E-1) are contained. According to the condensed heterocyclic compound-containing compositions of Examples 1 to 14, the dispersibility in acrylic rubber is high, and therefore, it is possible to exhibit a high anti-aging function for organic materials including acrylic rubber.
On the other hand, in Comparative Examples 1 to 4, which consisted only of the compound (A-1) and did not contain these compounds, the dispersibility in the acrylic rubber was not sufficient, and a sufficient anti-aging function could not be expected. .

Claims

a compound represented by the following general formula (A);
and at least one compound selected from the group consisting of compounds represented by the following general formulas (B) to (E).

(In general formula (A) above, R a and R b each independently represent an optionally substituted organic group having 1 to 30 carbon atoms.
Z a and Z b each independently represent a chemical single bond or —SO 2 —.
X 1 and X 2 each independently represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, a cyano group, a nitro group, -OR 1 , -OC( =O)-R 1 , -C(=O)-OR 1 , -O-C(=O)-OR 1 , -NR 2 (R 3 ), -NR 2 -C(=O)-R 1 , -C(=O)-NR 2 (R 3 ) or -OC(=O)-NR 2 (R 3 ). Here, R 1 , R 2 and R 3 each independently represent a hydrogen atom or an optionally substituted organic group having 1 to 20 carbon atoms.
n and m each independently represent an integer of 0 to 2, and one of n and m is not 0;
Also, when n and/or m is 2, two Ra 's and two Rb 's may be the same or different. )

(In general formula (B) above, Y 1 represents -S- or -S(=O)-, and R a , R b , Z a , Z b , X 1 , X 2 , n and m is synonymous with the above general formula (A).)

(In the above general formula (C), X 3 and X 4 are each independently a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, a cyano group, a nitro group, —OR 1 , -OC(=O)-R 1 , -C(=O)-OR 1 , -OC(=O)-OR 1 , -NR 2 (R 3 ), -NR 2 -C(= O)-R 1 , -C(=O)-NR 2 (R 3 ), or -O-C(=O)-NR 2 (R 3 ), where R 1 , R 2 and R 3 each independently represents a hydrogen atom or an optionally substituted organic group having 1 to 20 carbon atoms, and p and q each independently represents an integer of 0 to 7.)

(In general formula (D) above, X 3 and X 4 have the same definitions as in general formula (C) above, and r and s each independently represent an integer of 0 to 4.)

(In general formula (E) above, X 3 and X 4 have the same definitions as in general formula (C) above, t and u each independently represent an integer of 0 to 4, and v and w each independently represents an integer from 0 to 5.)
To the reaction solution containing the compound represented by the general formula (A) synthesized using a phenothiazine-based compound as a raw material,
The condensed heterocyclic compound-containing composition according to claim 1, which is obtained by adding at least one compound selected from the group consisting of compounds represented by formulas (B) to (E).
The compound represented by the general formula (A) and at least one compound selected from the group consisting of the compounds represented by the general formulas (B) to (E) are co-precipitated from a solution containing them. 3. The composition containing a condensed heterocyclic compound according to claim 1 or 2, which is a co-precipitate obtained by
The content of at least one compound selected from the group consisting of the compounds represented by the general formulas (B) to (E) is 1 mol or less per 1 mol of the compound represented by the general formula (A). The condensed heterocyclic compound-containing composition according to any one of claims 1 to 3.
The condensed heterocyclic compound-containing composition according to any one of claims 1 to 4, wherein the crystallinity of the compound represented by the general formula (A) is 35% or less.
The condensed heterocyclic compound-containing composition according to any one of claims 1 to 5, containing the compound represented by the general formula (A) and the compound represented by the general formula (B).
An organic material-containing composition comprising (a) an organic material and (b) the condensed heterocyclic compound-containing composition according to any one of claims 1 to 6.
The organic material-containing composition according to claim 7, wherein the (a) organic material is acrylic rubber.