JP2011252133A - Novel compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dioxadine pigment which is excellent in solubility to organic solvent.SOLUTION: The compound is represented by formula (I), wherein R-Reach independently represent hydrogen atom or 1-20C substituted or non-substituted alkyl (at least one of R-Ris 1-20C substituted or non-substituted alkyl.), Rand Reach independently represent hydrogen atom, halogen atom, alkyl, alkoxy, trifluoromethyl or nitro, and Z independently represents hydrogen atom, halogen atom, alkyl, alkoxy or phenoxy.

Description

  The present invention relates to a novel compound that can be suitably used for paints, printing inks, inkjet inks, plastic coloring materials, electroluminescent materials, coloring compositions for color filters, coloring compositions for electrophoretic display elements, and the like.

  Dioxazine-based dyes mainly have red, purple or blue color tones, and some of the dyes are known as pigments or dyes having good heat resistance and light resistance. In particular, 8,18-dichloro-5,15-diethyl-5,15-dihydrodiindolo [3,2-b: 3 ′, 2′-m, which has a chemical structure in which an indole ring is condensed to the triphenodioxazine mother nucleus. The organic pigment having a triphenodioxazine skeleton is C.I. I. Pigment Violet 23 is C.I. I. Direct blue 108 is put into practical use (Patent Document 1).

  However, C.I. I. Pigment Violet 23 has good heat resistance and light resistance, but it is a pigment, so it has low solubility in a solvent, and it has been necessary to go through a complicated pigment dispersion step in order to use it in various applications. And in terms of hue, it did not reach the clarity of the dye. In addition, C.I. I. Direct Blue 108 is a C.I. I. Although it has a chemical structure in which CI Pigment Violet 23 is sulfonated, it is hardly soluble in an organic solvent and is inappropriate for use as an organic solvent-based paint, ink, or plastic colorant. Furthermore, the molar extinction coefficient in water was low, and the coloring power was insufficient (Non-patent Document 1).

JP-A-53-16038

J. et al. Phys. Chem. , 87, 2578-2581 (1983)

  The object of the present invention is to provide organic solvent-based paints and various inks, plastic coloring materials, electroluminescent materials, coloring compositions for color filters, coloring compositions for electrophoretic display elements, and the like for organic solvents. The object is to provide a dioxazine dye having excellent solubility.

  The present inventors have found that a compound represented by the following formula (I) can solve the above problems.

  That is, the present invention provides a compound represented by the following formula (I).

[In Formula (I),
R ^{1 to} R ⁴ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms (provided that at least one of R ^{1 to} R ⁴ is substituted or unsubstituted. An alkyl group having 1 to 20 carbon atoms).
R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a trifluoromethyl group or a nitro group,
Z independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a phenoxy group. ]

  Since the compound of the present invention is a coloring compound having high solubility in an organic solvent, it is a paint, printing ink, inkjet ink, plastic coloring material, electroluminescent material, coloring composition for color filter, coloring composition for electrophoretic display element. It can use suitably for etc. Moreover, since the compound of the present invention has a high decomposition temperature, it is particularly suitable for applications requiring heat resistance.

Hereinafter, the present invention will be described in detail.
First, the definition of symbols in formula (I) used in the present invention will be described.
R ^{1 to} R ⁴ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and the alkyl group may be linear or branched. Of these, linear is preferable from the viewpoint of solubility in organic solvents.
Moreover, as a substituent of this alkyl group, a C3-C8 cycloalkyl group, a C6-C12 aryl group, a C3-C8 alkoxy group etc. can be mentioned, for example. Among these, a cycloalkyl group having 3 to 8 carbon atoms and an alkoxy group having 3 to 8 carbon atoms are preferable, and a cycloalkyl group having 3 to 8 carbon atoms is particularly preferable.
When R ^{1 to} R ⁴ are unsubstituted alkyl groups, the number of carbon atoms is 1 to 20, but from the viewpoint of solubility in organic solvents and heat resistance, the number of carbon atoms is preferably 1 to 18, and more preferably 2 to 18 Particularly, 6 to 18 is preferable.
On the other hand, when R ^{1 to} R ⁴ are substituted alkyl groups, the alkyl group has 1 to 20 carbon atoms, preferably 1 to 10, and particularly preferably 1 to 6. In this case, the total number of carbon atoms of the substituted alkyl group is preferably 2 to 20, and particularly preferably 5 to 18.
Among these, R ^{1 to} R ⁴ have an unsubstituted linear alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 8 carbon atoms from the viewpoint of solubility in organic solvents and heat resistance. An alkyl group having 1 to 20 carbon atoms is preferred.
At least one of R ^{1 to} R ⁴ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, but two or more of R ^{1 to} R ⁴ are substituted or unsubstituted carbon atoms. It is preferably 1 to 20 alkyl groups.

R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a trifluoromethyl group or a nitro group, and among them, a hydrogen atom and an alkyl group are preferable, and a hydrogen atom is particularly preferable. . 1-20 are preferable, as for carbon number of an alkyl group, 1-12 are more preferable, and carbon number of an alkoxy group has preferable 1-8, and 1-4 are more preferable. The alkyl group and alkoxy group may be linear or branched.

  Z represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a phenoxy group, among which an alkoxy group is preferable. As carbon number of an alkoxy group, 1-8 are preferable, and 1-4 are especially preferable. The alkoxy group may be linear or branched.

  Preferred specific examples of the compound represented by the formula (I) are shown in Tables 1 and 2 below, but are not limited thereto.

Next, the manufacturing method of the compound based on this invention is demonstrated based on suitable embodiment.
The compound represented by the formula (I) can be produced by various methods. For example, it can be produced through the following scheme.

(In the above scheme, R represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, X represents a leaving group in a nucleophilic substitution reaction, and R ⁵ , R ⁶ and Z are as defined above. )

  In the above scheme, compound A can be reacted with RX in the presence of a base to N-alkylate compound A to obtain compound B.

As the compound A, for example, a compound in which Z is an ethoxy group and R ⁵ and R ⁶ are hydrogen atoms (CI Pigment Violet 37) is commercially available from Ciba Specialty Chemicals. Alternatively, it may be synthesized by a known method.
In RX, examples of the leaving group represented by X include a halogen atom, an alkyl sulfonate group, and an aryl sulfonate group.
The amount of RX used in the above scheme is usually 4 times equivalent to compound A. For example, when 2 acetamide groups in compound A are N-alkylated, usually 2 times equivalent to compound A is used. do it. Thus, the amount of RX used can be appropriately selected according to the number of moles of Compound A to be N-alkylated.

Examples of the base include potassium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, sodium methylate, potassium t-butoxide, triethylamine, DBU, sodium hydride and the like.
The amount of the base used is usually 1 equivalent or more, preferably 2 times equivalent to HX eliminated by N-alkylation.

The above reaction is preferably carried out in a solvent. Examples of the solvent include amides such as N, N-dimethylformamide and N, N-dimethylacetamide, pyrrolidones such as N-methylpyrrolidone, and N, N ′. Examples thereof include imidazolidinone such as dimethylimidazolidinone, nitrile such as acetonitrile, ether such as tetrahydrofuran, alcohol such as methanol and ethanol. These solvents may be used alone or in admixture of two or more.
The amount of the solvent used is preferably 2 to 20 (w / V)%, more preferably 5 to 10 (w / V)% with respect to the mass of Compound A.

The reaction temperature is preferably 0 to 150 ° C, more preferably 20 to 100 ° C. Most preferably, it is 20 to 50 degreeC. Moreover, reaction time becomes like this. Preferably it is 1 to 24 hours, More preferably, it is 3 to 6 hours.
After completion of the reaction, the compound represented by the formula (I) can be isolated from the reaction solution by appropriately combining ordinary purification means such as filtration, washing, reprecipitation, recrystallization, centrifugation, chromatography and the like.

  The compound of the present invention thus obtained is soluble in various organic solvents including ketones such as cyclohexanone, and has an excellent heat resistance with a 5% mass reduction temperature of 300 ° C. or more in TG-DTA analysis. Can have sex.

  Therefore, the compound of the present invention can be suitably used as a paint, a printing ink, an inkjet ink, a color filter coloring composition, and the like. In that case, an organic solvent, a polymer compound, a color fading inhibitor, a curing monomer, light It can be used in combination with known components such as a polymerization initiator.

  Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

Example 1
Synthesis of Compound (14) in Table 2 1.96 g (17.5 mmol) of potassium t-butoxide, C.I. manufactured by Ciba Specialty Chemicals I. 1.63 g (2.2 mmol) of Pigment Violet 37 (hereinafter referred to as “PV-37”) and 20 mL of dimethylformamide were mixed and stirred at room temperature for 2 hours, and 1.10 g (4.4 mmol) of 1-bromododecane was further added. Stir for 5 hours. Thereafter, Celite filtration was performed, and the filtrate was reprecipitated with 300 mL of water. The obtained precipitate was washed with hexane to obtain 1.2 g of a purple solid. The ¹ H-NMR (solvent: deuterated chloroform) spectrum of the obtained compound was as follows and was confirmed to be the target compound.

¹ H-NMR: δ 7.95-7.44 (m, 10H), 7.00 (s, 2H), 6.66 (s, 2H), 3.98 (t, 4H), 3.20-3 .10 (m, 4H), 2.02 (m, 6H), 1.59-1.29 (m, 48H), 1.00 (t, 6H)

The compound obtained above was dissolved in 1-methoxy-2-propyl acetate to prepare a solution having a concentration of about 0.0010% by mass, and the absorption spectrum was measured. As a result, λmax = 562 nm and ε = 50000 mol ⁻¹ cm ⁻¹ L.
Further, the obtained compound was dissolved in cyclohexanone by 10% by mass or more.
Further, as a result of thermogravimetric-differential thermal simultaneous measurement analysis (hereinafter referred to as “TG-DTA”) of the obtained compound, the 5% mass reduction temperature was 303 ° C.

Example 2
Synthesis of Compound (16) in Table 2 1.96 g (17.5 mmol) of potassium t-butoxide, 1.63 g (2.2 mmol) of PV-37 and 20 mL of dimethylformamide were mixed and stirred at room temperature for 2 hours. -Bromocyclohexylmethane 0.78g (4.4mmol) was added, and it stirred for 5 hours. Thereafter, Celite filtration was performed, and the filtrate was reprecipitated in 300 mL of water. The obtained precipitate was washed with hexane to obtain 1.2 g of a purple solid. The ¹ H-NMR (solvent: deuterated chloroform) spectrum of the obtained compound was as follows and was confirmed to be the target compound.

¹ H-NMR: δ 7.95-7.34 (m, 10H), 6.95 (s, 2H), 6.56 (s, 2H), 3.97 (t, 4H), 3.20-3 .10 (m, 4H), 2.05 (m, 6H), 1.59-1.18 (m, 24H), 0.99 (t, 6H)

The compound obtained above was dissolved in 1-methoxy-2-propyl acetate to prepare a solution having a concentration of about 0.0010% by mass, and the absorption spectrum was measured. As a result, λmax = 565 nm and ε = 55000 mol ⁻¹ cm ⁻¹ L.
Further, the obtained compound was dissolved in cyclohexanone by 10% by mass or more.
Moreover, 5% mass reduction | decrease temperature was 310 degreeC as a result of TG-DTA of the obtained compound.

Example 3
Synthesis of Compound (13) in Table 2 1.96 g (17.5 mmol) of potassium t-butoxide, 1.63 g (2.2 mmol) of PV-37 and 20 mL of dimethylformamide were mixed and stirred at room temperature for 2 hours. -Bromohexane 0.73g (4.4mmol) was added, and it stirred for 5 hours. Thereafter, Celite filtration was performed, and the filtrate was reprecipitated in 300 mL of water. The obtained precipitate was washed with hexane to obtain 1.3 g of a purple solid. The ¹ H-NMR (solvent: deuterated chloroform) spectrum of the obtained compound was as follows and was confirmed to be the target compound.

¹ H-NMR: δ 7.95-7.44 (m, 10H), 6.98 (s, 2H), 6.56 (s, 2H), 3.97 (t, 4H), 3.20-3 .10 (m, 4H), 1.98 (m, 6H), 1.59-1.28 (m, 24H), 0.99 (t, 6H)

The compound obtained above was dissolved in 1-methoxy-2-propyl acetate to prepare a solution having a concentration of about 0.0010% by mass, and the absorption spectrum was measured. As a result, λmax = 558 nm and ε = 60000 mol ⁻¹ cm ⁻¹ L.
Further, the obtained compound was dissolved in cyclohexanone by 10% by mass or more.
Moreover, the 5% mass reduction | decrease temperature was 315 degreeC as a result of TG-DTA of the obtained compound.

Example 4
Synthesis of Compound (4) in Table 1 Sodium hydride 0.3 g (7.5 mmol), PV-37 1.63 g (2.2 mmol) and dimethylformamide 20 mL were mixed and stirred at room temperature for 2 hours. Bromodecane 2.19g (8.8mmol) was added and stirred for 3 hours. Thereafter, Celite filtration was performed, and the filtrate was reprecipitated in 300 mL of water. The obtained precipitate was washed with hexane to obtain 1.5 g of a purple solid. The ¹ H-NMR (solvent: deuterated chloroform) spectrum of the obtained compound was as follows and was confirmed to be the target compound.

¹ H-NMR: δ 7.95-7.44 (m, 10H), 6.98 (s, 2H), 6.56 (s, 2H), 3.97 (t, 4H), 3.20-3 .10 (m, 4H), 1.98 (m, 6H), 1.59-1.28 (m, 96H), 0.99 (t, 6H)

The compound obtained above was dissolved in 1-methoxy-2-propyl acetate to prepare a solution having a concentration of about 0.0010% by mass, and the absorption spectrum was measured. As a result, λmax = 542 nm and ε = 50000 mol ⁻¹ cm ⁻¹ L.
Further, the obtained compound was dissolved in cyclohexanone by 10% by mass or more.
Moreover, 5% mass reduction | decrease temperature was 310 degreeC as a result of TG-DTA of the obtained compound.

Comparative Example PV-37 was dissolved in 1-methoxy-2-propyl acetate to prepare a solution having a concentration of about 0.0010% by mass, and an absorption spectrum was measured. As a result, it was ε = 600 mol ⁻¹ cm ⁻¹ L at 562 nm.
Further, PV-37 did not dissolve even in 0.1% by mass in either 1-methoxy-2-propyl acetate or cyclohexanone.

Claims (3)

A compound represented by the following formula (I).

[In Formula (I),
R ^{1 to} R ⁴ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms (provided that at least one of R ^{1 to} R ⁴ is substituted or unsubstituted. An alkyl group having 1 to 20 carbon atoms).
R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a trifluoromethyl group or a nitro group,
Z independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a phenoxy group. ] At least one of the R ^{1 to} R ⁴ is an unsubstituted linear alkyl group having 1 to 20 carbon atoms, or is substituted with a cycloalkyl group having 3 to 8 carbon atoms. The compound of Claim 1 which is an alkyl group of these. The compound according to claim 1 or 2, wherein Z is an alkoxy group having 1 to 8 carbon atoms, and R ⁵ and R ⁶ are hydrogen atoms.