JP2019172848A - Quinophthalone compound, and pigment composition containing the same - Google Patents

Abstract

To provide a novel quinophthalone compound having excellent fastness such as heat resistance, and a pigment composition that includes the compound and is useful for a color liquid crystal display device or the like.SOLUTION: The present invention provides a quinophthalone compound represented by the formula (1) (where, n is an integer of 1 to 3, Rto Reach represent a hydrogen atom, a C 1-4 alkyl group, a C 1-4 alkoxy group, a halogen atom, a carboxyl group, a nitro group or a sulfo group), a pigment composition containing the compound, and a color resist containing the pigment composition.SELECTED DRAWING: None

Description

  The present invention relates to a quinophthalone compound used in a resist for optical filters used in the production of liquid crystal displays and imaging devices, and a pigment composition having excellent heat resistance, containing the compound.

  Dyes are used for color display using reflected light or transmitted light in the fields of fiber materials, liquid crystal display devices, ink jets, etc., and as such dyes, quinophthalone represented by the following formula (A) is used. A compound is known (Patent Document 1).

  A color liquid crystal display device is manufactured through a process in which a transparent electrode for driving liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning liquid crystal in a certain direction is formed thereon. Therefore, in these steps, the color filter is exposed to a high temperature of 200 ° C. or higher. For this reason, a color material for a color filter constituting the color liquid crystal display device is required to have high heat resistance.

  However, in general, a colored body using a quinophthalone compound represented by the above formula (A) has insufficient heat fastness and does not necessarily satisfy market demands.

International Publication No. 2007/058209

  The problem to be solved by the present invention is to provide a novel quinophthalone compound excellent in fastness such as heat resistance, and a pigment composition useful for applications such as a color liquid crystal display device using the compound. .

As a result of intensive studies to solve the above problems, the present inventor has found that the above problems can be solved by the following present invention.
That is, the present invention
(1) The following formula (1)

(In the formula (1), n is an integer of 1 to 3, R _{1 to} R ₄ are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a carboxyl group, nitro A quinophthalone compound represented by: a group or a sulfo group;
(2) The quinophthalone compound according to item (1), wherein R _{1 to} R ₄ are hydrogen atoms,
(3) The quinophthalone compound according to (1) or (2) above, wherein n is 1 or 2.
(4) A pigment composition containing the quinophthalone compound according to any one of (1) to (3) above, an organic pigment and a resin dispersant, and (5) a pigment composition according to (4) above , A color resist containing a binder resin and a polymerizable compound,
About.

  The quinophthalone compound represented by the formula (1) of the present invention is excellent in fastness such as heat resistance, and the pigment composition containing the compound is applied to a wide range of applications requiring fastness such as color filter inks. it can.

The present invention is described in detail below.
The quinophthalone compound of the present invention (hereinafter, for convenience, the “quinophthalone compound of the present invention” may be simply referred to as “the compound of the present invention”) has a structure represented by the following formula (1).

In formula (1), n is the number of substituents represented by the following formula (1-1), and represents an integer of 1 to 3. That is, the compound of the present invention is a compound represented by the above formula (A) and having 1 to 3 substituents represented by the following formula (1-1). The substitution position of the substituent represented by the formula (1-1) in the compound represented by the formula (A) is 11 carbon atoms whose positions are represented by a to k in the following formula (1-2). Any of 1 to 3 carbon atoms selected from may be used. Incidentally, R ₁ to R ₄ in the formula (1-1) has the same meaning as R ₁ to R ₄ in the formula (1).
N in Formula (1) is preferably 1 or 2, that is, the compound of the present invention preferably has one or two substituents represented by Formula (1-1).

In formula (1), R _{1 to} R ₄ represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a carboxy group, a nitro group, or a sulfo group.
The alkyl group having 1 to 4 carbon atoms represented by R _{1 to} R _{4 in} the formula (1) may be either linear or branched, but is preferably linear. Specific examples thereof include a methyl group, Examples include an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group, and a methyl group or an ethyl group is preferable.
The alkoxy group having 1 to 4 carbon atoms represented by R _{1 to} R _{4 in} the formula (1) may be linear or branched, and specific examples thereof include methoxy group, ethoxy group, n-propoxy group, iso -Propoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group and the like.

Specific examples of the halogen atom represented by R _{1 to} R _{4 in} the formula (1) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a bromine atom or a chlorine atom.
As R _{1 to} R ₄ in Formula (1), a hydrogen atom is preferable.

  The compound of the present invention can be synthesized by a known method. For example, in an acidic solvent such as concentrated sulfuric acid, paraformaldehyde and phthalimide, substituted phthalimide, bis-phthalimidomethyl ether, substituted bis-phthalimidomethyl ether, N-hydroxymethylphthalimide, or substituted N -A method of reacting hydroxymethylphthalimide with a quinophthalone compound can be used.

  Specific examples of the compound of the present invention are shown below.

The pigment composition of the present invention contains the compound of the present invention, an organic pigment and a resin dispersant.
The organic pigment contained in the pigment composition of the present invention is not particularly limited as long as it is a conventionally known one such as those described in the color index. For example, azo, ansanthrone, anthraquinone, isoindolinone, isoindoline, indanthrone, quinacridone, quinophthalone, dioxazine, diketopyrrolopyrrole, thioindigo, phthalocyanine, perylene and And benzimidazolone pigments, and diketopyrrolopyrrole pigments (pike having a diketopyrrolopyrrole skeleton) are preferred.
The content of the compound of the present invention in the pigment composition of the present invention is usually 0.1 to 70 parts by mass, preferably 0.5 to 60 parts by mass, more preferably 1 to 1 part by mass with respect to 100 parts by mass of the organic pigment. 50 parts by mass. By setting the addition amount of the compound of the present invention to the organic pigment within the above range, the intended dispersion stability of the pigment composition and the fine formation of the organic pigment can be achieved.

  The resin dispersant contained in the pigment composition of the present invention is not particularly limited as long as it is a known resin dispersant, but an anionic resin dispersant is preferable in consideration of the affinity with the compound of the present invention. Examples of the anionic resin dispersants include BYK102, 106, 111, 118, 170, 174 of Big Chemie Japan, Jonkrill 586, 611, 804, 819 of BASF Japan, etc. It is not limited. The addition amount of the resin dispersant is usually 5 to 100 parts by mass, preferably 10 to 50 parts by mass with respect to 100 parts by mass of the organic pigment. When the amount of the resin dispersant added to the organic pigment is less than 5 parts by mass, a pigment composition with good dispersion stability cannot be obtained.

  If necessary, an organic solvent can be added to the pigment composition of the present invention. The organic solvent that can be used is not particularly limited, for example, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve, cyclohexanone, cyclopentanone, ethylene glycol diethyl ether, Examples include diethylene glycol dimethyl ether, ethyl acetate, butyl acetate, methanol, ethanol, and isopropyl alcohol. These may be used alone or in admixture of two or more. The organic solvent is preferably used in an amount of 90% by mass or less in the pigment composition.

The color resist of the present invention contains the pigment composition of the present invention, a binder resin and a polymerizable compound.
The binder resin contained in the color resist of the present invention is not particularly limited. For example, styrene (co) polymer, (meth) acrylic acid ester (co) polymer, styrene-maleic acid ester copolymer, cellulose Examples thereof include acetate-based resins, polyester-based resins, polyurethane-based resins, polyamide-based resins, and polyimide-based resins. These may be used alone or in combination of two or more. The binder resin is used in an amount of 50% by mass or less in the color resist pigment composition of the present invention.

Examples of the polymerizable compound contained in the color resist of the present invention include a photopolymerization monomer, an epoxy compound, and a melamine compound. Specific examples of these polymerizable compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, and diethylene glycol di (meth). Acrylate, triethyleneglycol (meth) acrylate, tetraethylene glycol (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate, bisphenol-A type epoxy di (meth) acrylate, bisphenol Nord-F type epoxy di (meth) acrylate, bisphenol-fluorene type epoxy di (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, ethoxylated glycerin tri (meth) acrylate , Ethoxylated isocyanuric acid tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, cayarad RP-1040 (Nippon Kayaku), Kayrad DPCA-30 (Nippon Kayaku), UA-33H (Shin Nakamura Chemical), UA-53H (Shin Nakamura Chemical) and M-8060 (Toagoi) Methicacrylate monomers such as TEMPIC (made by Sakai Chemical), TMMP (made by Sakai Chemical), PEMP (made by Sakai Chemical) and DPMP (made by Sakai Chemical); NC of Nippon Kayaku products -6000, NC-6300, NC-6300H, NC-3000, EOCN-1020, XD-1000, EPPN-501H, BREN-S, NC-7300L, Daicel Chemicals' Celoxite 2021P, EHPE3150, Cyclomer M100, Epolide PB3600 , Japan Epoxy Resin products Epicoat 828, Epicoat YX8000, Epicoat YX4000, Printec products VG-3101L, Silaace S510 (Nisso), TEPIC (Nissan Chemical Industries) and other epoxy compounds; and methylolated melamine And melamine compounds such as Mw-30 (Sanwa Chemical), but are not limited thereto.
These polymerizable compounds are preferably used in combination with a polymerization initiator, a curing accelerator or the like, if necessary.

Examples of other additives that can be added to the color resist of the present invention as necessary include a thixotropic agent, a polymerization initiator and a curing agent, a curing accelerator, a polymerization inhibitor, an organic or inorganic filler, and a coupling agent. However, these may be selected depending on the specific purpose and usage of the color resist, and are not limited to the above. Further, the addition amount may be selected in accordance with a specific purpose application.
Of these additives, a thixotropic agent, an organic or inorganic filler, a coupling agent, and the like can be added to the pigment composition of the present invention as necessary.

The pigment composition of the present invention can be prepared, for example, by the following method. That is, as a method of blending the organic pigment and the compound of the present invention, various conventionally known methods, for example, a method of simply mixing each dry powder or press cake, various dispersions such as a kneader, a bead mill, a dissolver, an attritor, etc. Examples thereof include a method of mechanically mixing by a machine, a method of suspending an organic pigment in water or an organic solvent, and adding and mixing the compound of the present invention therein to deposit uniformly on the surface of the organic pigment. Next, the resulting organic pigment and the mixture of the compound of the present invention are mixed with a resin dispersant and various organic solvents and various additives as necessary, and dispersed with a sand mill, an annular bead mill, an attritor or the like. Thus, a desired pigment composition can be produced. Alternatively, for convenience, the organic pigment, the compound of the present invention, the resin dispersant, and other components as necessary may be mixed and dispersed in a lump.
In addition, the color resist of the present invention is produced by further blending a binder resin, a polymerizable compound, various additives, and the like with the pigment composition obtained above, and dispersing with a sand mill, an annular bead mill, an attritor or the like. be able to.

  The use of the pigment composition of the present invention is not particularly limited. For example, various printing inks such as gravure printing inks, paints, dry toners or wet toners for electrophotography, inks for inkjet recording, colorants for color filter resists, Can be used. In particular, the pigment composition of the present invention is useful as a colorant for resists for color filters that require finer pigments and high stability.

  Hereinafter, the present invention will be described specifically by way of examples. In the text, “parts” and “%” are based on mass unless otherwise specified. The maximum absorption wavelength in the examples is a value measured with a spectrophotometer “UV-3150 manufactured by Shimadzu Corporation”.

Example 1 (Synthesis of the compound represented by No. 1 of the above specific example compound)
To the reaction vessel, 3.4 parts of the compound represented by the above formula (A), 1.8 parts of N-hydroxymethylphthalimide and 20 parts of 98% concentrated sulfuric acid were added, reacted at 90 ° C. for 14 hours, and then cooled to room temperature. This reaction solution was added to 200 parts of water, and the precipitated solid was separated by filtration. The obtained solid was washed with water and dried with a hot air dryer at 80 ° C. 3.0 parts of the compound represented by 1 were obtained. The maximum absorption wavelength λmax of the compound was 461 nm (DMF).

Example 2 (Synthesis of a compound represented by No. 2 of the above specific example compound)
In a reaction vessel, 3.4 parts of a compound represented by the following formula (A), 3.5 parts of N-hydroxymethylphthalimide and 20 parts of 98% concentrated sulfuric acid were added, reacted at 90 ° C. for 14 hours, and then cooled to room temperature. This reaction solution was added to 200 parts of water, and the precipitated solid was separated by filtration. The obtained solid was washed with water and dried with a hot air dryer at 80 ° C. 3.3 parts of the compound represented by 2 was obtained. The maximum absorption wavelength λmax of the compound was 462 nm (DMF).

Synthesis example 1
A compound represented by the formula (A) was synthesized according to the method described in Patent Document 1.

(Heat resistance test)
The differential scanning calorimetry of the compounds obtained in Examples 1 and 2 and Comparative Example 1 was performed using a differential thermothermal gravimetric simultaneous measurement apparatus (TG / DTA 6200 manufactured by SII Nanotechnology). The amount of sample used for one measurement was 3 mg. In a nitrogen atmosphere, the temperature was increased from 30 ° C. at a rate of 10 ° C. per minute and measured to 550 ° C. to obtain a temperature T _{5 at} which the weight loss rate was 5%. The results are shown in Table 1.

  As is apparent from the results in Table 1, the compounds of Examples 1 and 2 have a higher temperature at which the weight loss rate is 5% compared to the compound of Comparative Example 1, and are excellent in heat fastness. .

The compound of the present invention has high heat fastness, and the pigment composition containing the compound can be applied to a wide range of applications requiring flexibility such as color filter inks.

Claims (5)

Following formula (1)

(In the formula (1), n is an integer of 1 to 3, R _{1 to} R ₄ are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a carboxyl group, nitro A quinophthalone compound represented by the formula: The quinophthalone compound according to claim 1, wherein R _{1 to} R ₄ are hydrogen atoms. The quinophthalone compound according to claim 1 or 2, wherein n is 1 or 2. A pigment composition comprising the quinophthalone compound according to any one of claims 1 to 3, an organic pigment, and a resin dispersant. A color resist comprising the pigment composition according to claim 4, a binder resin, and a polymerizable compound.