JP5642739B2 - Dye compound and method for producing the same, colored curable composition, colored cured film, color filter and method for producing the same, and display device - Google Patents

Description

  The present invention relates to a dye compound and a production method thereof, a colored curable composition, a colored cured film, a color filter and a production method thereof, and a display device.

  Conventionally, a small liquid crystal display device such as a mobile phone, a mobile game machine, a PDA, and an organic EL display device have been provided with a light source for backlight, and the light emitted from this light source displays a desired image through a color filter. Is done. As a color material used for a color filter constituting such a display device, a colorant having high luminance and capable of displaying a color by transmitting the bright line of the backlight well is advantageous. In recent years, liquid crystal display devices and organic EL display devices in applications such as display monitors for personal computers and televisions have been increased in size, and display devices having large screens have color reproducibility higher than that of small display devices. It is important. A colorant used for a color filter is required to be capable of enhancing color purity and contrast that influence improvement in image quality in addition to luminance.

  In response to such demands, studies are underway to use dyes with relatively easy hue adjustment as colorants instead of conventionally used pigments. By using a dye as a colorant, the hue and brightness of a display image when an image is displayed can be increased due to the color purity of the dye itself and the vividness of the hue, as in the case of using a pigment. There is no concern associated with coarse particles, and there is an advantage that high contrast is easily obtained.

  As examples of dyes, dye compounds having a wide variety of dye bases such as dipyrromethene dyes, pyrimidine azo dyes, pyrazole azo dyes, xanthene dyes and triarylmethane dyes have been proposed.

  In addition to the dyes described above, methine dyes having a specific structure have been disclosed as examples of dyes excellent in heat fastness and light fastness (see, for example, Patent Document 1). Furthermore, a dye having a structure in which two pyrazolotriazole rings are linked by a methine group is disclosed as a dye species for inkjet recording (see, for example, Patent Document 2).

JP-A-2005-250420 JP 2011-12256 A

  Various dyes have been proposed according to various uses and purposes so far, but the actual situation is that they do not necessarily satisfy sufficient characteristics from the viewpoint of recording material use. Among the performances that the color material should have, color purity, in particular, is extremely important as a characteristic that affects the quality of an image, and it is desired to exhibit a hue with a sharp absorption peak.

  Furthermore, the color material has not only good color purity itself, but also durability that can stably maintain the hue for a long period of time, specifically, for example, stability when exposed to heat. It is required that A color material having durability can maintain the intended color, brightness, and contrast of the formed image.

  The present invention has been made in view of the above, and a dye compound having high color purity and excellent heat resistance, and a method for producing the same, a colored cured film having excellent hue and high brightness, and excellent heat resistance are obtained. Colored curable composition obtained, a colored cured film having good hue and high brightness, excellent heat resistance, a color filter having good hue and high brightness, contrast and heat resistance, and a method for producing the same, It is another object of the present invention to provide a display device capable of stably displaying a clear image over a long period of time, and to achieve the object.

Specific means for achieving the above object are as follows.
<1> A dye compound represented by the following general formula (1). In the following general formula (1), R ¹ and R ² represent S ₂ O ₂ R ³ , and R ³ represents an alkyl group having 4 to 18 carbon atoms.

<2 > A dye compound represented by the general formula (1). In the above general formula (1), ^{R 1} and ^{R 2} represent COR ^{3, R 3} is to display the alkyl group having 6 to 18 carbon atoms.
<3> The dye fee compound that will be selected from the following structures.

< 4 > The dye compound according to <1> or < 2>, wherein R ¹ and R ² in the general formula (1) represent the same group and have a symmetric structure.
< 5 > A dye compound that produces the dye compound according to any one of <1> to < 4 > above by reacting a compound represented by the following general formula (2) with an orthoformate compound. It is a manufacturing method. In the following general formula (2), R ⁵ represents SO ₂ R ³ or COR ³ . R ³ represents an alkyl group having 4 to 18 carbon atoms when R ⁵ is SO ₂ R ³ , and represents an alkyl group having 6 to 18 carbon atoms when R ⁵ is COR ³ .

< 6 > The compound represented by the following general formula (2) is reacted with the aldehyde compound represented by the following general formula (3) or a tautomer thereof, and any one of the above <1> to < 4 > The manufacturing method of the dye compound which manufactures the dye compound as described in any one.
In the following general formula (2), R ⁵ represents SO ₂ R ³ or COR ³ . R ³ represents an alkyl group having 4 to 18 carbon atoms when R ⁵ is SO ₂ R ³ , and represents an alkyl group having 6 to 18 carbon atoms when R ⁵ is COR ³ . In the following general formula (3), R ⁶ represents SO ₂ R ³ or COR ³ , R ³ represents an alkyl group having 4 to 18 carbon atoms when R ⁶ is SO ₂ R ³ , and R ^{3 When 6} is COR ³ , it represents an alkyl group having 6 to 18 carbon atoms .

< 7 > A colored curable composition comprising at least the dye compound according to any one of <1> to < 4 > and a polymerizable compound.
< 8 > The colored curable composition according to < 7 >, further including a polymerization initiator.
< 9 > The coloring according to < 7 > or < 8 >, further including at least one selected from the group consisting of a copper phthalocyanine pigment, a zinc phthalocyanine pigment, a halogenated copper phthalocyanine pigment, and a halogenated zinc phthalocyanine pigment. It is a curable composition.
< 10 > The colored curable composition according to any one of < 7 > to < 9 >, further including at least one selected from a triarylmethane dye, a squarylium dye, and a phthalocyanine dye.
< 11 > A colored cured film comprising the dye compound according to any one of <1> to < 4 >.
< 12 > A color filter having the colored cured film according to < 11 >.
< 13 > The step of applying the colored curable composition according to any one of < 7 > to < 10 > on a support to form a colored film, and exposing the colored film in a pattern-like manner. And a step of forming a colored cured film by development.
< 14 > A display device including the color filter according to < 12 > or the color filter manufactured by the method for manufacturing a color filter according to < 13 >.

According to the present invention, a dye compound having high color purity and excellent heat resistance and a method for producing the same are provided. Also,
ADVANTAGE OF THE INVENTION According to this invention, the colored curable composition from which the colored cured film which has a favorable hue, has high brightness | luminance, and was excellent in heat resistance is provided. Furthermore,
According to the present invention, a color filter having a good hue, high luminance, excellent contrast and heat resistance and a method for producing the same are provided. Furthermore,
ADVANTAGE OF THE INVENTION According to this invention, the display apparatus which can perform a clear image display stably over a long term is provided.

Hereinafter, the novel dye compound of the present invention and a production method thereof, and a colored curable composition, a colored cured film, a color filter, a production method thereof, and a display device using the same will be described in detail.
In the present specification, (meth) acrylate is meant to include both acrylate and methacrylate, (meth) acryl is both acryl and methacryl, (meth) acryloyl is both acryloyl and methacryloyl. Are used to include each.

<Dye compound and production method thereof>
The dye compound of the present invention is a compound represented by the following general formula (1). This dye compound exhibits a yellow hue.

  Conventionally, dye compounds having a pyrazolotriazole ring are known to have various structures, but there is a high demand for color characteristics of display images, and further improvements to yellow color purity and heat resistance are required. ing. In view of such circumstances, the dye compound of the present invention is characterized by having a structure having a tertiary butyl group and a phenyl group substituted with a substituted amino group at the para position on the pyrazolotriazole ring in the molecule. With such a structure, the absorption peak of the maximum absorption wavelength in the yellow wavelength region (400 to 500 nm) is sharp, the color purity is high, and the heat resistance is excellent.

In the general formula (1), R ¹ and R ² each independently represents SO ₂ R ³ or COR ³ . R ³ represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms.

The alkyl group having 1 to 18 carbon atoms represented by R ³ may have a linear structure or a branched structure, and may be unsubstituted or further substituted with a substituent. Specific examples of the alkyl group represented by R ³ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, 3-heptyl group, octyl group. Group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, methoxyethoxyethyl group, ethoxycarbonylethyl group and the like. Among them, the alkyl group represented by R ^3, in view of color purity and heat resistance, preferably an alkyl group having 4 to 18 carbon atoms, more preferably an alkyl group having 6 to 18 carbon atoms, more preferably It is a C6-C12 alkyl group.

  In addition, examples of the substituent when the alkyl group has a substituent include a halogen atom, an alkoxy group, an ester group, an amide group, and a sulfonamide group.

The aryl group having 6 to 18 carbon atoms represented by R ³ may be unsubstituted or further substituted with a substituent. Specific examples of the aryl group represented by R ³ include a phenyl group, 2-methylphenyl group, 4-ethoxycarbonylphenyl group, 4-chlorophenyl group, and 3- (2-ethylhexyloxycarbonyl) phenyl group. Among these, from the viewpoints of color purity and heat resistance, the aryl group represented by R ³ is preferably an aryl group having 8 to 18 carbon atoms, and more preferably an aryl group having 10 to 18 carbon atoms.

  In addition, examples of the substituent in the case where the aryl group has a substituent include a halogen atom, an alkoxy group, an ester group, an amide group, and a sulfonamide group as described above.

  Specific examples of the dye compound represented by the general formula (1) include specific examples (exemplary compounds Y-1 to Y-26) having the following structures. However, the present invention is not limited to these compounds.

Among the above, R ¹ and R ² in the general formula (1) show a sharper absorption peak in the yellow wavelength region, and both R ¹ and R ² are more excellent in color purity and heat resistance. The case of representing SO ₂ R ³ is preferable, and R ³ in this case is preferably an alkyl group having 4 to 18 carbon atoms, more preferably an alkyl group having 6 to 18 carbon atoms, and still more preferably an alkyl group having 8 to 12 carbon atoms. It is a group.
In addition, R ¹ and R ² in the general formula (1) show a sharper absorption peak in the yellow wavelength region, and both R ¹ and R ² are COR ^{3 in that they} are excellent in color purity and heat resistance. In this case, R ³ is preferably an alkyl group having 6 to 18 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms.

Furthermore, in the general formula (1), R ¹ and R ² preferably both represent SO ₂ R ³ (R ³ : an alkyl group having 8 to 12 carbon atoms), and both R ¹ and R ² are both It represents SO ₂ R ^3, particularly preferred may represent the same alkyl groups ^{R 3} and ^{R 3} in ^{R 2} in ^{R 1.} Among these, the exemplified compounds Y-1, Y-3, and Y-6 are particularly preferable, and the exemplified compounds Y-1 and Y-3 are most preferable.

  Although the synthesis | combination of the dye compound represented by General formula (1) can be performed in accordance with a conventionally well-known method, in this invention, it synthesize | combines suitably by the following methods A and B.

<Method A (symmetric structure)>
The dye compound represented by the general formula (1) of the present invention is obtained by reacting a compound represented by the following general formula (2) with an orthoformate compound (HC (OR) ₃ , R: alkyl group). Is synthesized.
In General Formula (2), R ⁵ represents SO ₂ R ³ or COR ³ , and R ³ represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms. Here, the details _SO 2 ^{R 3} and COR ³ and ^{R 3,} have the same meaning as _SO 2 ^{R 3} and COR ³ and ^{R 3} in the general formula described above (1), a preferable embodiment thereof is also the same.

A specific synthesis method in this case is shown in the following scheme 1.
As shown in Scheme 1, for example, compound A prepared in advance is reacted with a compound having a desired SO ₂ R ³ or COR ³ moiety to produce a compound (intermediate) represented by general formula (2) To do. Next, by reacting this compound with an orthoformate compound, the compound represented by the general formula (2) is dimerized to synthesize a dye compound having a symmetric structure.
Here, Compound A is synthesized by the method described in EP 0571959.

  Examples of the orthoformate compound include trimethyl orthoformate and triethyl orthoformate.

<Method B (asymmetric structure)>
The dye compound represented by the general formula (1) of the present invention is synthesized by reacting the compound represented by the above general formula (2) with the aldehyde compound represented by the following general formula (3). The
In General Formula (3), R ⁶ represents SO ₂ R ³ or COR ³ , and R ³ represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms. Here, the details _SO 2 ^{R 3} and COR ³ and ^{R 3,} have the same meaning as _SO 2 ^{R 3} and COR ³ and ^{R 3} in the general formula described above (1), a preferable embodiment thereof is also the same.
In addition, the aldehyde compound represented by the general formula (3) exists as a tautomer as follows.

A specific synthesis method in this case is shown in the following scheme 2.
As shown in Scheme 2, for example, Compound A prepared in advance is reacted with the first compound having the desired SO ₂ R ³ or COR ³ moiety in the same manner as in Scheme 1 above, to give a general formula (2) The compound represented (Intermediate 1) is produced. Separately, compound A is reacted with a second compound having the desired SO ₂ R ³ or COR ³ moiety in the same manner as in scheme 1 above to give a compound represented by general formula (2) (intermediate) After the body 2) is formed, the aldehyde body of this intermediate 2 is formed. Next, a dye compound having an asymmetric structure is synthesized by reacting intermediate 1 and the aldehyde of intermediate 2 with each other.

<Colored curable composition>
The colored curable composition of the present invention is composed of at least the above-described dye compound of the present invention (the dye compound represented by the general formula (1)) and a polymerizable compound. As described above, the colored curable composition of the present invention contains the dye compound of the present invention, so that the absorption peak at the maximum absorption wavelength is sharp, the hue is excellent, and the brightness is high.
Further, the colored curable composition of the present invention preferably further contains a polymerization initiator, and if necessary, further contains other components such as a binder, a crosslinking agent, a surfactant, and an organic solvent. Also good.

-Dye-
The colored curable composition of the present invention is composed of one or more selected from the above-described dye compounds as a coloring component, but other color materials other than this dye compound may be used in combination. Good. The details and preferred embodiments of the dye compound of the present invention are as described above.

The content of the dye compound represented by the general formula (1) in the colored curable composition is preferably 5% by mass to 50% by mass with respect to the total solid content of the colored curable composition, 10 mass%-30 mass% is more preferable.
When the content ratio of the dye compound is 5% by mass or more, a good yellow hue is obtained, and the brightness is high and the heat resistance is excellent. Further, when the content ratio of the dye compound is 50% by mass or less, it is advantageous from the viewpoints of suppression of dye precipitation from the curable composition and developability during patterning.

As other colorants that can be used in combination in the colored curable composition of the present invention, a colorant having a different hue from that of the compound represented by the general formula (1) described above (hereinafter simply referred to as “colorant”). Also referred to as “other colorants”). The other colorant may be selected from known dyes, dye derivatives, pigments, and pigment dispersions having absorption in the visible light wavelength range.
In addition, since the compound represented by the general formula (1) described above has the maximum absorption peak wavelength (λ _max ) in the wavelength range of 400 nm to 500 nm, other colorants include those in the visible wavelength range. A colorant having a wavelength range in which an absorption peak at a maximum absorption wavelength in a range from 380 nm to 800 nm is more than 500 nm is preferably used.

  In the present invention, the absorption peak at the maximum absorption wavelength of the compound represented by the general formula (1) and the other colorant can be measured for a dye solution or a pigment dispersion containing a color material to be measured. It is a value measured with a CARY5 / UV-visible spectrophotometer (manufactured by Varian), adjusted with a solvent so as to have a concentration (for example, a concentration at which the absorbance is 0.8 to 1.0).

As a dye that can be used as another colorant, a dye that does not affect the hue or that is suitable for forming a desired hue can be selected. Any structure may be used, for example, a triarylmethane dye, Examples include squarylium dyes and phthalocyanine dyes.
As the triarylmethane dye, dyes described in JP-A-2007-94187 and JP-A-2008-304766 are preferable. As the squarylium dye, dyes described in JP-A-2004-099713 and JP-A-4413193 are preferable. As the phthalocyanine dye, dyes described in JP2009-51896A and JP2011-197670A are preferable.

  Examples of pigments that can be used as other colorants include perylene, perinone, quinacridone, quinacridonequinone, anthraquinone, anthanthrone, benzimidazolone, disazo condensation, disazo, azo, indanthrone, phthalocyanine, and triarylcarbonium. , Dioxazine, aminoanthraquinone, diketopyrrolopyrrole, indigo, thioindigo, isoindoline, isoindolinone, pyranthrone, or isoviolanthrone. More specifically, for example, perylene compound pigments such as Pigment Red 190, Pigment Red 224, and Pigment Violet 29, perinone compound pigments such as Pigment Orange 43, and Pigment Red 194, Pigment Violet 19, and Pigment Violet. 42, quinacridone such as Pigment Red 122, Pigment Red 192, Pigment Red 202, Pigment Red 207, or Pigment Red 209, quinacridone compound pigment, Pigment Red 206, Pigment Orange 48, or Pigment Orange 49 Quinone compound pigments, anthraquinone compound pigments such as pigment yellow 147, anthanthrone compound pigments such as pigment red 168, and pigments Benzimidazolone compound pigments such as Pigment 25, Pigment Violet 32, Pigment Orange 36, Pigment Yellow 120, Pigment Yellow 180, Pigment Yellow 181, Pigment Orange 62, or Pigment Red 185 Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 166, Pigment Orange 34, Pigment Orange 13, Pigment Orange 31, Pigment Red 144, Pigment Red 166, Pigment Red Red 220, Pigment Red 221, Pigment Red 242, Pigment Red 248, Pigment Red 262, or Pigment Red Disazo condensation compound pigments such as Rune 23, Pigment Yellow 13, Pigment Yellow 83, or Pigment Yellow 188 Disazo Compound Pigments, Pigment Red 187, Pigment Red 170, Pigment Yellow 74, Pigment Yellow 150, Pigment Red 48, Pigment Red 53, Pigment Orange 64, Pigment Red 247 and other azo compound pigments, Pigment Blue 60 and other indanthrone compound pigments, Pigment Green 7, Pigment Green 36, Pigment Green 37, phthalocyanine compound pigments such as Pigment Green 58, Pigment Blue 16, Pigment Blue 75, or Pigment Blue 15, Pigment Blue 56, Alternatively, a triarylcarbonium compound pigment such as Pigment Blue 61, a dioxazine compound pigment such as Pigment Violet 23, or Pigment Violet 37, an anthraquinone compound pigment such as Pigment Red 177, Pigment Red 254, and Pigment Red 255 Pigment Red 264, Pigment Red 272, Pigment Orange 71, or Pigment Orange 73, etc., Diketopyrrolopyrrole Compound Pigment, Pigment Red 88 or other thioindigo compound pigment, Pigment Yellow 139, Pigment Orange 66, etc. Isoindoline compound pigments such as Pigment Yellow 109, Pigment Orange 61, and Pigment Orange 61 0 or pyranthrone compound pigments such as Pigment Red 216, or isoviolanthrone compound pigments, such as Pigment Violet 31 and the like.

  If attention is paid to the structure of a preferred pigment, the colored curable composition of the present invention preferably contains a phthalocyanine pigment or a derivative thereof as another colorant. By including a phthalocyanine pigment or a derivative thereof, a colored curable composition that is excellent in dispersion stability and coloring power and can form a colored cured film having high luminance can be obtained.

  Examples of the phthalocyanine pigment or derivative thereof include copper phthalocyanine pigment, zinc phthalocyanine pigment, halogenated copper phthalocyanine pigment, and halogenated zinc phthalocyanine pigment. Specific examples of these pigments include Pigment Blue 15: 6, Pigment Green 7, Pigment Green 36, and Pigment Green 58. When a green colored cured film is formed, a halogenated phthalocyanine pigment such as Pigment Green 58 or Pigment Green 36 is preferable.

  A preferable phthalocyanine pigment includes a zinc phthalocyanine compound represented by the following general formula (P).

In formula ^{(P), A 1, A} 2, A 3, A 4, A 5, A 6, A 7, A 8, A 9, A 10, A 11, A 12, A 13, A 14, A ¹⁵ and A ¹⁶ each independently represent a halogen atom, an alkyl group, an alkoxy group, or a thioalkoxy group.
A ^{1 to} A ¹⁶ in the general formula (P) preferably each independently represent a hydrogen atom, a chlorine atom, or a bromine atom, and at least eight of these are preferably bromine atoms. Eight or more of A ^{1 to} A ¹⁶ are bromine atoms, and thus exhibit a yellowish green with high brightness and are suitable for forming a green colored region of the color filter. Furthermore, a zinc phthalocyanine compound having 10 or more bromine atoms is preferred.

The average composition of the zinc phthalocyanine compound can be easily obtained from mass spectrometry based on mass spectroscopy and halogen content analysis by flask combustion ion chromatography.
The zinc phthalocyanine compound can be produced by a known production method such as a chlorosulfonic acid method, a halogenated phthalonitrile method, or a melting method. More specific production methods are described in detail in JP 2008-19383 A, JP 2007-320986 A, JP 2004-70342 A, and the like.

As another colorant used in combination with the dye compound represented by the above-described general formula (1) exhibiting a yellow hue, from the viewpoint of being suitable for a color filter application, in a wavelength range of 380 nm to 800 nm, Those having a maximum absorption wavelength in a wavelength region of 500 nm to 800 nm are preferable, and those having a maximum absorption wavelength in a wavelength region of 600 nm to 700 nm are more preferable. In particular, a green hue, that is, one having a maximum absorption wavelength in a long region of 600 nm to 700 nm is preferable, and examples thereof include Pigment Green 36 and Pigment Green 58.
The pigment known as Pigment Green 58 is a pigment included in the brominated phthalocyanine pigment.

As the phthalocyanine pigment or derivative thereof, those having an average primary particle diameter in the range of 10 nm to 40 nm are preferable. By using a zinc phthalocyanine compound having an average primary particle size in this range in combination with the dye compound represented by the general formula (1), the dispersion stability and coloring power are excellent, the luminance is high, and the contrast is high. A colored curable composition can be obtained.
The average primary particle diameter is the longer diameter (major diameter) of 100 primary particles of zinc phthalocyanine pigment constituting the aggregate on the two-dimensional image obtained by photographing particles in the field of view with a transmission electron microscope. The average value of the shorter diameters (short diameters) was obtained and averaged.

When using a pigment as another colorant, it is preferable to prepare and use a pigment dispersion in advance. The pigment dispersion can be adjusted, for example, according to the description in JP-A-9-197118 and JP-A 2000-239544.
Content in the case of using together the dye or pigment as other coloring agents should just be a range which does not impair the effect of the present invention, specifically, with respect to the total solid content of the colored curable composition of the present invention. And 0.5 mass%-70 mass% are preferable. The content ratio of the other colorant is preferably 20 parts by mass to 500 parts by mass with respect to 100 parts by mass of the dye compound represented by the general formula (1).

-Polymerizable compound-
The colored curable composition of the present invention contains at least one polymerizable compound. A cured film can be formed by including a polymerizable compound. Examples of the polymerizable compound include addition polymerizable compounds having at least one ethylenically unsaturated double bond.

  The polymerizable compound having at least one ethylenically unsaturated double bond can be appropriately selected from known compounds, for example, paragraph numbers [0010] to [0020] of JP-A-2006-23696. And the compounds described in paragraphs [0027] to [0053] of JP-A-2006-64921.

  About a polymerizable compound, the details of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the final performance design of a colored curable composition. For example, from the viewpoint of sensitivity, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Also, from the viewpoint of increasing the strength of the colored cured film, those having three or more functionalities are preferable, and those having different functional numbers and different polymerizable groups (for example, acrylic acid esters, methacrylic acid esters, styrene compounds, vinyl ether compounds). It is also effective to adjust both sensitivity and intensity by using together. In addition, the selection of the polymerizable compound is also possible with respect to the compatibility and dispersibility with other components (for example, photopolymerization initiator, colorant (pigment), binder polymer, etc.) contained in the colored curable composition. The method of use is an important factor. For example, compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected from the viewpoint of improving adhesion to a hard surface such as a substrate.

  As the polymerizable compound, a urethane addition polymerizable compound produced by using an addition reaction of an isocyanate and a hydroxyl group is also suitable. JP-A-51-37193, JP-B-2-32293, JP-B-2-16765 And urethane acrylates described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418. Compounds are also suitable. Other examples include reacting polyester acrylates, epoxy resins and (meth) acrylic acid described in JP-A-48-64183, JP-B-49-43191, and JP-B-52-30490. And polyfunctional acrylates and methacrylates such as epoxy acrylates obtained by heating. Furthermore, the Japan Adhesion Association magazine vol. 20, no. 7, pages 300 to 308 (1984) are also introduced as photocurable monomers and oligomers.

Specific examples of the polymerizable compound include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and tri ((meth) acryloyloxyethyl). ) Isocyanurate, pentaerythritol tetra (meth) acrylate EO modified product, dipentaerythritol hexa (meth) acrylate EO modified product, and the like. As the polymerizable compound, a commercially available product may be used. Examples of the commercially available products include NK ester A-TMMT, NK ester A-TMM-3, NK oligo UA-32P, NK oligo UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), Aronix M-305. , Aronix M-306, Aronix M-309, Aronix M-450, Aronix M-402, TO-1382 (manufactured by Toagosei Co., Ltd.), V # 802 (Osaka Organic Chemical Industry Co., Ltd.), Kayrad Preferred examples include D-330, Kayrad D-320, Kayalad D-310, Kayalad DPHA (manufactured by Nippon Kayaku Co., Ltd.).
Two or more polymerizable compounds may be used in combination. For example, from the viewpoints of curing exposure sensitivity and developability adjustment, dipentaerythritol hexaacrylate and pentaerythritol tetra (meth) acrylate EO modified product, dipentaerythritol It is preferable to use in combination with an EO-modified product such as a hexa (meth) acrylate EO-modified product. Patterning suitability can be further improved by these combinations.

Only 1 type may be sufficient as the polymeric compound contained in a colored curable composition, and it may use 2 or more types together according to the objective.
The content of the polymerizable compound in the colored curable composition (the total content when two or more types are included) is the total solid content of the colored curable composition in that the effect of the present invention is more effectively achieved. 10% by mass to 80% by mass is preferable, 15% by mass to 75% by mass is more preferable, and 20% by mass to 60% by mass is particularly preferable based on the minute.

-Polymerization initiator-
The colored curable composition of the present invention preferably contains at least one polymerization initiator. The mode of curing in the present invention is not limited as long as it is a form that is cured by a polymerization reaction of a polymerizable compound, and may be cured by either thermal polymerization or photopolymerization. The colored curable composition of the present invention is preferably composed of a composition that is photopolymerized and cured, and the polymerization initiator is preferably a composition containing a photopolymerization initiator.

Hereinafter, it demonstrates centering on a photoinitiator. The photopolymerization initiator is a compound that initiates and accelerates polymerization of a polymerizable compound in response to light. Among them, a compound that is sensitive to an actinic ray having a wavelength of 300 nm or more and initiates and accelerates polymerization of a polymerizable compound is preferable. The photopolymerization initiator is not particularly limited as long as it can polymerize a polymerizable compound, and is preferably selected in consideration of characteristics, generation efficiency of starting species, absorption wavelength, availability, cost, and the like.
In addition, a photopolymerization initiator that does not directly respond to an actinic ray having a wavelength of 300 nm or more can be preferably used in combination with a sensitizer.

  Examples of the photopolymerization initiator include at least one active halogen compound selected from a halomethyloxadiazole compound and a halomethyl-s-triazine compound, a 3-aryl-substituted coumarin compound, a lophine dimer, a benzophenone compound, and an acetophenone compound. And derivatives thereof, cyclopentadiene-benzene-iron complex and salts thereof, and oxime compounds. Specific examples of the photopolymerization initiator include those described in paragraphs [0070] to [0077] of JP-A No. 2004-295116. Of these, organic halogenated compounds, hexaarylbiimidazole compounds, oxime compounds (hereinafter also referred to as oxime photopolymerization initiators) and the like are preferable. From the viewpoint of rapid polymerization reaction, oxime photopolymerization initiators are preferred. preferable.

The oxime photopolymerization initiator is not particularly limited, and examples thereof include oxime compounds described in JP 2000-80068 A, WO 02/100903 A1, JP 2001-233842 A, and the like.
Specific examples include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio). Phenyl] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (O-benzoyloxime) -1- [4 -(Phenylthio) phenyl] -1,2-heptanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (O-benzoyloxime)- 1- [4- (methylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (ethylphenylthio) phenyl] -1, -Butanedione, 2- (O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1- (O-acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9- Ethyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-butylbenzoyl) 9H-carbazol-3-yl] ethanone, 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone, 2- (acetoxyimino) -4- (4-chlorophenylthio) -1 -[9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1-butanone and the like. However, it is not limited to these.

  In the present invention, from the viewpoint of sensitivity, stability over time, and coloring during post-heating, the oxime photopolymerization initiator is selected from the group consisting of compounds represented by the following formula (1) or the following formula (2). The selected compound is more preferred.

  In formula (1), R and X each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. n is an integer of 0-5.

  R is preferably an acyl group from the viewpoint of increasing sensitivity, and for example, an acetyl group, a propionyl group, a benzoyl group, and a toluyl group are more preferable.

  A is an alkylene group substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heat aging, An alkylene group substituted with an alkenyl group (for example, vinyl group, allyl group), an aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) A substituted alkylene group is preferred.

  Ar is preferably a substituted or unsubstituted phenyl group from the viewpoint of increasing sensitivity and suppressing coloring due to heating. In the case of a substituted phenyl group, the substituent is preferably a halogen group such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

X is an alkyl group that may have a substituent, an aryl group that may have a substituent, or an alkenyl that may have a substituent from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region. Group, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthioxy group which may have a substituent, a substituent An arylthioxy group which may have an amino group and an amino group which may have a substituent are preferable.
Moreover, n in Formula (1) has a preferable integer of 0-2.

  As an example of a compound represented by Formula (1), a compound having a structure represented by the following (D-2) is preferable.

In Formula (2), X ¹ , X ² , and X ³ each independently represent a hydrogen atom, a halogen atom, or an alkyl group. R ¹ represents —R, —OR, —COR, —SR, —CONRR ′, or —CN, and R ² and R ³ each independently represent —R, —OR, —COR, —SR, or -NRR 'is represented. R and R ′ each independently represents an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these groups are substituted with one or more selected from the group consisting of a halogen atom and a heterocyclic group. May be. One or more carbon atoms constituting the alkyl chain in the alkyl group and the aralkyl group represented by R and R ′ may be replaced with an unsaturated bond, an ether bond, or an ester bond, and R and R ′ are bonded to each other. To form a ring.

  As an example of the compound represented by the formula (2), a compound having a structure represented by the following (D-3) is preferable.

  Examples of organic halogenated compounds include Wakabayashi et al., “Bull Chem. Soc. Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Examined Patent Publication No. 46-4605, 48-36281, JP-A-55-32070, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241 JP-A-62-212401, JP-A-63-70243, JP-A-63-298339, M.K. P. The compounds described in Hutt “Journal of Heterocyclic Chemistry” 1 (No. 3), (1970) and the like are mentioned, and in particular, an oxazole compound substituted with a trihalomethyl group and an s-triazine compound are preferable.

Examples of hexaarylbiimidazole compounds include those described in Japanese Patent Publication No. 6-29285, U.S. Pat. Nos. 3,479,185, 4,311,783, and 4,622,286. And, specifically, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) )) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 ′ -Bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5 5'-tetraphenylbiimidazole, 2,2'-bis o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2 , 2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and the like.
Moreover, you may use the well-known photoinitiator of Paragraph No. 0079 of Unexamined-Japanese-Patent No. 2004-295116.

  Especially, as a photoinitiator, an oxime type compound is suitable and the compound represented by said (D-2) and (D-3) is more preferable.

A photoinitiator can be contained individually by 1 type or in combination of 2 or more types.
The content of the photopolymerization initiator in the colored curable composition (the total content in the case of two or more) is the total solid content of the colored curable composition from the viewpoint of more effectively achieving the effects of the present invention. 0.5% by mass to 30% by mass is preferable, 3% by mass to 20% by mass is more preferable, 4% by mass to 19% by mass is further preferable, and 5% by mass to 18% by mass is particularly preferable based on the minute.

-Binder-
The colored curable composition of this invention can be comprised using a binder. The binder is preferably an alkali-soluble binder having alkali solubility, and can be selected from the viewpoints of heat resistance, developability, availability, and the like.

  The alkali-soluble binder is preferably a linear organic polymer, which is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-54-. 25957, JP-A-59-53836, JP-A-59-71048, etc., methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, Examples thereof include maleic acid copolymers and partially esterified maleic acid copolymers. An acidic cellulose derivative having a carboxylic acid in the side chain is also suitable. In addition, a polymer having a hydroxyl group with an acid anhydride added, a polyhydroxystyrene resin, a polysiloxane resin, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, etc. Preferably mentioned.

Among these, the alkali-soluble binder is preferably a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, or an acrylic / acrylamide copolymer resin from the viewpoint of heat resistance. From the viewpoint of control of developability, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable.
Among these, acrylic resins include copolymers composed of monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide and the like (for example, benzyl methacrylate / methacrylic acid). Acid (= 65/35 [molar ratio] copolymer) and commercially available products are exemplified by KS-resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P-series (Daicel). Chemical Industry Co., Ltd.) and the like are preferable.

Moreover, when comprising a colored curable composition in a positive composition, an alkali-soluble phenol resin can be used as an alkali-soluble binder. Examples of the alkali-soluble phenol resin include novolak resins and vinyl polymers.
Examples of the novolak resin include those obtained by condensing phenols and aldehydes in the presence of an acid catalyst. Here, examples of the phenols include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, bisphenol A, and the like. Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and the like. Phenols and aldehydes can be used singly or in combination of two or more.
Specific examples of the novolak resin include a condensation product of metacresol, paracresol, or a mixture thereof and formalin.
The novolac resin may be mixed with a low molecular weight component having a phenolic hydroxyl group such as bisphenol C or bisphenol A.

The weight average molecular weight of the binder (measured in terms of polystyrene by GPC method) is preferably from 1000-2 × 10 ^5, more preferably 2000-1 × 10 ^5, particularly preferably 5,000 to 5 × 10 ^4.

  The content of the binder in the colored curable composition is 10% by mass to 90% by mass with respect to the total solid content of the colored curable composition from the viewpoints of curability, developability, film strength, shape, and the like. % Is preferable, 20% by mass to 80% by mass is more preferable, and 30% by mass to 70% by mass is still more preferable.

-Other ingredients-
In addition to the above components, the colored curable composition of the present invention includes a sensitizer, a chain transfer agent, a polymerization inhibitor, an organic solvent, a crosslinking agent, a surfactant, an adhesion improver, and a development accelerator as necessary. In addition, various additives such as fillers, antioxidants, ultraviolet absorbers and anti-aggregation agents may be included.

(Sensitizer)
The colored curable composition of the present invention may contain a sensitizer. Examples of the sensitizer include those described in Crivello [JVCrivello, Adv. In Polymer Sci, 62, 1 (1984)]. Specifically, pyrene, perylene, acridine, thioxanthone, 2-chlorothioxanthone, Examples include benzoflavin, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, benzophenone, coumarin, ketocoumarin, phenanthrene, camphorquinone, and phenothiazine derivatives. The sensitizer is preferably added in a proportion of 50 to 200% by mass with respect to the photopolymerization initiator.
The sensitizer improves the sensitivity of the coexisting photopolymerization initiator. However, as described above, by using an appropriate sensitizer in combination with the photopolymerization initiator that is not directly sensitive to the exposure wavelength, it is also a colored curable composition. There is an advantage that it can be applied to things.

(Chain transfer agent)
The colored curable composition of the present invention may contain a chain transfer agent. Examples of the chain transfer agent include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, N -Heterocycles such as phenylmercaptobenzimidazole, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione And an aliphatic polyfunctional mercapto compound such as pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, and the like.
A chain transfer agent may be used individually by 1 type, and may use 2 or more types together. The content of the chain transfer agent is preferably 0.01% by mass to 15% by mass, and preferably 0.1% by mass to 10% by mass with respect to the total solid content of the colored curable composition in terms of reducing sensitivity variation. Is more preferable, and 0.5% by mass to 5% by mass is particularly preferable.

(Polymerization inhibitor)
The colored curable composition of the present invention may contain a polymerization inhibitor. A polymerization inhibitor means hydrogen donation (or hydrogen donation), energy donation (or energy donation), electron donation (or electron donation) to polymerization initiation species such as radicals generated in a colored curable composition by light or heat. Etc.) to inactivate the polymerization initiating species and to prevent the unintended polymerization reaction from starting. Examples of the polymerization inhibitor include polymerization inhibitors described in paragraphs 0154 to 0173 of JP2007-334322A. Especially, p-methoxyphenol is mentioned as a preferable polymerization inhibitor.
The content of the polymerization inhibitor in the colored curable composition is preferably 0.0001% by mass to 5% by mass, more preferably 0.001% by mass to 5% by mass with respect to the polymerizable compound, and 0.001. A mass% to 1 mass% is particularly preferred.

(Organic solvent)
The colored curable composition of the present invention can contain an organic solvent. The organic solvent is not particularly limited as long as it can satisfy the solubility of each component and the coating property when it is used as a colored curable composition, taking into consideration the solubility, coating property, and safety of solids such as a binder. To be elected.

  Examples of organic solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, Ethyl lactate, alkyl oxyacetates (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), 3- Oxypropionic acid alkyl esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate and the like (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy) Ethionic propionate Etc.), 2-oxypropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, 2-methoxypropion) Acid ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.)), methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate (for example, Methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate And ethyl 2-oxobutanoate

Examples of ethers include, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, Examples include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
Examples of ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.
Preferable examples of aromatic hydrocarbons include toluene and xylene.

  It is also preferable to mix two or more of these organic solvents from the viewpoints of the solubility of each component and, when an alkali-soluble binder is included, the solubility of the component and the improvement of the coated surface. In this case, particularly preferably, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol It is a mixed solution composed of two or more selected from acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

  The content of the organic solvent in the colored curable composition is preferably such that the total solid concentration in the composition is 5% by mass to 80% by mass, and more preferably 5% by mass to 60% by mass. An amount of 10% by mass to 60% by mass is particularly preferable.

(Crosslinking agent)
The colored curable composition of the present invention can additionally contain a crosslinking agent. By containing a crosslinking agent, the hardness of the colored cured film which hardened the colored curable composition is raised more.
The crosslinking agent is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, at least selected from (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Substituted with at least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group, substituted with one substituent, Phenol compounds, naphthol compounds or hydroxyanthracene compounds are mentioned. Of these, polyfunctional epoxy resins are preferred.
For details such as specific examples of the crosslinking agent, reference can be made to the descriptions in paragraph numbers 0134 to 0147 of JP-A No. 2004-295116.

(Surfactant)
The colored curable composition of the present invention may contain a surfactant. The surfactant may be anionic, cationic, nonionic, or amphoteric, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. . As the surfactant, commercially available products may be used. As examples of commercially available products, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F Top series (made by JEMCO), MegaFac (made by DIC Corporation), Florard (made by Sumitomo 3M Corporation), Asahi Guard, Surflon (made by Asahi Glass Co., Ltd.) PolyFox (made by OMNOVA), etc. be able to.

  As a surfactant, the structural unit A and the structural unit B represented by the following formula (1) are included, and the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography is 1,000 or more and 10,000 or less. The copolymer which is can be mentioned as a preferable example.

In Formula (1), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴ represents a hydrogen atom or An alkyl group having 1 to 4 carbon atoms is represented, and L represents an alkylene group having 3 to 6 carbon atoms. p and q are mass-based percentages representing a polymerization ratio, p represents a numerical value of 10% by mass to 80% by mass, and q represents a numerical value of 20% by mass to 90% by mass. r represents an integer of 1 to 18. n represents an integer of 1 to 10.

L in the formula (1) is preferably a branched alkylene group represented by the following formula (2).

In Formula (2), R ⁵ represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability with respect to the coated surface. An alkyl group of 3 or less is more preferable.

As for the weight average molecular weight (Mw) of the copolymer as a surfactant represented by Formula (1), 1,500 or more and 5,000 or less are more preferable.
Surfactant can be used individually by 1 type or in mixture of 2 or more types. Content in surfactant in the colored curable composition can be suitably selected in the range which does not impair the effect of this invention.

(Adhesion improver)
The colored curable composition of the present invention may contain an adhesion improving agent. The adhesion improver is a compound that improves the adhesion between a cured film and an inorganic substance serving as a substrate, for example, a silicon compound such as glass, silicon, silicon oxide, or silicon nitride, gold, copper, aluminum, or the like. Specific examples include silane coupling agents and thiol compounds. The silane coupling agent as the adhesion improving agent is for the purpose of modifying the interface, and any known silane coupling agent can be used without any particular limitation.
As the silane coupling agent, a silane coupling agent described in paragraph 0048 of JP-A-2009-98616 is preferable, and among them, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable.
The adhesion improver can be used alone or in combination of two or more. The content of the adhesion improving agent in the colored curable composition is preferably 0.1% by mass to 20% by mass, and preferably 0.2% by mass to 5% by mass with respect to the total solid content of the colored curable composition. More preferred.

(Development accelerator)
The colored curable composition of the present invention may contain a development accelerator. By containing the development accelerator, alkali solubility in the non-exposed area can be promoted, and the developability of the colored curable composition can be further improved. As the development accelerator, a low molecular weight organic carboxylic acid compound having a molecular weight of 1000 or less and a low molecular weight phenol compound having a molecular weight of 1000 or less are preferable.
Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, and umbellic acid.

(Other additives)
If necessary, the colored curable composition of the present invention may contain other various additives such as fillers, polymer compounds other than those described above, ultraviolet absorbers, antioxidants, anti-aggregation agents, and the like. it can. Examples of these additives include those described in paragraphs [0155] to [0156] of JP-A No. 2004-295116. The colored curable composition of the present invention can contain the light stabilizer described in paragraph [0078] of JP-A No. 2004-295116 and the thermal polymerization inhibitor described in paragraph [0081] of the same publication. .

-Preparation of colored curable composition-
The colored curable composition of the present invention is prepared, for example, by mixing the dye compound represented by the general formula (1) described above, a polymerizable compound, and if necessary, a photopolymerization initiator, a binder, and various additives. Can be prepared.

In preparing the colored curable composition, it is preferable to mix each component and then filter through a filter for the purpose of removing foreign substances and reducing defects. As the filter, those conventionally used for filtration and the like are not particularly limited. Specifically, for example, fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon-6 and nylon-6,6, polyolefin resins such as polyethylene and polypropylene (PP) (high density, ultrahigh And a filter formed using a resin material selected from (including molecular weight). Among these filter materials, polyamide resins such as nylon-6 and nylon-6, 6 and polypropylene (including high density polypropylene) are preferable.
The pore size of the filter is suitably about 0.01 μm to 7.0 μm, preferably about 0.01 μm to 2.5 μm, more preferably about 0.01 μm to 2.0 μm. By setting the pore size of the filter in the above range, fine foreign matters that obstruct the preparation of a uniform colored curable composition in the subsequent process are reliably removed, and a uniform and smooth colored curable composition layer can be formed. A colored curable composition.

When using filters, different filters may be combined. At that time, the filtering using the first filter may be performed only once, or may be performed twice or more. Moreover, it is good also as a 1st filtering by combining the filter of a different hole diameter within the range mentioned above, and making a 1st filter into a some filter. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co. .
As the second filter, a filter formed of the same material as the first filter described above can be used.
Further, for example, the filtering with the first filter may be performed only on the pigment dispersion, and the second filtering may be performed after mixing the other components with the pigment dispersion to obtain a colored curable composition. .

  The colored curable composition of the present invention can be applied to various uses such as a color filter for a solid-state imaging device, a color filter for a liquid crystal display device, a printing ink, and an inkjet ink.

<Colored cured film and color filter>
The colored cured film of the present invention is composed of at least the above-described dye compound of the present invention. The color filter of the present invention is configured by providing this colored cured film (and preferably a support on which the colored cured film is formed). By containing the dye compound of the present invention, the colored cured film of the present invention has a sharp absorption peak at the maximum absorption wavelength, excellent hue, and high brightness. Further, the color filter of the present invention contains the dye compound of the present invention, so that the hue of the colored region is good and high brightness is exhibited, and the contrast is excellent.

  Details and preferred embodiments of each component such as a dye compound and a polymerizable compound constituting the colored cured film and the color filter of the present invention are as described above.

  The colored cured film and the color filter of the present invention are not particularly limited except that the above-described dye compound of the present invention is included, and can be produced by a known method.

  When forming a colored curable film on a support, a colored film made of a colored curable composition is applied by a coating method of applying a colored curable composition or an immersion method of immersing a support in a colored curable composition. A colored cured film is obtained by forming and curing the colored film. In addition, when forming a patterned colored cured film, a colored film is formed on a support by selectively applying a colored curable composition to a desired region by an inkjet method, and the colored film is cured. May be. Alternatively, a known printing method such as textile printing or offset printing may be applied to selectively form a colored film in a desired region, and this colored film may be cured.

  In particular, when producing a color filter, the following method (the method for producing a color filter of the present invention) is preferable from the viewpoint of forming a high-definition pattern. That is, the color filter of the present invention is colored by applying a colored curable composition on a support, forming a colored film (colored film forming process), exposing the colored film in a pattern and developing it. It is most preferably produced by a production method having a step of forming a cured film (colored cured film forming step).

-Colored film formation process-
In the method for producing a color filter of the present invention, first, the colored curable composition of the present invention described above is applied to the support directly or via another layer by a desired method, and then from the colored curable composition. A colored film (colored curable composition layer) is formed. If necessary, the formed colored film may be pre-cured (pre-baked) and dried.
As the support, for example, non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these, used for solid-state imaging devices, etc. Examples of the photoelectric conversion element substrate include a silicon substrate and a plastic substrate. Further, on these supports, a black matrix for isolating each pixel may be formed, or a transparent resin layer may be provided for promoting adhesion. Further, if necessary, an undercoat layer may be provided on the support for improving adhesion to the upper layer, preventing diffusion of substances, or flattening the surface. It is preferable that the plastic substrate further has at least one layer selected from a gas barrier layer and a solvent resistant layer on the surface thereof.

A driving substrate on which a thin film transistor (TFT) of a thin film transistor (TFT) type color liquid crystal display device is arranged as a support (hereinafter referred to as a “TFT type liquid crystal driving substrate”) is used. In addition, a color filter formed using the colored curable composition of the present invention can be formed to produce a color filter.
Examples of the substrate in the TFT type liquid crystal driving substrate include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired. For example, a substrate in which a passivation film such as a silicon nitride film is formed on the surface of the TFT liquid crystal driving substrate can be used.

Examples of the method for applying the colored curable composition on the support include spin coating, slit coating, cast coating, roll coating, bar coating, and inkjet coating methods. Among the methods by slit coating, methods using a slit nozzle (hereinafter referred to as slit nozzle coating method) such as a slit-and-spin method and a spinless coating method are preferable. In the slit nozzle coating method, the slit-and-spin coating method and the spinless coating method have different conditions depending on the size of the coated substrate. For example, the fifth generation glass substrate (1100 mm × 1250 mm) is colored and cured by the spinless coating method. When the coating composition is applied, the discharge amount of the colored curable composition from the slit nozzle is usually 500 to 2000 microliters / second, preferably 800 to 1500 microliters / second, and the coating speed is usually 50 to 300 mm / second, preferably 100 to 200 mm / second.
Moreover, as solid content concentration of a colored curable composition, it is 10-20 mass% normally, Preferably it is 13-18 mass%.

  After forming the colored film, it is preferable to perform a pre-bake treatment, and if necessary, a vacuum treatment may be performed before the pre-bake. The vacuum drying condition is that the degree of vacuum is usually about 13.33 Pa (0.1 torr) to 133.32 Pa (1.0 torr), preferably about 26.66 Pa (0.2 torr) to 66.66 Pa (0.5 torr). It is. The pre-bake treatment is performed in a temperature range of 50 ° C. to 140 ° C., preferably about 70 ° C. to 110 ° C., using a hot plate, an oven, etc., and can be performed under conditions of 10 seconds to 300 seconds. Note that in the pre-bake treatment, a high-frequency treatment or the like may be used in combination with the heat treatment. Moreover, when drying a colored curable composition layer, it can replace with a prebaking process and can also perform a high frequency process independently.

  Moreover, the thickness of the colored film formed with the colored curable composition is appropriately selected according to the purpose. In the color filter for liquid crystal display devices, the range of 0.2 μm to 5.0 μm is preferable, the range of 1.0 μm to 4.0 μm is more preferable, and the range of 1.5 μm to 3.5 μm is the most preferable. Moreover, in the color filter for solid-state image sensors, the range of 0.2 micrometer-5.0 micrometers is preferable, The range of 0.3 micrometer-2.5 micrometers is more preferable, The range of 0.3 micrometer-1.5 micrometers is the most preferable. In addition, the thickness of the colored curable composition layer is a film thickness after pre-baking.

-Colored cured film forming step-
In the colored cured film forming step, pattern-like exposure (pattern exposure) and development are performed on the colored film (colored curable composition layer) formed on the support.

  Pattern exposure is performed by irradiating light through a photomask, for example. The exposure can be performed while flowing a nitrogen gas in the chamber in order to suppress oxidation fading of the coloring material in the colored film.

As light or radiation applicable to exposure, g-line, h-line, i-line, j-line, KrF light and ArF light are preferable, and i-line is particularly preferable. When using i line | wire for irradiation light, it is preferable to irradiate with the exposure amount of 100-10000mJ / cm < ² >. As the light source, ultra high pressure, high pressure, medium pressure, low pressure mercury lamp, chemical lamp, carbon arc lamp, xenon lamp, metal halide lamp, visible and ultraviolet laser light sources, fluorescent lamp, tungsten lamp, sunlight, etc. are used. May be.

In an exposure method using a laser light source, it is preferable to use an ultraviolet laser as the light source. The irradiation light is preferably an ultraviolet laser having a wavelength in the range of 300 nm to 380 nm, more preferably an ultraviolet laser having a wavelength in the range of 300 nm to 360 nm matches the photosensitive wavelength of the resist. Is preferable. Specifically, the Nd: YAG laser third harmonic (355 nm), which is a relatively inexpensive solid output, and the excimer laser XeCl (308 nm), XeF (353 nm) can be suitably used. .
The exposure amount of the exposure object ^(pattern), in the range of ^{1mJ / cm 2 ~100mJ / cm 2} , the range of 1mJ / cm ² ~50mJ / cm 2 is more preferable. An exposure amount within this range is preferable from the viewpoint of pattern formation productivity.

There are no particular restrictions on the exposure apparatus, but examples of commercially available exposure apparatuses include LE5565A (manufactured by Hitachi High-Technologies), Callisto (manufactured by Buoy Technology), EGIS (manufactured by Buoy Technology), and DF2200G (Dainippon Screen). Etc.) can be used. Also, devices other than those described above can be used.
When the method for producing a color filter of the present invention is applied to the production of a color filter for a liquid crystal display device, an exposure method in which mainly h rays and i rays are irradiated by a proximity exposure machine and a mirror projection exposure machine is preferable. Moreover, when applying the manufacturing method of the color filter of this invention to manufacture of the color filter for solid-state image sensors, the exposure method which mainly irradiates an i line with a stepper exposure machine is preferable. When manufacturing a color filter using a TFT type liquid crystal driving substrate, the photomask used is not only a pattern for forming a pixel (colored pattern) but also a through hole or a U-shaped depression. The thing in which the pattern for forming is provided is used.

Further, a light emitting diode (LED) and a laser diode (LD) can be used as the active radiation source. In particular, when an ultraviolet light source is required, an ultraviolet LED and an ultraviolet LD can be used. For example, a purple LED with a main emission spectrum having a wavelength between 365 nm and 420 nm, which is marketed by Nichia Corporation, can be used. If even shorter wavelengths are required, mention may be made of LEDs capable of emitting actinic radiation centered between 300 nm and 370 nm as described in US Pat. No. 6,084,250. Moreover, you may use the other ultraviolet LED which can be obtained. A particularly preferred actinic radiation source is a UV-LED, in particular a UV-LED having a peak wavelength at 340 to 370 m.
Since the parallelism of the ultraviolet laser is good, the pattern can be exposed without using a mask at the time of exposure. However, it is more preferable to expose the pattern using a mask because the linearity of the pattern is further increased.

Subsequently, the colored film after exposure is developed with a developer. Thereby, a negative type or a positive type coloring pattern can be formed. In development, the uncured portion after exposure is eluted in the developer, and only the cured portion remains on the substrate.
Development can be performed by a method such as a dip method, a shower method, or a spray method. Further, a swing method, a spin method, an ultrasonic method, or the like may be combined. The development may be carried out after the surface to be developed is moistened with water or the like in advance before the colored film comes into contact with the developer, and a process for preventing uneven development is taken. Further, the development treatment may be performed by tilting the support having the colored film after exposure. When manufacturing a color filter for a solid-state imaging device, paddle development in which development is performed while stirring the developing bath may be applied.

The developer can be used as long as it dissolves the colored film (colored curable composition layer) in the uncured part while not dissolving the cured part. For example, combinations of various organic solvents and alkaline aqueous solutions can be used. Examples of the organic solvent include the organic solvents described above that can be used when preparing the colored curable composition of the present invention.
Examples of alkaline aqueous solutions include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethyl. Concentration of an alkaline compound such as ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene is 0.001 to 10% by mass, preferably 0.01 to 1 An alkaline aqueous solution dissolved so as to be in mass% can be mentioned. In this case, the alkali concentration is preferably adjusted to be pH 11 to 13, more preferably pH 11.5 to 12.5.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution.

  The development temperature is usually preferably in the temperature range of 20 ° C. to 30 ° C., and the development time is preferably 20 seconds to 90 seconds.

After the development process, it is preferable to perform a rinsing process for washing and removing excess developer. The rinse treatment is usually performed with pure water. However, to save liquid, the used pure water may be used at the initial stage of cleaning, or the substrate may be tilted for cleaning, or ultrasonic irradiation may be used in combination. Good.
In addition, after the rinsing treatment, it is also preferable to perform a heat treatment (post-bake) in order to accelerate the curing after drying. Post-baking is usually performed by heat treatment at about 150 ° C to 250 ° C. Post-baking can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater or the like so that the coated film after development is in the above condition. .

  By sequentially repeating the above steps for each color according to the desired number of hues, a color filter in which a plurality of colored cured films (colored patterns) are formed as colored pixels can be produced.

  In addition to the above steps, in the method for producing a color filter of the present invention, the formed colored cured film (colored pixel) may be further exposed to ultraviolet rays for post-exposure.

  You may heat-process with respect to the colored cured film (colored pixel) in which post-exposure was performed. Further, the colored cured film can be further cured by heat treatment. The heat treatment can be performed by, for example, a hot plate, various heaters, an oven, or the like. The temperature during the heat treatment is preferably 100 ° C to 300 ° C, more preferably 150 ° C to 250 ° C. The heating time is preferably about 10 minutes to 120 minutes.

Since the colored curable film and the color filter of the present invention use the colored curable composition of the present invention, the coloring when displaying an image is bright, the contrast is high, and the heat resistance is excellent. In addition, as described later, not only the known CCFL but also a white LED is used as a backlight, there is an excellent effect that a good hue can be reproduced.
The color filter of the present invention can be used for a liquid crystal display device or a solid-state imaging device, and is particularly suitable for use in a liquid crystal display device. When used in a liquid crystal display device, it is possible to display an image excellent in spectral characteristics and contrast while achieving a good hue by using a dye as a colorant, and further excellent in suitability for a white LED. .

  As described above, the use of the colored curable composition of the present invention has been described mainly focusing on the formation of the color filter color pattern. However, the color curable composition of the present invention is used to form a black matrix that isolates the color pattern (pixels) constituting the color filter. Can also be applied. The black matrix uses a colored curable composition containing a black pigment light-shielding pigment such as carbon black or titanium black, and is subjected to coating, exposure, and development steps, and then post-baked as necessary. Can be formed.

  When a colored film is formed by applying the colored curable composition of the present invention on a substrate, the dry thickness of the colored film is generally 0.3 μm to 5.0 μm, preferably 0.5 μm to 3.5 μm. And most desirably 1.0 μm to 2.5 μm.

<Display device>
The display device of the present invention includes the color filter of the present invention described above or the color filter manufactured by the method of manufacturing the color filter of the present invention described above. Since the display device of the present invention includes the color filter using the colored curable composition of the present invention containing the dye compound represented by the general formula (1), the display image is vivid and has high contrast, and is long-term. It is possible to display a stable image over a wide range.

  For the definition of display devices and explanation of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Device (written by Junaki Ibuki, Industrial Book Co., Ltd.) Issue year)). The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next-generation liquid crystal display technology”.

  The color filter of the present invention is particularly effective when used in a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Further, the color filter of the present invention is a liquid crystal display device with a wide viewing angle, such as a lateral electric field driving method such as IPS, a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. Etc.

  The color filter of the present invention can also be used for a bright and fine COA (Color-filter On Array) system. In the case of a COA type liquid crystal display device, the required characteristics for the color filter must be the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the resistance to the stripping solution, in addition to the normal required characteristics as described above. The color filter of the present invention is considered to enhance the transparency of the ultraviolet light laser that is the exposure light by selecting the hue and film thickness of the pixels defined by the present invention in addition to the exposure method using the ultraviolet light laser. This improves the curability of the colored pixels, and can form pixels that are not chipped, peeled off, or twisted, so that the color layer provided directly or indirectly on the TFT substrate is particularly improved in the resistance to stripping liquid, and the COA method This is useful for liquid crystal display devices. In order to further improve the required characteristics of the low dielectric constant, a resin film may be further provided on the color filter layer.

The colored layer formed by the COA method has a rectangular shape with a side length of about 1 μm to 15 μm in order to connect the ITO electrode arranged on the colored layer and the terminal of the driving substrate below the colored layer. It is necessary to form a conduction path such as a through-hole or a U-shaped depression, and the dimension of the conduction path (that is, the length of one side) is particularly preferably 5 μm or less, but a colored layer having good curability By using the color filter of the present invention having the above, it is possible to easily form a conduction path of 5 μm or less.
The above-described image display method is described, for example, on page 43 of “EL, PDP, LCD display-technology and latest market trends (issued in 2001 by Toray Research Center Research Division)”.

The liquid crystal display device and organic EL display device of the present invention are composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film in addition to the color filter of the present invention. The color filter of the present invention can be applied to a liquid crystal display device and an organic EL display device composed of these known members.
Regarding these materials, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima, CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., 2003) ”.

  Regarding backlights, SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi), etc. Have been described.

When the color filter of the present invention is used in a liquid crystal display device, a high contrast can be realized when combined with a three-wavelength tube of a cold cathode tube or a red, green and blue LED light source (RGB-LED) as a backlight. The color filter having a colored pixel obtained by using the colored curable composition of the present invention has a particularly preferable hue when an LED light source having an emission spectrum at wavelengths of around 450 nm and around 550 nm is used as a backlight. High color reproducibility can be obtained.
A particularly preferable backlight includes an LED light source having a peak wavelength of emission intensity within a range of 430 nm to 470 nm.
That is, a liquid crystal display device comprising a color filter having a colored pixel obtained using the colored curable composition of the present invention and an LED backlight having a peak wavelength of emission intensity within a range of 430 nm to 470 nm, In particular, the liquid crystal display device can provide a good image.

  An organic EL display device comprising a color filter having a colored pixel obtained by using the colored curable composition of the present invention and a phosphor having a peak wavelength of emission intensity within a range of 430 nm to 470 nm, The display device can provide an image with high luminance and good color reproducibility.

  The LED backlight having a peak wavelength of emission intensity within the range of 430 nm to 470 nm includes Y phosphor: YAG phosphor, TAG phosphor, α-sialon phosphor, G phosphor: β-sialon phosphor, Examples include silicate phosphors, BSS phosphors, BSON phosphors, R phosphors: CASN phosphors, SCASN phosphors, and the like, all of which can be applied to the display device of the present invention.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.

Example 1
With reference to the synthesis scheme shown below, dyes Y-1 to Y-7 (dye compounds represented by the general formula (1) described above) were synthesized.

<Synthesis of Dye Y-1>
-Synthesis of Intermediate A-
The following compound (A) (synthesized by the method described in EP 0571959 A) was prepared, and according to the above synthesis scheme, first, a mixed solution of 100 parts by mass of compound (A) and 390 ml of pyridine was prepared. It cooled to 5 degreeC and 87 mass parts of octane sulfonyl chlorides were dripped at this at the reaction temperature of 25 degrees C or less. The reaction solution was stirred at room temperature for 2 hours, 2 L of 4N hydrochloric acid aqueous solution was added, and the mixture was stirred at room temperature. Then, it filtered. The crystal collected by filtration was washed with 500 ml of methanol and dried to obtain 153 g of intermediate A (yield 91%).
The results of confirming the structure of the obtained intermediate A by NMR are shown below.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 0.8 (t, 3H), 1.0-1.4 (m, 19), 1.6 (m, 2H), 3.2 (t, 2H), 5.6 (s, 1H), 7.3 (d, 2H), 7.9 (d, 2H), 10.2 (s, 1H), 12.9 (s, 1H)

-Synthesis of Y-1-
Subsequently, according to the above synthetic scheme, 68 g of ethyl orthoformate was added to a suspension of 110 g of Intermediate A and 650 ml of acetic acid at room temperature, and the reaction solution was stirred at 80 ° C. for 3 hours. To the reaction solution was added 1.1 L of methanol, and after cooling, it was filtered and washed with methanol to obtain 96 g of Y-1 (yield 88%).
The results of confirming the structure of the obtained Y-1 by NMR are shown below.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 0.8 (t, 6H), 1.2-2.0 (m, 41H), 3.3 (t, 4H), 7.3 (d, 4H), 7.6 (br, 2H), 7.8 (d, 4H), 8.4 (s, 1H)

<Synthesis of Dye Y-2>
In the synthesis of dye Y-1, dye Y-2 was synthesized in the same manner as the synthesis of dye Y-1, except that octanesulfonyl chloride was replaced with butanesulfonyl chloride.
The result of confirming the structure of the obtained Y-2 by NMR is shown below.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 0.9 (t, 6H), 1.1-1.8 (m, 26H), 3.3 (t, 4H), 7.3 (d, 4H), 7.6 (br, 2H), 7.8 (d, 4H), 8.4 (s, 1H)

<Synthesis of Dye Y-3>
In the synthesis of dye Y-1, dye Y-3 was synthesized in the same manner as the synthesis of dye Y-1, except that octanesulfonyl chloride was replaced with dodecylsulfonyl chloride.
The result of confirming the structure of the obtained Y-3 by NMR is shown below.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 0.8 (t, 6H), 1.1-2.0 (m, 58H), 3.3 (t, 4H), 7.3 (d, 4H), 7.6 (br, 2H), 7.8 (d, 4H), 8.4 (s, 1H)

<Synthesis of Dye Y-4>
In the synthesis of dye Y-1, dye Y-4 was synthesized in the same manner as dye Y-1, except that octanesulfonyl chloride was replaced with 2-ethylhexanoyl chloride.
The result of confirming the structure of the obtained Y-4 by NMR is shown below.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 0.8-0.9 (m, 12H), 1.0-1.6 (m, 34H), 2.9 (m, 2H), 7.5 (d , 4H), 7.8 (d, 4H), 8.5 (s, 1H), 9.8 (br, 2H)

<Synthesis of Dye Y-5>
-Synthesis of Intermediate B-
A mixed solution of 43 parts by mass of the intermediate A and 500 ml of dimethylformamide was cooled to 5 ° C., and 17 parts by mass of phosphorus oxychloride was added thereto at a reaction solution temperature of 15 ° C. or less as shown in the above synthesis scheme. . After stirring at room temperature for 2 hours, 2 L of 2N aqueous sodium hydroxide solution was added and stirred for 1 hour. Thereafter, the precipitated crystals were collected by filtration and washed with 300 ml of methanol to obtain 35 g of Intermediate B (yield 76%).
The results of confirming the structure of the obtained intermediate B by NMR are shown below.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 0.8 (t, 3H), 1.1-1.8 (m, 21H), 3.1 (t, 2H), 7.2 (d, 2H), 7.9 (d, 2H), 8.1 (s, 1H), 9.9 (s, 1H)

-Synthesis of Y-5-
Subsequently, according to the above synthesis scheme, 5 g of the obtained intermediate B, 4 g of intermediate A (butanesulfonamide) obtained by reacting butanesulfonyl chloride during the synthesis of dye Y-2, and 20 ml of acetic acid are mixed. The solution was stirred at 120 ° C. for 3 hours. After completion of the stirring, the reaction solution was poured into 100 ml of water to precipitate crystals. The obtained crystals were collected by filtration and washed with methanol to obtain 8 g of dye Y-5 (yield 96%).
The result of confirming the structure of the obtained Y-5 by NMR is shown below.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 0.8-0.9 (m, 6H), 1.2-2.0 (m, 34H), 3.3 (m, 4H), 7.3 (d , 4H), 7.6 (br, 2H), 7.8 (d, 4H), 8.4 (s, 1H)

<Synthesis of Dye Y-6>
In the synthesis of the above dye Y-5, the same procedure as in the synthesis of the dye Y-5 was performed except that the intermediate A (butanesulfonamide) was replaced with a dodecylsulfonamide obtained by reacting dodecanesulfonyl chloride. Dye Y-6 was synthesized.
The results of confirming the structure of the obtained Y-6 by NMR are shown below.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 0.8 (t, 6H), 1.2-2.0 (m, 49H), 3.3 (t, 4H), 7.3 (d, 4H), 7.6 (br, 2H), 7.8 (d, 4H), 8.4 (s, 1H)

<Synthesis of Dye Y-7>
In the synthesis of the above dye Y-5, the same procedure as in the synthesis of the dye Y-5 was performed except that the intermediate A (butanesulfonamide) was replaced with the following intermediate C in the synthesis of the dye Y-4. Y-7 was synthesized.
The results of confirming the structure of the obtained Y-7 by NMR are shown below.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 0.8-0.9 (m, 9H), 1.0-1.8 (m, 38H), 2.9 (m, 1H), 3.3 (t , 2H), 7.3 (d, 2H), 7.5 (d, 2H), 7.7 (d, 2H), 7.8 (m, 3H), 8.4 (s, 1H), 9 .8 (s, 1H)

(Example 2)
-Fabrication of yellow filter-
The THF solution of the dye Y-1 synthesized above was mixed with a PGMEA solution having a solid content of 30% by mass of a benzyl methacrylate / methacrylic acid copolymer (= 80/20 [molar ratio], weight average molecular weight: 30000). At this time, the concentration of the dye Y-1 in the total solid content was set to 10% by mass. The obtained mixed solution was applied to a glass substrate with a spin coater so that the dry coating amount was 1.6 g / m ² (applied film thickness was about 2 μm) and dried to prepare a yellow filter.

  Further, the dye Y-1 was sequentially replaced with the dyes Y-2 to Y-6 synthesized above, and five types of yellow filters were further produced by the same method as described above.

  Further, in order to prepare a comparative yellow filter, the following comparative compounds 1 and 2 were prepared, and the dye Y-1 was sequentially replaced with the comparative compounds 1 and 2, and two kinds of comparative compounds were prepared in the same manner as described above. A yellow filter was produced.

-Evaluation of filter characteristics-
Each of the produced yellow filters was subjected to heat treatment at 230 ° C. for 60 minutes.
Subsequently, using UV-2400PC (manufactured by Shimadzu Corporation), the transmission spectrum of the yellow filter after the heat treatment was measured, and from this transmission spectrum, the absorbance ratio of 490 nm to 460 nm before and after heating (absorbance at 490 nm / at 460 nm). Absorbance) was determined. The absorbance ratio is shown in Table 1 below.

  As shown in Table 1, the dye compound of the present invention (the dye compound represented by the general formula (1)) has a higher absorbance ratio before and after the heat treatment than the comparative yellow filter, and is excellent as a filter. I understand that.

Example 3
-Preparation of colored curable composition-
Each component in the composition shown below is blended in the amounts shown in Table 1 below, mixed for 10 minutes at room temperature (25 ° C.), allowed to stand for 10 minutes, and filtered with HDC II (manufactured by Nippon Pole Co., Ltd.). 5 types of colored curable compositions A1 and BE were prepared.
In addition, in the following Table 1, a numerical value shows content (mass%) of each component, "-" shows not containing the component.

<Composition>
Dye Y-1 synthesized above (dye compound represented by general formula (1))
・ C. I. 14.9 parts of Pigment Green 58 and 7.1 parts of an acrylic pigment dispersant [methyl methacrylate / methacrylic acid copolymer (= 80/20 [mass ratio], weight average molecular weight: 12,000)] Pigment dispersion obtained by mixing with 78.0 parts of propylene glycol monomethyl ether acetate and sufficiently dispersing the pigment using a bead mill. Phthalocyanine pigment derivative described in paragraph 0350 of JP2011-197670A [ZnPc- {Α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {β- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _3.8-x H _0.8 Cl _11.4 ] (0 ≦ x <3.8)
・ Kayarad DPHA (manufactured by Nippon Kayaku Co., Ltd .; polymerizable compound)
2- (benzoyloxyimino) -1- [4 ′-(phenylthio) phenyl] -1-octanone (IRGACURE OXE01, manufactured by BASF; photopolymerization initiator)
-The following compound D-2 (oxime photopolymerization initiator)
-The following compound D-3 (oxime-based photopolymerization initiator)
・ Propylene glycol monomethyl ether acetate (solvent)
・ Ethyl 3-ethoxypropionate (solvent)
Pentaerythritol tetrakis (3-mercaptobutyrate) [polyfunctional mercapto compound; chain transfer agent]
・ Benzyl methacrylate / methacrylic acid copolymer (= 65/35 [molar ratio]; binder)
・ P-methoxyphenol (polymerization inhibitor)
・ Megafac F781-F (manufactured by DIC; surfactant)

Example 4
In the preparation of the colored curable composition A of Example 3, the colored curable composition A of Example 3 was prepared except that the dye Y-1 was replaced with the dyes Y-2 to Y-7 synthesized above. In the same manner, 6 types of colored curable compositions A2 to A7 were prepared.

(Evaluation)
The following evaluation was performed about the colored curable composition A1-A7 and BE prepared in Examples 3-4. The evaluation results are shown in Table 3 below.

-1. Heat resistance
After coating the colored curable compositions A1 to A7 and B to E obtained above on glass [manufactured by Corning; EAGLE-XG (trade name: thickness 0.7 mm)] by spin coating, Volatile components were volatilized at 80 ° C. for 2 minutes to form a coating film (colored film) 1. After cooling, the coating film 1 was irradiated with i-line [wavelength 365 nm]. As a light source for i-line irradiation, an ultra-high pressure mercury lamp was used, and irradiation was performed after adjusting to parallel light. The irradiation light quantity at this time was 50 mJ / cm ² . Subsequently, the irradiated coating film 1 was post-baked at 230 ° C. for 90 minutes to obtain a colored cured film 1 having a thickness of 2 μm. The color difference (ΔEab) before and after post-baking of the obtained colored cured film was measured and evaluated. ΔEab indicates that the smaller the value, the smaller the hue change and the better the heat resistance.

-2. Contrast and brightness
After forming a colored cured film in the same manner as in “1. Heat resistance” above, the colored cured film is sandwiched between two polarizing films, and perpendicular to the case where the polarizing axes of the two polarizing films are parallel to each other. The brightness values of the two cases with the case of the above were measured with a color luminance meter (manufactured by Topcon Corporation, model number: BM-5A). A value obtained by dividing the luminance when the polarization axes of the two polarizing films were made parallel by the luminance when the polarizing axes were made vertical was used as an index for evaluating the contrast. The higher the contrast, the better the performance as a color filter for a liquid crystal display.

-3. Patterning aptitude-
In the same manner as in “1. Heat resistance”, the colored curable compositions A1 to A7 and B to E are sequentially applied by a spin coating method, and a coating film (colored film) 1 is formed by volatilizing volatile components. On the other hand, i-line (wavelength 365 nm) was irradiated through a mask on which a pattern with a line width of 20 μm was formed under the same conditions as in “1. Heat resistance”. Then, it developed with the developing solution (The density | concentration 2.4 mass% sodium carbonate / sodium hydrogencarbonate aqueous solution), and washed with water. Thereafter, the thin line of the formed colored cured film in a pattern was observed with an optical microscope at a magnification of 200 times, and whether or not a pattern as designed was formed was evaluated according to the following evaluation criteria. Ranks A to B are practically acceptable levels.
<Evaluation criteria>
A: Fine line width of 19 μm or more B: Fine line width of 17 μm or more and less than 19 μm C: Fine line width of less than 17 μm

As shown in Table 3, the colored curable composition of the present invention had higher image brightness, better contrast, and better patterning suitability than the comparative curable composition. Moreover, it was excellent also in heat resistance.
On the other hand, the comparative colored curable composition that does not use the dye compound represented by the general formula (1) has a low luminance and is significantly inferior in contrast. Moreover, although it has a certain degree of patterning suitability, the heat resistance was remarkably inferior.

Claims (14)

A dye compound represented by the following general formula (1).


[Wherein, R ¹ and R ² represent SO ₂ R ³ , and R ³ represents an alkyl group having 4 to 18 carbon atoms. ] A dye compound represented by the following general formula (1).


[In the formula, R ¹ And R ² Is COR ³ Represents R ³ Represents an alkyl group having 6 to 18 carbon atoms. ] Dye fee compound from the following structures Ru is selected.

The dye compound according to claim 1 or 2, wherein R ¹ and R ² in the general formula (1) represent the same group and have a symmetric structure. The manufacturing method of the dye compound which makes the compound represented by following General formula (2), and an orthoformate compound react, and manufactures the dye compound of any one of Claims 1-4 .


[Wherein R ⁵ represents SO ₂ R ³ or COR ³ . R ³ represents an alkyl group having 4 to 18 carbon atoms when R ⁵ is SO ₂ R ³ , and represents an alkyl group having 6 to 18 carbon atoms when R ⁵ is COR ³ . ] The compound represented by the following general formula (2) is reacted with an aldehyde compound represented by the following general formula (3) or a tautomer thereof, and any one of claims 1 to 4. The manufacturing method of the dye compound which manufactures the dye compound of this.


[Wherein R ⁵ represents SO ₂ R ³ or COR ³ . R ³ represents an alkyl group having 4 to 18 carbon atoms when R ⁵ is SO ₂ R ³ , and represents an alkyl group having 6 to 18 carbon atoms when R ⁵ is COR ³ . ]


Wherein, ^{R 6} represents _SO 2 ^{R 3} or COR ^{3, R 3} represents an alkyl group having 4 to 18 carbon atoms when ^{R 6} is _SO 2 ^{R 3,} when ^{R 6} is COR ³ Represents an alkyl group having 6 to 18 carbon atoms . ] A colored curable composition comprising at least the dye compound according to any one of claims 1 to 4 and a polymerizable compound. Furthermore, the colored curable composition of Claim 7 containing a polymerization initiator. The colored curable composition according to claim 7 or 8 , further comprising at least one selected from the group consisting of a copper phthalocyanine pigment, a zinc phthalocyanine pigment, a halogenated copper phthalocyanine pigment, and a halogenated zinc phthalocyanine pigment . The colored curable composition according to any one of claims 7 to 9 , further comprising at least one selected from a triarylmethane dye, a squarylium dye, and a phthalocyanine dye. The colored cured film containing the dye compound of any one of Claims 1-4 . A color filter having the colored cured film according to claim 11 . The claims 7 to colored curable composition according to any one of claims 10 to impart on a support, and forming a colored film,
Exposing the colored film in a pattern-like manner and developing it to form a colored cured film; and
The manufacturing method of the color filter which has this. A display device comprising the color filter according to claim 12 or the color filter manufactured by the method for manufacturing a color filter according to claim 13 .