JP2011221310A - Photocuring blue colorant composition for color filter, color filter, manufacturing method for color filter and a liquid crystal display apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocuring blue colorant composition for color filter excellent in pattern forming property by UV light laser which is excellent in hue and with which the chipping and peeling of the pattern-like film formed can be suppressed and which is good in pixel shape and can form a coloring pattern excellent in contact hole formation property, a color filter in which the composition is used, a manufacturing method thereof, and a liquid crystal display apparatus having the color filter.SOLUTION: A photocuring blue colorant composition for color filter of UV light laser exposure includes (A) an organic solvent, (B) a pigment, (C) silica fine particles, (D) a photopolymerization initiator, (E) an ethylenic unsaturated compound, and (F) a resin. The content of the (C) silica fine particles is 5-15% by mass with respect to the total nonvolatile amount.

Description

  The present invention relates to a photocurable blue coloring composition for a color filter, a color filter using the same, a method for producing the same, and a liquid crystal display device using the color filter.

  Color filters are indispensable components for liquid crystal displays. The liquid crystal display is compact compared to the CRT as a display device, and can save power, and has become more than equivalent in terms of performance due to technological advancement. Therefore, TV screens, personal computer screens, and other display devices It is being replaced by CRT.

  In recent years, the development of liquid crystal displays has been expanded from the use of personal computers and monitors having a relatively small screen area to TV applications that require a large screen and high image quality. Therefore, in order to improve the productivity of the color filter used for this purpose, studies have been made to increase the substrate size. Furthermore, the mask size used for pattern exposure of this color filter is also used in accordance with this, so that the mask itself is very expensive, and it is important to keep the mask cost low. It has become a challenge.

For this reason, a method of forming a color filter using patterning with a laser beam is disclosed. (For example, refer to Patent Document 1) However, in this method using a semiconductor laser, the output of the laser is small, and it takes time for exposure, and the productivity cannot be increased.

  In addition, a method for manufacturing a color filter that does not use a large photomask at the time of exposure has been proposed in terms of reducing the total price when manufacturing the color filter. (For example, refer to Patent Documents 2 and 3.) However, when high-power laser exposure is combined in order to obtain high productivity, pattern chipping, peeling, or twisting occurs in the pixels, which improves productivity and is favorable. Therefore, there is a demand for compatibility with the formation of a pixel having a simple shape.

  In a color-filter on array (hereinafter referred to as COA) type liquid crystal display device, the role of an interlayer insulating film on a thin film transistor (hereinafter sometimes referred to as TFT). A color filter layer that also serves as a layer is formed. For this reason, the required characteristics for the color filter layer must include the required characteristics as a correlation insulating film such as contact hole formability, low dielectric constant, and resistance to stripping liquid in addition to the normal required characteristics as described above. In order to satisfy the characteristics, a resin film is also provided as a protective layer on the color filter layer.

  On the other hand, phthalocyanine blue pigments are used for blue pixels for reasons such as heat resistance and light resistance. However, since the phthalocyanine blue pigment has a high absorbance in the ultraviolet region and does not easily transmit ultraviolet light, the patterning using the ultraviolet laser as described above does not sufficiently cure the pixel, and the pixel shape deteriorates. there were. In particular, in the case of the COA method, the length of one side is about 1 to 40 μm on the colored pixel in order to make the ITO electrode arranged on the colored layer and the terminal of the driving substrate below the colored layer conductive. It is necessary to form a contact hole (conducting path) having a rectangular cross section from a rectangular shape, a circular shape or an elliptical shape having a diameter of 1 to 40 μmφ, or a U-shaped shape. When the absorbance at is high, there is a problem that curing due to exposure does not proceed and heat flow occurs at a high temperature during post-baking and the formed contact hole is crushed.

JP 2007-114602 A JP 2008-76709 A JP 2008-51866 A

The present invention provides a color filter light that is excellent in hue, has a suppressed pixel pattern in a formed pattern film, and has a good pixel shape and a contact hole formability. A curable blue coloring composition, in particular, a photocurable blue coloring composition for a color filter that is sensitive to ultraviolet light and can form a good coloring pattern for a color filter even by ultraviolet laser exposure. The issue is to provide.
A further object of the present invention is to provide a color filter having a colored pattern formed from the photocurable blue coloring composition of the present invention, a production method capable of producing the color filter with high productivity, An object of the present invention is to provide a liquid crystal display device provided with the color filter.

Means for solving the above-mentioned problems are as follows.
<1> containing (A) an organic solvent, (B) a pigment, (C) silica fine particles, (D) a photopolymerization initiator, (E) an ethylenically unsaturated compound, and (F) a resin, (C) A photocurable blue coloring composition for an ultraviolet light-sensitive color filter, wherein the content of silica fine particles is 3% by mass or more and 30% by mass or less with respect to the total nonvolatile content.
<2> The photocurable blue coloring composition for a color filter according to <1>, wherein the (B) pigment includes a phthalocyanine pigment.
<3> The pigment (B) is a phthalocyanine pigment, C.I. I. The photocurable blue coloring composition for color filters as described in <1> or <2> containing Pigment Violet 23.

<4> The photocurable blue coloring composition for a color filter according to any one of <1> to <3>, wherein the (F) resin is a resin having an unsaturated double bond in a side chain.
<5> The photocuring property for a color filter according to any one of <1> to <4>, wherein the addition amount of the pigment (B) is 10% by mass to 25% by mass with respect to the total nonvolatile content. Blue coloring composition.
<6> The photocuring property for a color filter according to any one of <1> to <5>, wherein the (C) silica fine particles are added in a dispersed manner in an organic solvent having a boiling point of 110 ° C. or higher and 110 ° C. or lower. Blue coloring composition.

<7> The color according to any one of <1> to <6>, wherein when a cured film having a thickness of 2 μm after drying is formed, the transmittance of the cured film at a wavelength of 355 nm is 2% or less. Photocurable blue coloring composition for filters.
<8> The photocurable blue coloring composition for a color filter according to any one of <1> to <7>, which is sensitive to an ultraviolet laser having a wavelength of 300 nm to 380 nm.
<9> The photocurable blue coloring composition for a color filter according to any one of <1> to <8>, which is for a color filter of a Color-filter On Array method.

<10> A color filter comprising a blue colored pixel formed on the support by the photocurable blue coloring composition for a color filter according to any one of <1> to <9>.
<11> A colored layer that provides the photocurable blue colored composition for color filter according to any one of <1> to <9> on the substrate to form a colored layer made of the blue colored composition. A color including a forming step, an exposure step of exposing the colored layer in a pattern using an ultraviolet laser having a wavelength of 300 nm to 380 nm, and a developing step of developing the colored layer after exposure to form a colored pattern A method for manufacturing a filter.
<12> A liquid crystal display device comprising the color filter according to <10>.

According to the present invention, a color filter that is excellent in hue, suppresses chipping and peeling in the formed pattern film, has a good pixel shape, and forms a colored pattern with excellent contact hole formability. Photocurable Blue Coloring Composition, especially for color filters that are sensitive to ultraviolet light and can produce good colored patterns for color filters with high productivity even by ultraviolet laser exposure Blue colored compositions can be provided.
Further, according to the present invention, a color filter provided with a colored pattern formed from the photocurable blue coloring composition of the present invention, a manufacturing method capable of manufacturing the color filter with high productivity, A liquid crystal display element provided with the color filter can be provided.

Hereinafter, the present invention will be described in detail.
The photocurable blue coloring composition for color filters of the present invention comprises (A) an organic solvent, (B) a pigment, (C) silica fine particles, (D) a photopolymerization initiator, (E) an ethylenically unsaturated compound, and And (F) the resin and the content of the silica fine particles (C) is 3% by mass or more and 30% by mass or less with respect to the total non-volatile content. It is characterized by having.
First, the characteristic “for ultraviolet light laser” of the photocurable blue coloring composition for color filter of the present invention will be described.
<Pattern exposure>
The photocurable blue coloring composition for a color filter of the present invention is cured with high sensitivity by ultraviolet laser exposure. Accordingly, the exposure region is cured and a colored pattern is formed by pattern exposure such as scanning exposure using an ultraviolet laser or exposure through a mask.
By the pattern exposure process, the polymerization curing reaction of the ethylenically unsaturated compound occurs and proceeds in the patterned exposure area of the photocurable blue colored composition by the initiation species generated from the photopolymerization initiator, and the exposure area is cured. By doing so, a pattern composed of a cured region and an uncured region is formed.
Hereinafter, this process will be described in detail as an exposure process.

[Exposure process]
In the exposure process for patterning the photocurable blue coloring composition for a color filter of the present invention, an ultraviolet laser is used as an exposure light source.
Laser is an acronym for English Light Amplification by Stimulated Emission of Radiation. This is an oscillation / amplifier that produces monochromatic light with stronger coherence and directivity by amplifying and oscillating light waves using the phenomenon of stimulated emission that occurs in materials with an inversion distribution. Examples of the excitation medium include crystals, glass, liquid, pigment, gas, and the like, and the types of these media can be classified into types such as solid laser, liquid laser, gas laser, and semiconductor laser.
In the present invention, any conventionally known laser can be used as long as it has an oscillation wavelength in the ultraviolet region. Among these, a solid laser or a gas laser is preferable from the viewpoint of laser output and oscillation wavelength.

  In the present invention, an ultraviolet laser having an oscillation wavelength in the range of 300 nm to 380 nm is preferable, and more preferably, an ultraviolet laser having an oscillation wavelength in the range of 300 nm to 360 nm is used for photosensitizing the photocurable blue coloring composition of the present invention. This is preferable in that it matches the wavelength.

  More specifically, in the present invention, the third harmonic (355 nm) of the Nd: YAG laser, the XeCl (308 nm), and the XeF (353 nm) of the excimer laser, which is a solid laser that has a particularly large output and is relatively inexpensive. Can be suitably used.

In the exposure with the ultraviolet laser as described above, the preferable illuminance is preferably 10 W / cm ² or more, and more preferably 100 W / cm ² or more.
As the exposure amount of the exposure object (photocurable blue colored composition) is ^preferably in the range of ^{1mJ / cm 2 ~100mJ / cm 2} , more in the range of 1mJ / cm ² ~50mJ / cm 2 preferable. When the exposure amount is within this range, it is preferable from the viewpoint of productivity during pattern formation.

  The exposure apparatus applicable to the exposure process in the present invention is not particularly limited, but commercially available devices such as EGIS (buoy technology) or DF2200G (Dainippon Screen) can be used. It is.

  The ultraviolet laser used in the present invention has good parallelism of light, so that pattern exposure is possible without using a mask during exposure, but the pattern shape is the shape of the output light of the ultraviolet laser. And may be affected by the profile. For this reason, in the exposure process of the present invention, it is preferable to perform pattern exposure by combining a mask with an ultraviolet laser because the linearity of the pattern becomes higher.

  One feature of the ultraviolet laser used in the present invention is that the illuminance is high, and heat is generated in the photocurable blue coloring composition in the exposure process, causing uneven curing inside the formed pixel. There is. Therefore, in order to control the temperature of the object to be exposed (photocurable blue coloring composition) used for pixel formation, it is preferable to keep the exposure stage at a constant temperature, and it is necessary to consider the shape of the exposure stage. Further, since the ultraviolet laser has a high degree of parallelism of light, the influence of the distance to the substrate is small, and it is also preferable that the exposure is performed while the substrate is lifted with air and conveyed.

<Photocurable blue coloring composition>
The photocurable blue coloring composition for ultraviolet laser exposure of the present invention comprises (A) an organic solvent, (B) a pigment, (C) silica fine particles, (D) a photopolymerization initiator, and (E) an ethylenically unsaturated compound. And (F) a resin, and the content of the (C) silica fine particles is 3% by mass or more and 30% by mass or less, preferably (B) phthalocyanine as a pigment. Contains blue pigments. This colored composition is used for forming a colored pattern of a color filter.
Below, each structural component of the photocurable blue coloring composition of this invention is explained in full detail.
First, (C) silica fine particles, which is a characteristic component of the present invention, will be described.

[(C) Silica fine particles]
The photocurable blue coloring composition of the present invention contains silica fine particles. Known types of silicas and production methods can be used, but vapor phase method silica, hydrous silica fine particles, colloidal silica, organosilica sol, or the like can be used. Among these, an organosilica sol having good dispersibility in an organic solvent can be preferably used.

  The particle diameter of the silica fine particles is preferably 5 nm to 50 nm, more preferably 10 nm to 30 nm. When the particle diameter of the silica fine particles is within this range, a color filter that is optically transparent and has no haze can be obtained. In addition, it is difficult to cause aggregation and viscosity increase, and is excellent in handleability. The silica fine particles are preferably spherical. By having a true spherical shape, it is possible to obtain a clear coating film in which haze, aggregation, and viscosity increase do not occur.

  The silica fine particles are preferably transparent in the visible light region. In particular, since it is used for a blue pixel, it is preferable to have a high transmittance at 400 nm to 500 nm. Moreover, it is preferable not to emit fluorescence in the visible range. When fluorescence is emitted in the visible region, the polarization is canceled and there is a case where a significant reduction in contrast is caused.

When the (C) silica fine particles are blended in the photocurable blue coloring composition of the present invention, it is preferable to use those dispersed in an organic solvent in advance.
The organic solvent used as the dispersion medium preferably has a boiling point of 110 ° C. or higher and 200 ° C. or lower. By using an organic solvent having a boiling point in the above range, clogging of nozzles during coating and surface defects such as photosensitive unevenness are suppressed, and drying and pre-baking using a drying process, for example, a vacuum drying apparatus (VCD) described later. In the process, the solvent is easily removed.
An example of silica fine particles dispersed in such an organic solvent is an organosilica sol. More specifically, methanol silica sol and the like can be mentioned. Silica fine particles dispersed in an organic solvent are also available as commercial products. For example, IPA-ST, IPA-ST-UP, IPA-ST-ZL, EG-ST, NPC-ST-30, DMAC- ST, MEK-ST, MIBK-ST, XBA-ST, PMA-ST, PGM-ST, MIBK-SD (trade names: all manufactured by Nissan Chemical Co., Ltd.) and the like can be mentioned. Among these critical products, PMA-ST, MIBK-ST, and MIBK-SD do not cause aggregation of the blue pigment used together, and the boiling point of the organic solvent used for literary work is also moderate. This is more preferable because there is no concern about blistering due to poor drying.

The addition amount of the silica fine particles is preferably in the range of 1% by mass to 30% by mass, more preferably in the range of 5% by mass to 15% by mass, with respect to the total nonvolatile content of the composition of the present invention. % Range is most preferred. When the amount of silica fine particles added is within this range, the shape of the pixel end and the shape of the contact hole are improved, and the developability, contrast, and brightness are improved, which is preferable.
In the present invention, “nonvolatile content” refers to a component remaining in a cured film obtained by drying a coating film coated with the composition at 100 ° C. for 2 minutes.
Therefore, in the composition of the present invention, (B) pigment, (C) silica fine particles, (D) photopolymerization initiator, (E) ethylenically unsaturated compound, and (F) resin are included in the nonvolatile content. Is done.

[(B) Pigment]
The pigment used in the present invention contains at least a blue pigment in order to form a blue coloring pattern, but preferably contains a phthalocyanine blue pigment.
Suitable phthalocyanine blue pigments for the present invention include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16,17: 1, 75, 79, and the like. Especially, C.I. I. Pigment Blue 15: 6 is excellent in terms of heat resistance, light resistance, and contrast, and can be used more suitably.
The content ratio of the phthalocyanine blue pigment to the total amount of the pigment (B) used in the composition of the present invention is preferably 50% by mass or more. By setting the ratio of the phthalocyanine blue pigment to the total pigment to 50% by mass or more, it becomes possible to obtain high heat resistance, light resistance, and contrast value.

In addition to the phthalocyanine blue pigment, the composition of the present invention preferably contains a violet pigment as a pigment for adjusting chromaticity. By including a violet pigment, a deep blue color that can achieve a high NTSC ratio can be provided.
Examples of violet pigments include C.I. I. Pigment Violet 19, 23, 32, etc. can be used. Especially, C.I. I. Pigment Violet 23 is more preferable because it provides brightness, light resistance, heat resistance, and high contrast.
(B) Although the addition amount of a pigment can be selected at any time according to desired chromaticity, luminance, and film thickness, a range of 10% by mass to 25% by mass with respect to the total nonvolatile content is preferable. When the added amount of the pigment is within this range, it becomes easy to obtain desired chromaticity, luminance, and film thickness, and the shape of the pixel and the contact hole is also improved.

In the present invention, a small amount of a pigment other than the blue pigment and the violet pigment can be added as an auxiliary pigment. Examples of auxiliary pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, Red such as 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, and 279 Pigments.
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, and Orange pigments such as 73; I. And green pigments such as Pigment Green 7, 10, 36, 37, and 58.

(Coating pigment)
The pigment used in the present invention is an organic pigment, and it is preferable to use an organic pigment coated with a polymer compound in the step of miniaturizing or dispersing the organic pigment.
By coating the pigment with the polymer compound, the formation of secondary aggregates can be suppressed even in the miniaturized pigment, and the pigment can be dispersed in the form of primary particles. In other words, the coated pigment has improved dispersibility and excellent dispersion stability in which the dispersed primary particles are stably maintained.
With respect to the polymer compound used for the coating pigment and the method for coating the pigment, it is more preferable to use the treatment methods and polymer compounds described in paragraphs [0025] to [0078] of JP-A-2009-144269.

In the present invention, the pigment is preferably used as a pigment dispersion composition by dispersing the pigment using at least one dispersant. The same applies to the case where the above-described coated pigment is used. By using this dispersant, the dispersibility of the pigment can be improved.
As the dispersant, for example, a known pigment dispersant or surfactant can be appropriately selected and used.

Specifically, many types of compounds can be used as the dispersant. For example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. Cationic surfactants such as 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene Nonionic surfactants such as octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; anionic systems such as W004, W005, and W017 (manufactured by Yusho Co., Ltd.) Surfactant: EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals) Polymer dispersants such as Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (all manufactured by San Nopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, Various Solsperse dispersants (manufactured by Nippon Lubrizol Corp.) such as 26000, 28000; Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by Asahi Denka Co., Ltd.) and Ionnet S-20 (manufactured by Sanyo Chemical Co., Ltd.), Disperbyk 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 62,163,164,166,167,170,171,174,176,180,182,2000,2001,2050,2150 (manufactured by BYK-CHEMIE Co., Ltd.).
In addition, an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer, may be mentioned.

  As content of a dispersing agent, 1 mass%-100 mass% are preferable with respect to the mass of the above-mentioned (B) pigment, and 3 mass%-70 mass% are more preferable.

In addition, when (B) the pigment is added to the photocurable blue coloring composition, a pigment dispersion composition containing a pigment and a dispersant is prepared in advance and blended with this from the viewpoint of pigment dispersibility. Although preferable, a pigment derivative is added to the pigment dispersion composition as necessary.
The pigment is dispersed in the pigment dispersion composition in the form of fine particles by adsorbing the pigment derivative having a part having affinity with the dispersant or a polar group-introduced pigment to the pigment surface and using it as the adsorption point of the dispersant. Can be made. Since the photocurable blue coloring composition containing such a pigment dispersion composition can prevent reaggregation of the pigment, it is effective in forming a color filter having high contrast and excellent transparency. .

Specifically, the pigment derivative is a compound in which an organic pigment is used as a base skeleton, and an acidic group, a basic group, or an aromatic group is introduced into the base skeleton as a substituent.
Specific examples of organic pigments serving as a base skeleton include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, benzoic pigments. Examples include imidazolone pigments. In general, pale yellow aromatic polycyclic compounds such as naphthalene-based, anthraquinone-based, triazine-based, and quinoline-based compounds that are not called pigments can also be used as the base skeleton.
Examples of pigment derivatives include JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A-8-295810, and JP-A-11-199796. JP, 2005-234478, JP 2003-240938, JP 2001-356210, etc. can be used.

  As content in the pigment dispersion composition of the pigment derivative based on this invention, 1 mass%-30 mass% are preferable with respect to the mass of a pigment, and 3 mass%-20 mass% are more preferable. When the content is within the above range, the dispersion can be performed satisfactorily while keeping the viscosity low, and the dispersion stability after dispersion can be improved. As a result, a photocurable blue coloring composition containing such a pigment dispersion composition has a high transmittance, an excellent color characteristic is obtained, and a high-contrast color filter having a good color characteristic is produced. Is preferred.

  The method for dispersing the pigment is, for example, by mixing the pigment and the dispersant in advance and finely dispersing the material previously dispersed with a homogenizer using a bead disperser using zirconia beads or the like. Done.

[dye]
The photocurable blue coloring composition of the present invention may use a dye as a colorant in addition to the pigment as long as the effects of the present invention are not impaired.
There is no restriction | limiting in particular as dye which can be used as a coloring agent, The well-known dye conventionally used as a color filter use can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like.

  The chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, A dye such as xanthene, phthalocyanine, benzopyran, or indigo can be used.

[(A) Organic solvent]
The photocurable blue coloring composition of the present invention can be prepared using a general solvent. Moreover, the pigment dispersion composition and silica fine particle dispersion described above can also be prepared using a solvent. The organic solvent used in the present invention is preferably an organic solvent having a boiling point of 110 ° C. or higher and 200 ° C. or lower from the viewpoints of coating properties, suppression of nozzle clogging during coating, and solvent removability when forming a cured film.
Examples of the organic solvent that can be used in the present invention 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, and alkyl. Esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-oxypropionate, 3 -3-oxypropionic acid alkyl esters such as ethyl oxypropionate (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2- Oki 2-oxypropionic acid alkyl esters such as methyl propionate, ethyl 2-oxypropionate, propyl 2-oxypropionate (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate) Methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2- Ethyl ethoxy-2-methylpropionate), and methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 1,3-butane Diol diacetate, etc.

  Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether Acetate, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, propylene glycol n-propyl ether acetate, propylene glycol di Cetate, propylene glycol n-butyl ether acetate, propylene glycol phenyl ether, propylene glycol phenyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol n-propyl ether acetate, dipropylene glycol n-butyl ether acetate, tripropylene glycol mono n- Butyl ether, tripropylene glycol methyl ether acetate, etc .;

Ketones such as acetone, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Alcohols such as ethanol, isopropyl alcohol, propylene glycol methyl ether, propylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether,
Aromatic hydrocarbons such as toluene and xylene are exemplified.

Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, Propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate and the like are suitable.
You may use a solvent in combination of 2 or more types besides using independently.
The content of the organic solvent (A) in the photocurable blue coloring composition of the present invention is appropriately selected according to the purpose, but from the viewpoint of applicability, the nonvolatile content concentration is 10% by mass to 30% by mass. A range is preferable.

[(D) Photopolymerization initiator]
The photocurable blue coloring composition in the present invention contains (D) a photopolymerization initiator.
The photopolymerization initiator is a compound that decomposes by light and initiates and accelerates the polymerization of the (E) ethylenically unsaturated compound, and preferably has sensitivity to the wavelength of the ultraviolet laser.
The photopolymerization initiator preferably has absorption at the exposure wavelength of the laser, and even when there is no absorption at the wavelength of the ultraviolet laser, it can be adjusted to the wavelength of the ultraviolet laser by using in combination with a sensitizing dye described later. It is possible to have sensitivity. Moreover, a photoinitiator can be used individually or in combination of 2 or more types.

  Examples of the photopolymerization initiator used in the present invention include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, Examples include metallocene compounds, hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds.

  Specific examples of the 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, Japanese Unexamined Patent Publication No. 48-36281, Japanese Unexamined Patent Publication No. 55-3070, Japanese Unexamined Patent Publication No. 60-239736, Japanese Unexamined Patent Publication No. 61-169835, Japanese Unexamined Patent Publication No. 61-169837, Japanese Unexamined Patent Publication No. 62-58241. JP, 62-21401, JP 63-70243, 63-298339, M.M. P. Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970) ”, and the oxazole compound and s-triazine compound substituted with a trihalomethyl group.

  Examples of the carbonyl compound include benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and other benzophenone derivatives, 2,2-dimethoxy-2 -Phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy -1- (p-dodecylphenyl) ketone, 2-methyl-1- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-mol) Linophenyl) -butanone-1,2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 1,1,1-trichloromethyl- (p-butylphenyl) ketone, 2-benzyl-2-dimethylamino-4-morpholino Acetophenone derivatives such as butyrophenone, thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, p- Examples thereof include benzoic acid ester derivatives such as ethyl dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

  As the hexaarylbiimidazole compound, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, 4,622,286, etc. 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'-tetraphenylbi Dazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5 Examples include 5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

  Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP-A 2000-66385, JP-A 2000-80068, JP-T 2004-534797 And the compounds described. Specific examples include Irgacure OXE-01 and OXE-02 manufactured by Ciba Specialty Chemicals.

  As photopolymerization initiators, from the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oximes Compounds, triallylimidazole dimer, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, 3-aryl substitution Compounds selected from the group consisting of coumarin compounds are preferred.

More preferably, they are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, and trihalo. Most preferred is at least one compound selected from the group consisting of a methyltriazine compound, an α-aminoketone compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound.
Hereinafter, the details of the oxime compound which is a polymerization initiator preferably used in the present invention will be described.
Examples of oxime compounds suitable as polymerization initiators in the present invention include oxime ester compounds represented by the following general formula (5) or (6).

In the general formula (5), R ⁸ and P each independently represent a monovalent substituent, Q ¹ and Q ² each independently represent a divalent organic group, and Ar represents an aryl group. n is an integer of 0-5. When a plurality of P are present, each of the plurality of P independently represents a monovalent substituent.

The monovalent substituent represented by R ⁸ is preferably a monovalent nonmetallic atomic group shown below.
Examples of the monovalent nonmetallic atomic group represented by R ⁸ include an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkenyl group that may have a substituent, and a substituent. An alkynyl group which may have a group, an alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, and a substituent. An arylsulfonyl group which may have a substituent, an acyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, and a substituent May have a phosphinoyl group, a heterocyclic group which may have a substituent, an alkylthiocarbonyl group which may have a substituent, an arylthiocarbonyl group which may have a substituent, or a substituent. Dialkylaminoca Examples thereof include a sulfonyl group and a dialkylaminothiocarbonyl group which may have a substituent.

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, Octadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2-methylphenacyl group , 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, 3-nitro Enashiru group, and the like.

  The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, such as a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, and a 9-phenanthryl. Group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m-, and p-cumenyl, mesityl, pentarenyl, binaphthalenyl, tarnaphthalenyl, quarternaphthalenyl, heptaenyl, biphenylenyl, indacenyl, fluoranthenyl, acenaphthylenyl, aceanthrylenyl Group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, taran Rasenyl group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, Examples include a hexaphenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an ovalenyl group.

  As an alkenyl group which may have a substituent, a C2-C10 alkenyl group is preferable, for example, a vinyl group, an allyl group, a styryl group etc. are mentioned.

  The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

  The alkylsulfinyl group which may have a substituent is preferably an alkylsulfinyl group having 1 to 20 carbon atoms. For example, a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, a butylsulfinyl group, and a hexylsulfinyl group. Group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, methoxymethylsulfinyl group and the like.

  The arylsulfinyl group which may have a substituent is preferably an arylsulfinyl group having 6 to 30 carbon atoms, such as a phenylsulfinyl group, 1-naphthylsulfinyl group, 2-naphthylsulfinyl group, 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenylsulfuric group Iniru group, 4-dimethylaminophenyl sulfinyl group and the like.

  The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms. For example, a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group. Group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methoxymethylsulfonyl group, perfluoroalkylsulfonyl group, etc. It is done.

  The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, such as a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, 4-dimethylaminopheny Sulfonyl group, and the like.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, for example, acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1-naphthoyl. Group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxybenzoyl Group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxybenzoyl Groups and the like.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as a methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, octyl. Examples thereof include an oxycarbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.

  The aryloxycarbonyl group which may have a substituent includes a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, a 2-naphthyloxycarbonyl group, a 4-methylsulfanylphenyloxycarbonyl group, and a 4-phenylsulfanylphenyloxycarbonyl group. 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3 -Chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-fur B phenyloxycarbonyl group, 4-cyanophenyl oxycarbonyl group, and 4-methoxyphenyloxycarbonyl group.

  The phosphinoyl group which may have a substituent is preferably a phosphinoyl group having 2 to 50 carbon atoms, for example, dimethylphosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group, diphenylphosphinoyl group. Group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group and the like.

  The heterocyclic group that may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. For example, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group, 4H- Quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group, perimidinyl group Nyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group Group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group and the like.

  Examples of the alkylthiocarbonyl group which may have a substituent include, for example, methylthiocarbonyl group, propylthiocarbonyl group, butylthiocarbonyl group, hexylthiocarbonyl group, octylthiocarbonyl group, decylthiocarbonyl group, octadecylthiocarbonyl group, Examples thereof include a trifluoromethylthiocarbonyl group.

  Examples of the arylthiocarbonyl group which may have a substituent include 1-naphthylthiocarbonyl group, 2-naphthylthiocarbonyl group, 4-methylsulfanylphenylthiocarbonyl group, 4-phenylsulfanylphenylthiocarbonyl group, 4-dimethyl. Aminophenylthiocarbonyl group, 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3-chlorophenylthiocarbonyl group Group, 3-trifluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenylthiocarbonyl group Boniru group, 4-methoxyphenyl thiocarbonyl group.

  Examples of the dialkylaminocarbonyl group that may have a substituent include a dimethylaminocarbonyl group, a dimethylaminocarbonyl group, a dipropylaminocarbonyl group, and a dibutylaminocarbonyl group.

  Examples of the dialkylaminothiocarbonyl group which may have a substituent include a dimethylaminothiocarbonyl group, a dipropylaminothiocarbonyl group, and a dibutylaminothiocarbonyl group.

Among these, from the viewpoint of increasing sensitivity, R ⁸ is more preferably an acyl group, and specifically, an acetyl group, a propionyl group, a benzoyl group, or a toluyl group is preferable.

The divalent organic group represented by Q ² may have a C1-C12 alkylene which may have a substituent, cyclohexylene which may have a substituent, or a substituent. Alkynylene is mentioned.
Examples of the substituent that can be introduced into these groups include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, phenoxy group, p- Aryloxy groups such as tolyloxy group, alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, acyloxy groups such as acetoxy group, propionyloxy group, benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group Group, acyl group such as methacryloyl group, methoxalyl group, methylsulfanyl group, alkylsulfanyl group such as tert-butylsulfanyl group, arylsulfanyl group such as phenylsulfanyl group, p-tolylsulfanyl group, methylamino group, Alkylamino groups such as hexylamino group, dimethylamino groups, diethylamino groups, morpholino groups, dialkylamino groups such as piperidino groups, phenylamino groups, arylamino groups such as p-tolylamino groups, methyl groups, ethyl groups, tert- In addition to alkyl groups such as butyl group and dodecyl group, phenyl groups, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group and the like, hydroxy group, carboxy group, formyl group, mercapto Group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammonium group, dimethylsulfonyl group Group, triphenylphenacylphos Niumiru group, and the like.
Among these, Q ² is 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 coloring due to heating. An alkylene group, an alkylene group substituted with an alkenyl group (eg, vinyl group, allyl group), an aryl group (eg, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl) An alkylene group substituted with a group) is preferred.

The aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms and may have a substituent.
Specifically, phenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m-, and p-cumenyl group, mesityl group, pentalenyl group, binaphthalenyl group, Turnaphthalenyl group, Quarter naphthalenyl group, Heptaenyl group, Biphenylenyl group, Indacenyl group, Fluoranthenyl group, Acenaphthylenyl group, Aceantrirenyl group, Phenalenyl group, Fluorenyl group, Anthryl group, Bianthracenyl group, Teranthracenyl group, Quarter Anthracenyl group, anthraquinolyl group, phenanthri Group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, rubicenyl group, coronenyl group, A trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyrantrenyl group, an obalenyl group, and the like can be given. Of these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

  When the phenyl group has a substituent, examples of the substituent include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group. Group, aryloxy group such as phenoxy group, p-tolyloxy group, methylthioxy group, ethylthioxy group, alkylthioxy group such as tert-butylthioxy group, arylthiooxy group such as phenylthioxy group, p-tolyloxy group, methoxycarbonyl Groups, butoxycarbonyl groups, alkoxycarbonyl groups such as phenoxycarbonyl groups, acyloxy groups such as acetoxy groups, propionyloxy groups, benzoyloxy groups, acetyl groups, benzoyl groups, isobutyryl groups, acryloyl groups, methacryloyl groups, methoxalyl groups, etc. Group, Alkylsulfanyl groups such as tilsulfanyl group, tert-butylsulfanyl group, arylsulfanyl groups such as phenylsulfanyl group, p-tolylsulfanyl group, alkylamino groups such as methylamino group, cyclohexylamino group, dimethylamino group, diethylamino group, Dialkylamino groups such as morpholino group and piperidino group, arylamino groups such as phenylamino group and p-tolylamino group, alkyl groups such as ethyl group, tert-butyl group and dodecyl group, hydroxy group, carboxy group, formyl group, mercapto Group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammonium group, di Chill sulfo Niu mill group, triphenyl phenacyl phosphonium Niu mill group, and the like.

  In the general formula (5), it is preferable from the viewpoint of sensitivity that the structure of “SAr” formed by Ar and adjacent S is the following structure.

  Examples of the monovalent substituent represented by P include an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. 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, and a substituent. A good arylthiooxy group, a halogenated alkyl group that may have a substituent, an amide group that may have a substituent on N, an acyloxy group that may have a substituent, and a substituent May have an alkylsulfanyl group, an arylsulfanyl group which may have a substituent, an alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, or a substituent. Alkylsulfonyl group, with substituent Arylsulfonyl group which may have a substituent, acyl group which may have a substituent, alkoxycarbonyl group which may have a substituent, carbamoyl group which may have a substituent, sulfamoyl group which may have a substituent And an amino group which may have a substituent, a phosphinoyl group which may have a substituent, a heterocyclic group which may have a substituent, a halogen group and the like.

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, Octadecyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group 4-methylphenacyl group, 2-methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, 3-ni Rofenashiru group, and the like.

  The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, such as a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, and a 9-phenanthryl. Group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m-, and p-cumenyl, mesityl, pentarenyl, binaphthalenyl, tarnaphthalenyl, quarternaphthalenyl, heptaenyl, biphenylenyl, indacenyl, fluoranthenyl, acenaphthylenyl, aceanthrylenyl Group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, taran Rasenyl group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, Examples include a hexaphenyl group, a hexacenyl group, a ruvicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an oberenyl group.

  As an alkenyl group which may have a substituent, a C2-C10 alkenyl group is preferable, for example, a vinyl group, an allyl group, a styryl group etc. are mentioned.

  The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

  The alkoxy group which may have a substituent is preferably an alkoxy group having 1 to 30 carbon atoms, for example, a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, an isobutoxy group, or a sec-butoxy group. Tert-butoxy group, pentyloxy group, isopentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, ethoxycarbonylmethyl group, 2 -Ethylhexyloxycarbonylmethyloxy group, aminocarbonylmethyloxy group, N, N-dibutylaminocarbonylmethyloxy group, N-methylaminocarbonylmethyloxy group, N-ethylaminocarbonylmethyloxy group, N-octylaminocarb Methylpropenylmethyl group, N- methyl -N- benzylaminocarbonyl methyloxy group, a benzyloxy group, and a cyanomethyloxy group.

  The aryloxy group which may have a substituent is preferably an aryloxy group having 6 to 30 carbon atoms, such as a phenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 2-chlorophenyloxy group, 2-methylphenyloxy group, 2-methoxyphenyloxy group, 2-butoxyphenyloxy group, 3-chlorophenyloxy group, 3-trifluoromethylphenyloxy group, 3-cyanophenyloxy group, 3-nitrophenyloxy group, Examples include 4-fluorophenyloxy group, 4-cyanophenyloxy group, 4-methoxyphenyloxy group, 4-dimethylaminophenyloxy group, 4-methylsulfanylphenyloxy group, 4-phenylsulfanylphenyloxy group, and the like.

  The alkylthioxy group which may have a substituent is preferably a thioalkoxy group having 1 to 30 carbon atoms. For example, a methylthioxy group, an ethylthioxy group, a propylthioxy group, an isopropylthioxy group, a butylthioxy group, an isobutylthio group. Oxy group, sec-butylthioxy group, tert-butylthioxy group, pentylthioxy group, isopentylthioxy group, hexylthioxy group, heptylthioxy group, octylthioxy group, 2-ethylhexylthioxy group, decylthioxy group, dodecyl Examples include a thioxy group, an octadecyl thioxy group, and a benzyl thioxy group.

  The arylthioxy group which may have a substituent is preferably an arylthioxy group having 6 to 30 carbon atoms, such as a phenylthioxy group, a 1-naphthylthioxy group, a 2-naphthylthioxy group, 2 -Chlorophenylthioxy group, 2-methylphenylthioxy group, 2-methoxyphenylthioxy group, 2-butoxyphenylthioxy group, 3-chlorophenylthioxy group, 3-trifluoromethylphenylthioxy group, 3-cyano Phenylthioxy group, 3-nitrophenylthioxy group, 4-fluorophenylthioxy group, 4-cyanophenylthioxy group, 4-methoxyphenylthioxy group, 4-dimethylaminophenylthioxy group, 4-methylsulfanyl Examples thereof include a phenylthioxy group and a 4-phenylsulfanylphenylthioxy group.

  The acyloxy group which may have a substituent is preferably an acyloxy group having 2 to 20 carbon atoms, such as an acetyloxy group, a propanoyloxy group, a butanoyloxy group, a pentanoyloxy group, or trifluoromethylcarbonyloxy. Group, benzoyloxy group, 1-naphthylcarbonyloxy group, 2-naphthylcarbonyloxy group and the like.

  The alkylsulfanyl group which may have a substituent is preferably an alkylsulfanyl group having 1 to 20 carbon atoms. For example, a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, an isopropylsulfanyl group, a butylsulfanyl group, or a hexylsulfanyl group. Group, cyclohexylsulfanyl group, octylsulfanyl group, 2-ethylhexylsulfanyl group, decanoylsulfanyl group, dodecanoylsulfanyl group, octadecanoylsulfanyl group, cyanomethylsulfanyl group, methoxymethylsulfanyl group and the like.

  The arylsulfanyl group which may have a substituent is preferably an arylsulfanyl group having 6 to 30 carbon atoms, such as a phenylsulfanyl group, 1-naphthylsulfanyl group, 2-naphthylsulfanyl group, 2-chlorophenylsulfanyl group, 2-methylphenylsulfanyl group, 2-methoxyphenylsulfanyl group, 2-butoxyphenylsulfanyl group, 3-chlorophenylsulfanyl group, 3-trifluoromethylphenylsulfanyl group, 3-cyanophenylsulfanyl group, 3-nitrophenylsulfanyl group, 4-fluorophenylsulfanyl group, 4-cyanophenylsulfanyl group, 4-methoxyphenylsulfanyl group, 4-methylsulfanylphenylsulfanyl group, 4-phenylsulfanylphenylsulfuric group Aniru group, 4-dimethylamino-phenylsulfanyl group and the like.

  The alkylsulfinyl group which may have a substituent is preferably an alkylsulfinyl group having 1 to 20 carbon atoms. For example, a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, a butylsulfinyl group, and a hexylsulfinyl group. Group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, methoxymethylsulfinyl group and the like.

  The arylsulfinyl group which may have a substituent is preferably an arylsulfinyl group having 6 to 30 carbon atoms, such as a phenylsulfinyl group, 1-naphthylsulfinyl group, 2-naphthylsulfinyl group, 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenylsulfuric group Iniru group, 4-dimethylaminophenyl sulfinyl group and the like.

  The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms. For example, a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group. Group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methoxymethylsulfonyl group and the like.

  The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, such as a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, 4-dimethylaminopheny Sulfonyl group, and the like.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, for example, acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1-naphthoyl. Group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxybenzoyl Group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxybenzoyl Groups and the like.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as a methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, octyl. Oxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, phenoxycarbonyl group, trifluoromethyloxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4- Phenylsulfanylphenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group Group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group , 3-nitrophenyloxycarbonyl group, 4-fluorophenyloxycarbonyl group, 4-cyanophenyloxycarbonyl group, 4-methoxyphenyloxycarbonyl group and the like.

  The carbamoyl group which may have a substituent is preferably a carbamoyl group having 1 to 30 carbon atoms, for example, an N-methylcarbamoyl group, an N-ethylcarbamoyl group, an N-propylcarbamoyl group, or an N-butylcarbamoyl group. N-hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2-methylphenylcarbamoyl group, N-2- Chlorophenylcarbamoyl group, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyl) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N-3-cyanophenyl Carbamoyl group N-4-methoxyphenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-dibutylcarbamoyl group, N, N-diphenylcarbamoyl group and the like can be mentioned.

  The sulfamoyl group which may have a substituent is preferably a sulfamoyl group having 0 to 30 carbon atoms, for example, a sulfamoyl group, an N-alkylsulfamoyl group, an N-arylsulfamoyl group, N, N- Examples thereof include a dialkylsulfamoyl group, an N, N-diarylsulfamoyl group, and an N-alkyl-N-arylsulfamoyl group. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfur group. Famoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2- Methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxyphenyl Nylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl Group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diphenylsulfamoyl group and the like.

The amino group which may have a substituent is preferably an amino group having 0 to 50 carbon atoms in total, for example, —NH ₂ , N-alkylamino group, N-arylamino group, N-acylamino group, N— Examples include sulfonylamino group, N, N-dialkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, N, N-disulfonylamino group and the like. More specifically, N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-tert-butylamino group, N-hexylamino group, N-cyclohexylamino group, N-octylamino group, N-2-ethylhexylamino group, N-decylamino group, N-octadecylamino group, N-benzylamino group, N-phenylamino group, N-2-methylphenylamino Group, N-2-chlorophenylamino group, N-2-methoxyphenylamino group, N-2-isopropoxyphenylamino group, N-2- (2-ethylhexyl) phenylamino group, N-3-chlorophenylamino group, N-3-nitrophenylamino group, N-3-cyanophenylamino group, N-3-trifluoromethylphenyla Group, N-4-methoxyphenylamino group, N-4-cyanophenylamino group, N-4-trifluoromethylphenylamino group, N-4-methylsulfanylphenylamino group, N-4-phenylsulfanylphenylamino Group, N-4-dimethylaminophenylamino group, N-methyl-N-phenylamino group, N, N-dimethylamino group, N, N-diethylamino group, N, N-dibutylamino group, N, N-diphenyl Amino group, N, N-diacetylamino group, N, N-dibenzoylamino group, N, N- (dibutylcarbonyl) amino group, N, N- (dimethylsulfonyl) amino group, N, N- (diethylsulfonyl) Amino group, N, N- (dibutylsulfonyl) amino group, N, N- (diphenylsulfonyl) amino group, morpholino group, 3, - dimethyl morpholino group, and a carbazolyl group.

  The phosphinoyl group which may have a substituent is preferably a phosphinoyl group having 2 to 50 carbon atoms, for example, dimethylphosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group, diphenylphosphinoyl group. Group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group and the like.

  The heterocyclic group that may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. For example, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group, 4H- Quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group, perimidinyl group Nyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group Group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group and the like.

  Examples of the halogen group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the halogenated alkyl group which may have a substituent include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a dichloromethyl group, a trichloromethyl group, a monobromomethyl group, a dibromomethyl group, and a tribromomethyl group. Etc.

  Examples of the amide group which may have a substituent on N include N, N-dimethylamide group and N, N-diethylamide group.

  Furthermore, the alkyl group which may have a substituent mentioned above, the aryl group which may have a substituent, the alkenyl group which may have a substituent, the alkynyl group which may have a substituent, a substituent An alkoxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylthioxy group that may have a substituent, an arylthioxy group that may have a substituent, and a substituent. An acyloxy group which may have a substituent, an alkylsulfanyl group which may have a substituent, an arylsulfanyl group which may have a substituent, an alkylsulfinyl group which may have a substituent, and a substituent. Good arylsulfinyl group, alkylsulfonyl group which may have a substituent, arylsulfonyl group which may have a substituent, acyl group which may have a substituent, alkoxycarbonyl which may have a substituent Base The carbamoyl group which may have a substituent, the sulfamoyl group which may have a substituent, the amino group which may have a substituent, and the heterocyclic group which may have a substituent may be further substituted. It may be substituted with a group.

  Examples of such a substituent include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, phenoxy group and p-tolyloxy group. Aryloxy group, alkoxycarbonyl group such as methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, acyloxy group such as acetoxy group, propionyloxy group, benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group , Acyl group such as methoxalyl group, alkylsulfanyl group such as methylsulfanyl group, tert-butylsulfanyl group, arylsulfanyl group such as phenylsulfanyl group, p-tolylsulfanyl group, methylamino group, cyclohexyl Alkylamino group such as mino group, dimethylamino group, diethylamino group, morpholino group, dialkylamino group such as piperidino group, arylamino group such as phenylamino group, p-tolylamino group, methyl group, ethyl group, tert-butyl group In addition to alkyl groups such as dodecyl group, phenyl groups, p-tolyl groups, xylyl groups, cumenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, etc., hydroxy groups, carboxy groups, formyl groups, mercapto groups, Sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammonium group, dimethylsulfonyl group, Triphenylphenacylphosphoniumyl group And the like.

Among these, P has an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region. An alkenyl group which may have a substituent, 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 which may have a substituent A group, an arylthioxy group which may have a substituent, a halogenated alkyl group which may have a substituent, an amino group which may have a substituent, or a substituent on N Good amide groups are preferred.
Moreover, although n in General formula (5) represents the integer of 0-5, the integer of 0-3 is preferable from a viewpoint of the ease of a synthesis | combination, and the integer of 0-2 is more preferable.
In the general formula (5), when a plurality of P are present, the plurality of P may be the same or different.

Examples of the divalent organic group represented by Q ¹ include the structures shown below. In the groups shown below, “*” represents the bonding position between Q ¹ and the adjacent carbon atom in the general formula (5).

  Among these, from the viewpoint of increasing sensitivity, the following structures are preferable.

  The photopolymerization initiator represented by the general formula (5) is particularly preferably a photopolymerization initiator represented by the following general formula (6) because of high sensitivity.

In the general formula (6), R ⁸ and P each independently represent a monovalent substituent, Q ² represents a divalent organic group, and Ar represents an aryl group. n is an integer of 0-5. When a plurality of P are present, each of the plurality of P independently represents a monovalent substituent.
R ⁸ , Q ² , Ar, P, and n in the general formula (6) are synonymous with R ⁸ , Ar, P, and n in the general formula (5), and preferred examples are also the same.

  Specific examples of the photopolymerization initiator represented by the general formula (5) are shown below.

  The compound represented by the general formula (5) used in the present invention has an absorption wavelength in a wavelength region of 250 nm to 500 nm. More preferably, the thing which has an absorption wavelength in the wavelength range of 300 nm-380 nm can be mentioned. In particular, those having high absorbance at 308 nm and 355 nm are preferable.

  (D) It is preferable that content of a photoinitiator is 0.1 mass%-20 mass% with respect to the total non volatile matter in a photocurable blue coloring composition, More preferably, it is 0.5 mass%. -15% by mass, particularly preferably 3% by mass to 15% by mass. Within this range, good sensitivity and pattern formability can be obtained.

[Sensitizing dye]
It is preferable to add a sensitizing dye to the photocurable blue coloring composition in the present invention from the viewpoint of improving sensitivity. Exposure to a wavelength that can be absorbed by the sensitizing dye promotes radical generation reaction of the photopolymerization initiator component and polymerization reaction of the ethylenically unsaturated compound thereby.
Examples of such a sensitizing dye include a known spectral sensitizing dye or dye, or a dye or pigment that absorbs light and interacts with a photopolymerization initiator.

  Preferred spectral sensitizing dyes or dyes that can be used in the present invention include polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, Rose bengal), cyanines (for example, thiacarbocyanine, oxacarbocyanine), merocyanines (for example, merocyanine, carbomerocyanine), thiazines (for example, thionine, methylene blue, toluidine blue), acridines (for example, acridine orange, Chloroflavin, acriflavine), phthalocyanines (eg, phthalocyanine, metal phthalocyanine), porphyrins (eg, tetraphenylporphyrin, central metal-substituted porphyrin), chlorophylls (eg, chlorophyllin) Phil, chlorophyllin, center metal-substituted chlorophyll), metal complexes, anthraquinones (e.g., anthraquinone), squaryliums (e.g., squarylium), and the like.

The example of a more preferable spectral sensitizing dye or dye is illustrated below.
A styryl dye described in JP-B-37-13034; a cationic dye described in JP-A-62-143044; a quinoxalinium salt described in JP-B-59-24147; described in JP-A-64-33104 A new methylene blue compound; anthraquinones described in JP-A No. 64-56767; benzoxanthene dyes described in JP-A No. 2-1714; acridines described in JP-A Nos. 2-226148 and 2-226149 Pyryllium salts described in JP-B-40-28499; Cyanines described in JP-B-46-42363; Benzofuran dyes described in JP-A-2-63053; JP-A-2-85858, JP-A-2-216154 Conjugated ketone dyes disclosed in Japanese Patent Publication No. 57-10605; Azocinnamylidene derivatives described in Japanese Patent No. 0321; cyanine dyes described in Japanese Patent Laid-Open No. 1-287105; Japanese Patent Laid-Open Nos. 62-31844, 62-31848, 62-1443043 Xanthene dyes described above; aminostyryl ketone described in JP-B-59-28325; dye described in JP-A-2-17943; merocyanine dye described in JP-A-2-244050; described in JP-B-59-28326 Merocyanine dyes described in JP-A-59-89303; merocyanine dyes described in JP-A-8-129257; benzopyran dyes described in JP-A-8-334897.

Other preferred embodiments of the sensitizing dye include dyes belonging to the following compound group and having a maximum absorption wavelength at 350 to 450 nm.
For example, polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanine (Eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squalium (eg, , Squalium).

  The content of the sensitizing dye is preferably 0.1% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass with respect to the total nonvolatile content in the photocurable blue coloring composition. It is.

[Thiol compound]
The photocurable blue coloring composition in the present invention preferably contains a thiol compound.
The thiol compound in the present invention acts as a co-sensitizer or exhibits an effect of improving the adhesion between the formed colored pixel and the substrate. The co-sensitizer has functions such as further improving the sensitivity of the sensitizing dye and the photopolymerization initiator to actinic radiation, or suppressing polymerization inhibition due to oxygen of the ethylenically unsaturated compound.

Specific examples of the thiol compound include ethylene glycol bisthiopropionate (EGTP), butanediol bisthiopropionate (BDTP), trimethylolpropane tristhiopropionate (TMTP), pentaerythritol tetrakisthiopropionate ( PETP), mercaptopropionic acid derivatives such as THEIC-BMPA represented by the following formula; ethylene glycol bisthioglycolate (EGTG), butanediol bisthioglycolate (BDTG), hexanediol bisthioglycolate (HDTG), triglyceride Thioglycolic acid derivatives such as methylolpropane tristhioglycolate (TMTG) and pentaerythritol tetrakisthioglycolate (PETG); 1,2-benzenedithiol, 1,3-benzene Thiol, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2,2 ′-(ethylenedithio) diethanethiol, meso-2,3-dimercaptosuccinic acid, p- Examples include thiols such as xylenedithiol and m-xylenedithiol; mercaptoethers such as di (mercaptoethyl) ether.
These can be used alone or in combination of two or more.

  As for the thiol compound used by this invention, what is represented by the following general formula (I) is more preferable.

  In general formula (I), R represents a hydrogen atom, an alkyl group, or an aryl group, and A represents an atomic group that forms a heterocycle with N═C—N.

In general formula (I), R represents a hydrogen atom, an alkyl group, or an aryl group.
Examples of the alkyl group represented by R include a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and a linear or carbon atom having 1 to 12 carbon atoms. A branched alkyl group having 3 to 12 and a cyclic alkyl group having 5 to 10 carbon atoms are more preferable.
Specific examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group. , Eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group , 2-norbornyl group and the like.

  As the aryl group represented by R, in addition to those having a single ring structure, one to three benzene rings form a condensed ring, a benzene ring and a five-membered unsaturated ring form a condensed ring, etc. Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, a fluorenyl group, and the like. Among these, a phenyl group and a naphthyl group are more preferable. preferable.

  These alkyl groups and aryl groups may further have a substituent. Examples of the substituent that can be introduced include linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms, and the number of carbon atoms. A linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, and 2 carbon atoms -20 alkoxycarbonyloxy group, aryloxycarbonyloxy group having 7-20 carbon atoms, carbamoyloxy group having 1-20 carbon atoms, carbonamido group having 1-20 carbon atoms, 1-20 carbon atoms Sulfonamide group, carbamoyl group having 1 to 20 carbon atoms, sulfamoyl group, substituted sulfamoyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, carbon atom An aryloxy group having 6 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an N-acylsulfamoyl group having 1 to 20 carbon atoms, and 1 carbon atom -20 N-sulfamoylcarbamoyl group, C1-C20 alkylsulfonyl group, C6-C20 arylsulfonyl group, C2-C20 alkoxycarbonylamino group, C7-20 Aryloxycarbonylamino group, amino group, substituted amino group having 1 to 20 carbon atoms, imino group having 1 to 20 carbon atoms, ammonio group having 3 to 20 carbon atoms, carboxyl group, sulfo group, oxy group, Mercapto group, alkylsulfinyl group having 1 to 20 carbon atoms, arylsulfinyl group having 6 to 20 carbon atoms, and 1-2 carbon atoms Alkylthio group, arylthio group having 6 to 20 carbon atoms, ureido group having 1 to 20 carbon atoms, heterocyclic group having 2 to 20 carbon atoms, acyl group having 1 to 20 carbon atoms, sulfamoylamino group A substituted sulfamoylamino group having 1 to 2 carbon atoms, a silyl group having 2 to 20 carbon atoms, an isocyanate group, an isocyanide group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, A nitro group, an onium group, etc. are mentioned.

In the general formula (I), A represents an atomic group that forms a heterocycle with N═C—N.
Examples of atoms constituting this atomic group include a carbon atom, a nitrogen atom, a hydrogen atom, a sulfur atom, and a selenium atom.
The heterocycle formed by A and N═C—N may further have a substituent. Examples of the substituent that can be introduced include substituents that can be introduced into the alkyl group and aryl group. The same thing is mentioned.

  Further, the thiol compound is more preferably a compound represented by the following general formula (II) or general formula (III).

In general formula (II), R ¹ represents an aryl group, and X represents a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group, or an aryl group.

In general formula (III), R ² represents an alkyl group or an aryl group, and X represents a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group, or an aryl group.

  In general formula (II) and general formula (III), as a halogen atom represented by X, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferable.

  In the general formula (II) and general formula (III), the alkoxy group represented by X includes a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, a pentyloxy group, a hexyloxy group, and a dodecyloxy group. Group, benzyloxy group, allyloxy group, phenethyloxy group, carboxyethyloxy group, methoxycarbonylethyloxy group, ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy Group, morpholinopropyloxy group, allyloxyethoxyethoxy group, phenoxy group, tolyloxy group, xylyloxy group, mesityloxy group, cumenyloxy group, methoxyphenyloxy group, ethoxyphenyloxy group Chlorophenyl group, bromophenyl group, acetyloxy group, benzoyloxy group, naphthyloxy group and the like.

Formula (II) and general formula (III), the alkyl group represented by R ² or X has the same meaning as the alkyl group represented by R in formula (I), and also the preferred ranges thereof .
In the general formulas (II) and (III), the aryl groups represented by R ¹ , R ² , and X are each independently an aryl group represented by R in the general formula (I) It is synonymous and the preferable range is also the same.

In general formula (II) and general formula (III), each group represented by R ¹ , R ² , or X may further have a substituent, and as the substituent, the general formula (I The same as those listed as substituents that can be introduced into the alkyl group or aryl group represented by R).

In general formula (II) and general formula (III), it is more preferable that X is a hydrogen atom from the viewpoint of solubility of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA as appropriate).
In general formula (II), R ¹ is most preferably a phenyl group from the viewpoints of sensitivity and PGMEA solubility.
In general formula (III), R ² is more preferably a methyl group, an ethyl group, a phenyl group, or a benzyl group from the viewpoints of sensitivity and PGMEA solubility.

  Of the compounds represented by the general formula (II) and the compounds represented by the general formula (III), the compounds represented by the general formula (III) are most preferable from the viewpoint of solubility of PGMEA.

  These thiol compounds are described in J. Org. Appl. Chem. , 34, 2203-2207 (1961).

  In the photocurable blue coloring composition of the present invention, the compound represented by the general formula (I) may be used alone or in combination of two or more, and the compound represented by the general formula (II) You may use together the compound selected from the compound selected from the compound represented, the compound selected from the compound represented from general formula (III), respectively.

  The content of the thiol compound in the photocurable blue coloring composition is preferably 0.1% by mass to 5.0% by mass with respect to the solid content of the photocurable blue coloring composition. More preferably, it is 4% by mass. It exists in this range since it does not impair the polymerizability of a photocurable blue coloring composition.

[(E) ethylenically unsaturated compound]
The photocurable blue coloring composition in the present invention contains (E) an ethylenically unsaturated compound.
The ethylenically unsaturated compound that can be used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and has at least one, preferably two or more terminal ethylenically unsaturated bonds. Selected from compounds. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, that is, dimers, trimers and oligomers, or mixtures thereof, and copolymers thereof.
Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or A dehydration condensation reaction product with a polyfunctional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid There are EO-modified triacrylate and the like.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.
Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59- Those having an aromatic skeleton described in Japanese Patent No. 5241 and JP-A-2-226149, those containing an amino group described in JP-A-1-165613, and the like are also preferably used.
Furthermore, the ester monomers described above can also be used as a mixture.

Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like.
Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (V) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

Formula (IV)
^{_{CH 2 = C (R 4)}} COOCH 2 CH (R 5) OH (IV)
(However, R ⁴ and R ⁵ each independently represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56- Urethane compounds having an ethylene oxide skeleton described in JP 17654, JP-B 62-39417, and JP-B 62-39418 are also suitable. Furthermore, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. Can obtain a photocurable blue coloring composition having an excellent photosensitive speed.

  Other examples include polyester acrylates, epoxy resins and (meth) described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates reacted with acrylic acid. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and vinylphosphonic acid compounds described in JP-A-2-25493 Etc. can also be mentioned. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, the Japan Adhesion Association magazine vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

About these ethylenically unsaturated compounds, the details of usage, such as the structure, single use or combination, addition amount, etc. can be arbitrarily set according to the performance design of the final photosensitive material. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. In order to increase the strength of the colored pixels, those having three or more functionalities are preferable, and those having different functional numbers and different polymerizable groups (for example, acrylic esters, methacrylic esters, styrene compounds, vinyl ether compounds). It is also effective to adjust both sensitivity and intensity by using together. From the viewpoint of curing sensitivity, it is preferable to use a compound containing two or more (meth) acrylic acid ester structures, more preferably a compound containing three or more, and most preferably a compound containing four or more. preferable. Moreover, it is preferable to contain an EO modified body from a viewpoint of hardening sensitivity and developability of an unexposed part. Moreover, it is preferable to contain a urethane bond from a viewpoint of hardening sensitivity and exposure part intensity | strength.
In addition, the selection / use method of the addition polymerization compound is an important factor for compatibility with other components (for example, alkali-soluble resin, photopolymerization initiator) in the photocurable blue coloring composition, For example, the 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 for the purpose of improving the adhesion between the substrate and the colored pixels.

  From the above viewpoint, bisphenol A diacrylate, bisphenol A diacrylate EO modified product, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, penta Erisrito Preferred examples include tetraacrylate EO modified products, dipentaerythritol hexaacrylate EO modified products, and commercially available products include urethane oligomers UAS-10, UAB-140 (manufactured by Nippon Paper Chemicals), DPHA (Nippon Kasei). Yakuhin Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) are preferred.

  Among them, bisphenol A diacrylate EO modified product, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modified product, Dipentaerythritol hexaacrylate EO modified products such as DPHA (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (Kyoeisha) Chemical Industries, Ltd.) is more preferable.

  (E) The content of the ethylenically unsaturated compound is preferably 5% by mass to 55% by mass in the total nonvolatile content in the photocurable blue colored composition in the present invention, and is preferably 10% by mass to 50% by mass. It is more preferable that it is 15 mass%-45 mass%.

[(F) Resin]
The photocurable blue coloring composition used in the present invention contains a resin for the purpose of improving film properties and imparting development properties. Here, examples of the resin include alkali-soluble resins, epoxy resins, pigment coating resins, and polymer compounds such as polymer dispersants. In consideration of development with an alkali, it is preferable to include at least an alkali-soluble resin.
The alkali-soluble resin and epoxy resin in these resins will be described in detail below. The pigment coating resin and the polymer dispersant will be described later.

  The alkali-soluble resin used in the present invention is a linear organic polymer, and at least one molecule in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having a group that promotes alkali solubility (for example, carboxyl group, phosphoric acid group, sulfonic acid group, hydroxyl group, etc.).

  More preferable as the alkali-soluble resin is a polymer having a carboxylic acid in the side chain, for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54- No. 25957, JP-A-59-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, Acrylics such as crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., acidic cellulose derivatives having a carboxylic acid in the side chain, and polymers having a hydroxyl group added with an acid anhydride The thing of a system copolymer is mentioned.

  The acid value is preferably in the range of 20 mgKOH / g to 200 mgKOH / g, preferably 30 mgKOH / g to 180 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g.

The alkali-soluble resin used in the present invention is particularly preferably a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith.
Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.
As the alkyl (meth) acrylate and aryl (meth) acrylate, CH ₂ ═C (R) (COOR ′) [wherein R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ′ represents carbon. An alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms is represented. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate , Octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyalkyl (meth) acrylate (alkyl is 1 to 3 carbon atoms) 8 alkyl group), hydroxyglycidyl methacrylate, tetrahydrofurfuryl methacrylate and the like.

As the vinyl _compounds, CH ² = ^CR 1 ^R 2 [wherein, ^{R 1} represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, ^{R 2} represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms. Specific examples include styrene, α-methylstyrene, vinyl toluene, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like.

The other copolymerizable monomers as described above can be used singly or in combination of two or more.
Of the above, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are particularly suitable.

A resin having a polyalkylene oxide chain in the molecular side chain is also preferable as the alkali-soluble resin.
As the polyalkylene oxide chain, a polyethylene oxide chain, a polypropylene oxide chain, a polytetramethylene glycol chain, or a combination thereof can be used, and the end of these chains is a hydrogen atom or a linear or branched alkyl group.
1-20 are preferable and, as for the repeating unit of a polyethylene oxide chain and a polypropylene oxide chain, 2-12 are more preferable.
Examples of the acrylic copolymer having a polyalkylene oxide chain in the side chain include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate, and the like. A compound in which these terminal OH groups are alkyl-blocked, for example, methoxypolyethylene glycol mono (meth) acrylate, ethoxypolypropylene glycol mono (meth) acrylate, methoxypoly (ethylene glycol-propylene glycol) mono (meth) acrylate, etc. as a copolymerization component The acrylic copolymer containing is preferable.

As described above, the acrylic resin has an acid value in the range of 20 mgKOH / g to 200 mgKOH / g. If the acid value is 200 mgKOH / g or less, the acrylic resin does not become too soluble in alkali, and the appropriate development range (development latitude) can be prevented from becoming narrow. On the other hand, if it is 20 mgKOH / g or more, the solubility in alkali is unlikely to be reduced, so that it is possible to prevent the development time from being prolonged.
In addition, the weight average molecular weight Mw (polystyrene conversion value measured by GPC method) of the acrylic resin is used in order to realize a viscosity range in which a photocurable blue coloring composition can be easily used in a process such as coating, and film strength. In order to ensure the above, it is preferably 2,000 to 100,000, more preferably 3,000 to 50,000.

Moreover, in order to improve the crosslinking efficiency of the photocurable blue coloring composition that can be used in the present invention, it is preferable to use an alkali-soluble resin having a polymerizable group. This alkali-soluble resin having a polymerizable group may be used alone or in combination with an alkali-soluble resin having no polymerizable group.
As the alkali-soluble resin having a polymerizable group, a polymer containing an aryl group, a (meth) acryl group, an aryloxyalkyl group or the like in the side chain is useful. Such an alkali-soluble resin having a polymerizable double bond is preferable because it can be developed with an alkaline developer and further has photocurability and thermosetting properties. Among them, a resin having an aryl group as a side chain polymerizable group is more preferable because it has high resist curability and high thermal decomposition resistance.
Hereinafter, suitable examples of the alkali-soluble resin containing a polymerizable group will be shown, but in one molecule, an alkali-soluble group such as a COOH group and an OH group, and a polymerizable double bond (carbon-carbon unsaturated bond). Are not limited to those shown below.

That is,
(1) By reacting an isocyanate group and an OH group in advance, leaving one unreacted isocyanate group and reacting with a compound containing at least one (meth) acryloyl group and an acrylic resin containing a carboxyl group Urethane-modified polymerizable double bond-containing acrylic resin obtained (2) Contains unsaturated group obtained by reaction of acrylic resin containing carboxyl group and compound having both epoxy group and polymerizable double bond in molecule Acrylic resin (3) Acid pendant type epoxy acrylate resin (4) A polymerizable double bond-containing acrylic resin obtained by reacting an acrylic resin containing an OH group with a dibasic acid anhydride having a polymerizable double bond.
Among the above, the resins (1) and (2) are particularly preferable.

As a specific example, a copolymer of an OH group, for example, 2-hydroxyethyl acrylate, a COOH group, for example, methacrylic acid, and a monomer such as an acrylic or vinyl compound copolymerizable therewith. A compound obtained by reacting a compound with an epoxy ring having reactivity with an OH group and a compound having a polymerizable double bond (for example, a compound such as glycidyl acrylate) can be used. In the reaction with the OH group, in addition to the epoxy ring, a compound having an acid anhydride, an isocyanate group, or an acryloyl group can also be used.
Further, a compound obtained by reacting an unsaturated carboxylic acid such as acrylic acid with a compound having an epoxy ring described in JP-A-6-102669 and JP-A-6-1938 is saturated or unsaturated polybasic. A reaction product obtained by reacting an acid anhydride can also be used.

  Examples of the compound having both an alkali solubilizing group such as a COOH group and a polymerizable double bond include, for example, Dainar NR series (manufactured by Mitsubishi Rayon Co., Ltd.); Photomer 6173 (COOH group-containing Polyanethane acrylic oligomer, Diamond Shamrock Co., Ltd.). Ltd.); Biscote R-264, KS resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.); Cyclomer P series, Plaxel CF200 series (both manufactured by Daicel Chemical Industries, Ltd.); Ebecryl 3800 (Daicel Cytech) Etc.).

  (F) The addition amount in the case of using an alkali-soluble resin as the resin is preferably in the range of 3% by mass to 50% by mass in the total nonvolatile content of the photocurable blue colored composition, and is preferably 5% by mass to 30%. The mass% is more preferable.

In preparing the photocurable blue coloring composition, it is preferable to add the following epoxy resin in addition to the alkali-soluble resin. Examples of the epoxy resin include compounds having two or more epoxy rings in the molecule, such as bisphenol A type, cresol novolak type, biphenyl type, and alicyclic epoxy compound.
For example, as bisphenol A type, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 and the like ( As described above, manufactured by Toto Kasei Co., Ltd.), Denacol EX-1101, EX-1102, EX-1103, etc. Daicel Chemical Industries, Ltd.) and the like, and bisphenol F type and bisphenol S type epoxy resins similar to these can also be used.
Epoxy acrylates such as Ebecryl 3700, 3701, and 600 (manufactured by Daicel Cytec Co., Ltd.) can also be used.

  Examples of the cresol novolak type include Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above, manufactured by Toto Kasei Co., Ltd.), Denacol EM-125, etc. (above, manufactured by Nagase ChemteX) As the biphenyl type, 3,5,3 ′, 5′-tetramethyl-4,4′-diglycidylbiphenyl and the like, and as the alicyclic epoxy compound, ceroxide 2021, 2081, 2083, 2085, Epolide GT-301 GT-302, GT-401, GT-403, EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.), Santo Tote ST-3000, ST-4000, ST-5080, ST-5100, etc. Manufactured by Co., Ltd.), Epiclon 430, 673, 695, 85 S, the 4032 (manufactured by DIC (Ltd.)), and the like.

  1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o-phthalic acid diglycidyl ester, terephthalic acid Diglycidyl ester, amine type epoxy resins such as Epototo YH-434 and YH-434L, and glycidyl ester obtained by modifying dimer acid in the skeleton of bisphenol A type epoxy resin can also be used.

Among these, “molecular weight / number of epoxy rings” is preferably 100 or more, and more preferably 130 to 500. If the “molecular weight / number of epoxy rings” is small, the curability is high, the shrinkage at the time of curing is large, and if it is too large, the curability is insufficient, the reliability is poor, and the flatness is deteriorated.
Specific preferred compounds satisfying this condition include Epototo YD-115, 118T, 127, YDF-170, YDPN-638, YDPN-701, Plaxel GL-61, GL-62, 3, 5, 3 ′, 5 Examples include '-tetramethyl-4,4' diglycidyl biphenyl, ceroxide 2021, 2081, epolide GT-302, GT-403, and EHPE-3150.

  (F) The amount of addition in the case of using an epoxy resin as the resin is preferably in the range of 0.1% by mass to 30% by mass in the total nonvolatile content of the photocurable blue coloring composition, and 0.5% by mass. % To 20% by mass is more preferable, and 1% to 10% by mass is most preferable. When the addition amount is within this range, sufficient exposure sensitivity can be obtained without impairing photopolymerizability, and high heat resistance and chemical resistance can be imparted because it also has thermal polymerizability. The storage stability of can also be maintained.

[Other additives]
In addition to the above components, various known additives can be used in the photocurable blue coloring composition used in the present invention depending on the purpose.
Hereinafter, such additives will be described.

(Surfactant)
When the pigment concentration is increased, the thixotropy of the coating solution generally increases, so after the photocurable blue colored composition layer (colored layer coating film) is formed by applying or transferring the photocurable blue colored composition on the substrate It is easy to cause film thickness unevenness. In particular, in the formation of a photocurable blue colored composition layer (colored layer coating film) by the slit coating method, the coating liquid for forming the photocurable blue colored composition layer is leveled by drying until the coating film has a uniform thickness. It is important to form For this reason, it is preferable to contain an appropriate surfactant in the photocurable blue coloring composition. Preferred examples of the surfactant include surfactants disclosed in JP-A Nos. 2003-337424 and 11-133600.
Nonionic surfactants, fluorosurfactants, silicone surfactants, and the like are added as surfactants for improving coating properties.

  Nonionic surfactants include, for example, polyoxyethylene glycols, polyoxypropylene glycols, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, polyoxypropylene alkyl ethers. Nonionic surfactants such as polyoxypropylene alkyl aryl ethers, polyoxypropylene alkyl esters, sorbitan alkyl esters and monoglyceride alkyl esters are preferred.

  Specifically, polyoxyalkylene glycols such as polyoxyethylene glycol and polyoxypropylene glycol; polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxypropylene stearyl ether and polyoxyethylene oleyl ether; polyoxy Polyoxyethylene aryl ethers such as ethylene octyl phenyl ether, polyoxyethylene polystyryl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene-propylene polystyryl ether, polyoxyethylene nonylphenyl ether; polyoxyethylene dilaurate , Polyoxyalkylene dialkyl esters such as polyoxyethylene distearate, sorbitan fatty acids Ester, there is nonionic surfactants such as polyoxyalkylene sorbitan fatty acid esters.

  Specific examples of these include, for example, the Adeka Pluronic series, the Adecanol series, the Tetronic series (above made by ADEKA), the Emulgen series, the Leodore series (above made by Kao Corporation), the Eleminor series, and the Nonipole series. , Octopole series, Dodecapol series, New Pole series (Sanyo Kasei Co., Ltd.), Pionein series (Takemoto Yushi Co., Ltd.), Nissan Nonion series (Nippon Yushi Co., Ltd.), etc. . These commercially available products can be used as appropriate. A preferable HLB value is 8 to 20, more preferably 10 to 17.

As the fluorosurfactant, a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain can be suitably used.
Specific commercial products include, for example, MegaFac F142D, F172, F173, F176, F176, F177, F183, 780, 781, R30, R08, (DIC Corporation), Florard FC- 135, FC-170C, FC-430, FC-431 (manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145, Same S-382, Same SC-101, Same SC-102, Same SC-103, Same SC-104, Same SC-105, Same SC-106 (Asahi Glass Co., Ltd.), F Top EF351, Same 352, Same 801 and 802 (manufactured by JEMCO).

  Examples of the silicone-based surfactant include Toray Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, SF- 8428, DC-57, DC-190 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 ( As mentioned above, Momentive Performance Materials Japan, etc.) can be mentioned.

  These surfactants are preferably used in an amount of 5 parts by mass or less, more preferably 2 parts by mass or less, with respect to 100 parts by mass of the coating liquid for forming the photocurable blue coloring composition layer. When the amount of the surfactant exceeds 5 parts by mass, surface roughness due to coating and drying tends to occur, and smoothness tends to deteriorate.

  In addition, in order to promote alkali solubility of the uncured part and further improve the developability of the photocurable blue coloring composition, addition of an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less Can be performed. 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 Others such as phenoxyacetic acid, methoxyphenoxyacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, umberic acid Carboxylic acid is mentioned.

(Alkoxysilane compound)
From the viewpoint of improving the adhesion to the substrate, an alkoxysilane compound, especially a silane coupling agent can be used for the photocurable blue coloring composition used in the present invention.
The silane coupling agent preferably has an alkoxysilyl group as a hydrolyzable group that can be chemically bonded to an inorganic material, and (meth) acryloyl or phenyl that exhibits affinity by interacting or forming a bond with an organic resin. , Mercapto, and epoxysilane, and (meth) acryloylpropyltrimethoxysilane is more preferable among them.
The addition amount when using a silane coupling agent is preferably in the range of 0.2% by mass to 5.0% by mass in the total nonvolatile content in the photocurable blue coloring composition used in the present invention. 0.5 mass% to 3.0 mass% is more preferable.

(Co-sensitizer)
The photocurable blue coloring composition used in the present invention preferably contains a co-sensitizer if desired. In the present invention, the co-sensitizer has functions such as further improving the sensitivity of the sensitizing dye and initiator to actinic radiation or suppressing polymerization inhibition of the polymerizable compound (ethylenically unsaturated compound) by oxygen.
Examples of such cosensitizers include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. No. 60-84305, JP-A 62-18537, JP-A 64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

  Another example of the co-sensitizer includes sulfides such as disulfide compounds disclosed in JP-A-56-75643, and specifically includes 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2 -Mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene and the like.

  Other examples of the co-sensitizer include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), JP-B 55- Examples include a hydrogen donor described in Japanese Patent No. 34414, a sulfur compound (eg, trithiane) described in Japanese Patent Laid-Open No. 6-308727, and the like.

  The content of these co-sensitizers is 0.1% by mass to 30% by mass with respect to the total nonvolatile content of the photocurable blue coloring composition from the viewpoint of improving the curing rate due to the balance between polymerization growth rate and chain transfer. The range of 1 mass%-25 mass% is more preferable, and the range of 1.5 mass%-20 mass% is still more preferable.

(Polymerization inhibitor)
In the present invention, it is desirable to add a small amount of a thermal polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable ethylenically unsaturated compound during the production or storage of the photocurable blue coloring composition.
Examples of the thermal polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6). -T-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt, phenoxazine, phenothiazine and the like.

  As for the addition amount of a thermal-polymerization inhibitor, 0.01 mass%-5 mass% are preferable with respect to a photocurable blue coloring composition. If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide can be added to prevent polymerization inhibition due to oxygen and can be unevenly distributed on the surface of the photosensitive layer during the drying process after coating. . The addition amount of the higher fatty acid derivative is preferably 0.5% by mass to 10% by mass of the photocurable blue coloring composition.

(Plasticizer)
Furthermore, in this invention, in order to improve the physical property of a photocurable blue coloring composition, you may add an inorganic filler, a plasticizer, etc.
Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, and the like. 10 mass% or less can be added with respect to the total mass with resin.
The photocurable blue coloring composition of the present invention containing the above components is cured with high sensitivity to ultraviolet laser exposure, has excellent pattern formability, and the formed colored pattern has a shape and a visible light It has good transparency and is suitably used for forming a colored pattern for a color filter.

<Color filter manufacturing method>
A colored pattern is formed by applying the photocurable blue coloring composition of the present invention on a suitable substrate, curing the exposed area by pattern exposure with an ultraviolet laser, and developing and removing the unexposed area.
The method for producing a color filter of the present invention includes a colored layer forming step of forming a colored layer comprising the blue colored composition by applying the photocurable blue colored composition for a color filter of the present invention on a substrate, An exposure step of exposing the colored layer in a pattern using an ultraviolet laser having a wavelength of 300 nm to 380 nm and a developing step of developing the colored layer after exposure to form a colored pattern are included.
Hereinafter, the manufacturing method of the color filter which has the coloring pattern (blue coloring pixel) by the photocurable blue coloring composition containing each above components is demonstrated in order of a process.

[Colored layer forming step]
First, the colored layer formation process (application | coating process) which provides the photocurable blue coloring composition for color filters of the said this invention on a board | substrate and forms the colored layer which consists of this blue coloring composition is implemented.
In this case, examples of the substrate used include non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these, and solid-state imaging devices. The photoelectric conversion element board | substrate used for etc. is mentioned. Furthermore, a plastic substrate is also possible. In these substrates, a black matrix is formed in a lattice shape or the like, and colored pixels are formed in the empty portions of the lattice.
In the present invention, a substrate provided with the TFT electrode described above can also be used, and a substrate provided with a planarization layer on a substrate provided with a TFT electrode or a substrate provided with an adhesion layer can also be used.
In the present invention, the “TFT substrate” is a substrate in which a TFT (Thin Film Transistor) electrode is provided on a transparent substrate such as non-alkali glass, soda glass, Pyrex (registered trademark) glass, or quartz glass. .

  Further, if necessary, an undercoat layer may be provided on these substrates in order to improve adhesion with an upper layer, prevent diffusion of substances, or planarize the substrate surface. It is preferable that the substrate is large (generally 1 m or more per side) from the standpoint of achieving the effects of the present invention.

There is no restriction | limiting in particular in the method of providing a photocurable blue coloring composition on a board | substrate, and forming a colored layer, It can take well-known methods, such as the method of apply | coating and the method of transferring the coating film produced previously. it can. As the coating method, application methods such as various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing can be applied. Of these, slit coating is preferred from the viewpoints of accuracy and speed.
Further, as described above, a method of transferring a coating film previously formed on the temporary support by the above-described application method onto the substrate can also be applied.
Regarding the transfer method, the production methods described in JP-A-2006-23696, paragraph numbers [0023] and [0036] to [0051] and JP-A-2006-47592, paragraphs [0096] to [0108]. Can also be suitably used in the present invention.

  The thickness of the coating film of the photocurable blue coloring composition is preferably formed so that the film thickness after drying is 2.0 μm to 5.0 μm in order to obtain a sufficient color reproduction region. More preferably, the thickness is 3 μm to 3.0 μm. In the case of COA applications, the film thickness after drying is more preferably 3.0 μm to 4.5 μm in order to obtain good insulation.

[Drying process]
After the application of the photocurable blue coloring composition as described above is completed, the solvent can be dried by vacuum drying (VCD). Furthermore, the coating film on a board | substrate may be heat-dried (prebaked) and a photocurable blue coloring composition layer may be obtained.
The prebaking temperature of the coating film is preferably 60 ° C to 140 ° C, more preferably 80 ° C to 120 ° C. The pre-bake time is preferably 30 seconds to 300 seconds, and more preferably 80 seconds to 200 seconds.

[Exposure process]
Thereafter, pattern exposure with an ultraviolet laser as described above is performed on the photocurable blue coloring composition layer formed on the substrate. The exposure process is as described in detail above. The pattern exposure may be either exposure through a mask or scanning exposure. By this exposure, the exposed area is polymerized and cured.

[Development process]
In the present invention, after the pattern exposure as described above is completed, the unexposed area (uncured area) of the photocurable blue colored composition layer is removed to form a colored pixel (colored pattern).
Hereinafter, a process (developing process) for removing the unexposed area will be described.
In addition, when forming a colored pixel, another process can also be provided after this image development process as needed.

In the present invention, in the development step, the photocurable blue colored composition layer after exposure is developed.
The exposed area is cured in a pattern shape, and in the development process, by performing an alkali development process, the non-irradiated part (uncured part) in the above exposure process is removed by eluting into the developer and photocured. By leaving only the part, a colored pixel pattern is formed.

As the developer, an organic alkali developer, an inorganic alkali developer or a mixture thereof is used.
Examples of the alkali agent used in the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxy. And organic alkaline compounds such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, and the concentration of these alkaline compounds is 0.001 mass. An alkaline aqueous solution diluted with pure water so as to be from 10% by mass to 10% by mass, preferably from 0.01% by mass to 1% by mass, is preferably used as the developer.
In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

The development temperature is preferably 20 ° C to 35 ° C, more preferably 23 ° C to 30 ° C. The development time is preferably 30 seconds to 120 seconds, and more preferably 40 seconds to 90 seconds. Among these, a preferable combination of the development temperature and the development time is, for example, 50 seconds to 100 seconds at a temperature of 25 ° C. and 40 seconds to 80 seconds at a temperature of 30 ° C.
The shower pressure is preferably 0.01 MPa to 0.5 MPa, preferably 0.05 MPa to 0.3 MPa, and preferably 0.1 MPa to 0.3 MPa.
By selecting these conditions, it is possible to arbitrarily design the shape of the colored pixel pattern to be rectangular or forward tapered.

[Post-baking process]
In the post-baking step, the developed photocurable blue colored composition layer is baked in order to complete the curing of the photocurable blue colored composition layer. The baking method is to apply a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, etc., to a substrate having a photocurable blue colored composition layer (patterned) after development and rinsing. It can be performed by heating continuously or batchwise.
As conditions for baking, the temperature is preferably 150 ° C to 260 ° C, more preferably 180 ° C to 260 ° C, and most preferably 200 ° C to 240 ° C. The baking time is preferably 10 minutes to 150 minutes, more preferably 20 minutes to 120 minutes, and most preferably 30 minutes to 90 minutes.

<Color filter>
In this way, a blue coloring pattern (blue coloring pixel) is formed on an arbitrary substrate.
The color filter of the present invention has a blue coloring pattern formed on a substrate using at least the photocurable blue coloring composition of the present invention, and is produced by the method for producing the color filter of the present invention. Manufactured with good quality.

In the color filter manufacturing method, only the formation of the blue colored pixel (B), which is a feature of the present invention, has been described. Instead of the photocurable blue colored composition of the present invention, a red pigment and a green pigment are used. By using the photocurable coloring composition which each contains, a red pixel (R) and a green pixel (G) are formed by the same process.
Therefore, when forming a colored pattern of a plurality of hues, such as colored pixels of RGB3 hue, a light-shielding layer, application of a photocurable coloring composition having each hue onto the substrate, pre-baking, exposure, development performed as desired, In addition, a method of repeating the cycle of post-baking for the desired number of hues may be used, and after applying the photocurable coloring composition for each hue, pre-baking, exposing, and developing, finally the total hue content You may post-bake collectively.
As a result, a color filter including colored pixels having a desired hue is produced.

<Liquid crystal display device>
The color filter having a colored pattern made of the composition of the present invention is particularly excellent in the hue of a blue pixel, the pixel shape is good, and the shape of the contact hole is good, so that it is a color filter for a liquid crystal display device. Is preferred.
A liquid crystal display device including such a color filter can display a high-quality image.
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 Books 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 for 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.)”. Furthermore, the present invention is applied to 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. it can.
In addition, the color filter of the present invention is particularly suitable for use in a bright and high-definition COA (Color-filter On Array) system. In the case of a COA type liquid crystal display device, the required characteristics for the color filter layer must be the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the resistance to the peeling 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. As a result, the curability of the colored pixel is improved, and a pixel free from chipping, peeling, or twisting can be formed. Therefore, the resistance to the peeling liquid of the colored layer provided directly or indirectly on the TFT substrate is improved. Useful for liquid crystal display devices. In order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.

Further, the colored layer formed by the COA method has a rectangular shape with a side length of about 1 to 40 μm in order to connect the ITO electrode arranged on the colored layer and the terminal of the driving substrate below the colored layer. Alternatively, it is necessary to form a contact hole (conduction path) having a pixel cross-sectional shape that is rectangular to tapered, such as a circle or an ellipse having a diameter of 1 to 40 μmφ, or a U-shape. That is, the length of one side is preferably 5 μm or less, but it is possible to form a conduction path of 5 μm or less by using the present invention. When the shape of the pixel cross section of the contact hole is not rectangular to taper, or when the opening is insufficient, the transparent conductive film is disconnected or defective in conduction, and such a color filter is used for an image display device. In some cases, it may cause display defects, but the use of the colored composition of the present invention also has the advantage that the occurrence of problems due to deterioration and collapse of the contact hole is suppressed.
These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-Technology and latest trends in the market (issued by Toray Research Center Research Division 2001)".

The liquid crystal display device of the present invention includes 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 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 issue, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi), etc. Are listed.

  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 conventionally known three-wavelength tube of a cold cathode tube, but further, red, green and blue LED light sources (RGB-LED). By using as a backlight, a liquid crystal display device having high luminance and high color purity and good color reproducibility can be provided.

  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, “%” means “mass%”.

[Example 1]
-Synthesis of polymer compounds having a heterocyclic ring in the side chain-
(Synthesis of polymer 1)
M-6 (the following structure) 27.0 g, methyl methacrylate 126.0 g, methacrylic acid 27.0 g, and 1-methoxy-2-propanol 420.0 g were introduced into a nitrogen-substituted three-necked flask, and a stirrer (Shinto) The mixture was stirred with a scientific (three-motor) and heated to 90 ° C. while flowing nitrogen into the flask. To this was added 1.80 g of 2,2-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 90 ° C. for 2 hours. After 2 hours, 1.80 g of V-65 was further added, and after heating and stirring for 3 hours, a 30% by mass solution of polymer 2 was obtained. It was 21,000 as a result of measuring the weight average molecular weight of the obtained polymer 1 by the gel permeation chromatography method (GPC) which used polystyrene as the standard substance. Moreover, the acid value per solid content was 99 mgKOH / g from the titration using sodium hydroxide.

(Preparation of coated pigment 1)
50 g of pigment (CI Pigment Blue 15: 6), 500 g of sodium chloride, 20 g of the above polymer 1 solution, and 100 g of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 9 hours. Next, this mixture was poured into about 3 liters of water, stirred for about 1 hour with a high speed mixer, filtered, washed with water to remove sodium chloride and solvent, and dried to prepare coated pigment 1.

(Preparation of coated pigment 2)
The coated pigment 2 was prepared in the same manner except that the pigment (CI Pigment Blue 15: 6) used in the adjustment of the coated pigment 1 was changed to a pigment (CI Pigment Violet 23).

-Photocurable blue coloring composition layer forming step-
(Preparation of pigment dispersion composition 1)
Pigment dispersion composition 1 was prepared as follows.
That is, with the composition described below, using a homogenizer, the rotational speed was 3,000 r. p. m. The mixture was stirred for 3 hours to prepare a mixed solution, and further subjected to a dispersion treatment for 8 hours with a bead disperser Ultra Apex Mill (manufactured by Kotobuki Kogyo Co., Ltd.) using 0.1 mmφ zirconia beads.

・ Coated pigment 1 16.5%
・ Disperbyk161 Big Chemie [30% by mass solution] 8%
・ Alkali-soluble resin: benzyl methacrylate / methacrylic acid =
75/25 [mass ratio] copolymer 2%
(Weight-average molecular weight Mw: 5000 PGMEA solution (solid content 50% by mass))
・ Propylene glycol methyl ether acetate (PGMEA) 73.5%

(Preparation of pigment dispersion composition 2)
・ Coating pigment 1 11.55%
・ Coated pigment 2 4.95%
・ Disperbyk161 Big Chemie [30% by mass solution] 8%
Alkali-soluble resin: benzyl methacrylate / methacrylic acid = 75/25 [mass ratio] copolymer 2%
(Weight-average molecular weight Mw: 5000 PGMEA solution (solid content 50% by mass))
・ Propylene glycol methyl ether acetate (PGMEA) 73.5%

(Preparation of a photocurable blue coloring composition)
Components of the following composition were further added to the obtained pigment dispersion compositions 1 and 2, and stirred and mixed to prepare a photocurable blue coloring composition B-1 for blue (B).
・ Surfactant (F-554 Dainippon Ink & Co. 0.2wt% PGMEA solution) 10.0%
・ Silane coupling agent (the following structure) 0.40%
-Polymerization initiator (structure below) 1.37%
Dipentaerythritol hexaacrylate (DPHA) 4.97%
Resin (allyl methacrylate / methacrylic acid = 80/20 mol% copolymer)
Molecular weight 30000 20 wt% PGMEA solution) 32.08%
Silica fine particle dispersion (MIBK-ST, manufactured by Nissan Chemical Industries, Ltd .: solid content concentration 30% by mass) 3.33%
-Pigment dispersion composition 1 18.16%
-Pigment dispersion composition 2 11.18%
Propylene glycol methyl ether acetate (PGMEA) 18.5%

(Photocurable blue colored composition layer formation)
The obtained photocurable blue coloring composition B-1 for blue was applied to a glass substrate.
Specifically, the gap between the slit and the glass substrate and the discharge amount are adjusted so that the layer thickness of the photocurable blue colored composition layer after post-baking is 3.2 μm, and the coating speed is 120 mm / second. Applied.

-Pre-bake process, exposure process-
Next, after performing heating (pre-baking treatment) at 100 ° C. for 120 seconds using a hot plate, with an exposure apparatus using an Nd: YAG laser (Pulseo, third harmonic 355 nm, manufactured by Spectra-Physics), The optical system was adjusted so that the irradiation energy was about 1.0 mJ / cm ² with respect to the surface of the photocurable blue coloring composition layer, and exposure was performed through a photomask. Pattern exposure was performed by performing 20 times of multiple exposure with respect to the photocurable blue coloring composition layer surface.

-Development process, post-bake process-
Thereafter, using a developing device (manufactured by Hitachi High-Technologies Corporation), 1 part by mass of 1.0% developer (CDK-1) of potassium hydroxide developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.) The solution was diluted with 99 parts by mass of pure water, 25 ° C.), the shower pressure was set to 0.2 MPa, developed for 45 seconds, and washed with pure water.
Next, a post-baking process was performed for 30 minutes in a 220 ° C. clean oven to form a substrate having heat-treated blue pixels.

-Evaluation-
<Contact hole opening diameter, contact hole remaining rate after post-baking>
Using a mask having a perfect circular pattern for forming a 25 μmφ contact hole (hereinafter sometimes referred to as “CH”) in the pixel portion, a blue pixel for a color filter is formed in the above process with an exposure GAP = 200 μm, The CH opening diameter after the post-baking process was measured. Moreover, the CH residual ratio was calculated using the following equation based on the CH opening diameter before post-baking and the CH opening diameter after the post-baking step.

CH residual ratio (%) =
[CH opening diameter (after post-baking) / CH opening diameter (before post-baking)] × 100

<Contrast>
A polarizing plate is placed on the colored resin film of the colored filter substrate, the colored resin film is sandwiched, and the luminance when the polarizing plate is parallel and the luminance when orthogonal are measured using a BM-5 manufactured by Topcon Corporation. A value obtained by dividing the luminance of the above by the luminance at the time of orthogonality (= the luminance at the time of parallel / the luminance at the time of orthogonality) was used as an index for evaluating the contrast. Larger values indicate higher contrast.

<Luminance>
The luminance of the blue pixel formed in the above process was measured using an Olympus microspectrophotometer OSP-SP2000, and the Y value when y = 0.082 was defined as the luminance.

<Haze>
The blue pixel formed in the above process was visually observed and evaluated for the presence or absence of haze. ◯: No haze at all. Δ: Slight haze was observed, but in a practically acceptable range. It is done.

[Examples 2 to 5]
A substrate having a blue pixel was formed in the same manner as in Example 1 except that the photocurable blue coloring composition was prepared by changing the content of each component to the amounts described in Table 1 below. Similarly, the evaluation of CH opening diameter, CH residual ratio, contrast, luminance, and haze was performed. The results are also shown in Table 1 below.

[Comparative Example 1]
A substrate having a blue pixel was formed in the same manner as in Example 1 except that the photocurable blue coloring composition was prepared by changing the content of each component to the amounts described in Table 1 below. Similarly, the evaluation of CH opening diameter, CH residual ratio, contrast, luminance, and haze was performed. The results are also shown in Table 1.

  From the results in Table 1, the color filters of the examples (color filters having colored pixels obtained by the photocurable blue coloring composition of the present invention) have a wide CH opening diameter and a good CH residual ratio. all right. From this, it can be seen that in the colored pattern formed by the photocurable blue coloring composition of the present invention, thermal deformation due to post-baking was moderately suppressed, and collapse of contact holes due to heat treatment was suppressed. It can also be seen that the contrast of the color filter of the example is equal to or higher than that of the comparative example, and the luminance is equal to or higher. As described above, it can be seen that the ultraviolet laser-sensitive blue colored composition of the present invention is particularly excellent in the use of a color filter for forming a colored pattern, as compared with a conventional product.

Claims (12)

  (A) an organic solvent, (B) a pigment, (C) silica fine particles, (D) a photopolymerization initiator, (E) an ethylenically unsaturated compound, and (F) a resin, and (C) A photocurable blue coloring composition for ultraviolet laser exposure color filters, wherein the content of silica fine particles is 3% by mass or more and 30% by mass or less with respect to the total nonvolatile content.   The photocurable blue coloring composition for a color filter according to claim 1, wherein the (B) pigment contains a phthalocyanine pigment.   The pigment (B) is a phthalocyanine pigment, C.I. I. The photocurable blue coloring composition for color filters of Claim 1 or Claim 2 containing Pigment Violet 23.   The photocurable blue coloring composition for a color filter according to any one of claims 1 to 3, wherein the (F) resin is a resin having an unsaturated double bond in a side chain.   The photocurable blue coloring composition for a color filter according to any one of claims 1 to 4, wherein the amount of the (B) pigment added is 10% by mass or more and 25% by mass or less based on the total nonvolatile content. object.   The photocurable blue coloring for a color filter according to any one of claims 1 to 5, wherein the (C) silica fine particles are dispersed and added in advance in an organic solvent having a boiling point of 110 ° C or higher and 200 ° C or lower. Composition.   The color filter light according to any one of claims 1 to 6, wherein when a cured film having a thickness of 2 µm after drying is formed, the transmittance of the cured film at a wavelength of 355 nm is 2% or less. Curable blue coloring composition.   The photocurable blue coloring composition for color filters according to any one of claims 1 to 7, which is sensitive to an ultraviolet laser having a wavelength of 300 nm to 380 nm.   The photocurable blue coloring composition for a color filter according to any one of claims 1 to 5, which is used for a color filter of a Color-filter On Array method.   A color filter provided with the blue coloring pixel formed with the photocurable blue coloring composition for color filters of any one of Claims 1-9 on a support body.   A colored layer forming step of forming a colored layer comprising the blue colored composition by applying the photocurable blue colored composition for a color filter according to any one of claims 1 to 9 on a substrate. And a color filter comprising: an exposure step of exposing the colored layer in a pattern using an ultraviolet laser having a wavelength of 300 nm to 380 nm; and a developing step of developing the colored layer after exposure to form a colored pattern. Method.   A liquid crystal display device comprising the color filter according to claim 10.