JP5566919B2 - Colored curable composition, color filter and method for producing the same, solid-state imaging device, liquid crystal display device, and organic EL display device - Google Patents

Description

  The present invention relates to a colored curable composition, a color filter and a method for producing the same, a solid-state imaging device, a liquid crystal display device, and an organic EL display device.

In recent years, with the development of personal computers, particularly large-screen liquid crystal televisions, the demand for liquid crystal display devices (LCD), organic EL display devices, particularly color liquid crystal display devices, has been increasing. The spread of organic EL display devices is also awaited due to the demand for higher image quality. On the other hand, with the widespread use of digital cameras and camera-equipped mobile phones, the demand for solid-state imaging devices such as CCD image sensors has greatly increased.
Color filters are used as key devices for these display devices and solid-state imaging devices, and the demand for cost reduction is increasing along with the demand for higher image quality. Such a color filter is usually provided with a coloring pattern of three primary colors of red (R), green (G), and blue (B), and in the display device, three primary colors are imparted to light passing therethrough, Further, in the solid-state image sensor, it plays a role of splitting the light passing therethrough into the three primary colors.

  The colorant used in the color filter is commonly required to have the following characteristics. In other words, optical disturbances such as having favorable spectral characteristics in terms of color reproducibility, light scattering that causes a decrease in contrast in a display device, and unevenness in optical density that causes color unevenness and roughness in a solid-state imaging device. There is no need for it, fastness under the environmental conditions to be used, for example, heat resistance, light resistance, moisture resistance, etc., a large molar extinction coefficient and a thin color filter layer are required. Has been.

  As one of the methods for producing the color filter, a pigment dispersion method is employed. A method for producing a color filter by a photolithographic method or an ink jet method using a colored curable composition in which a pigment is dispersed in various curable compositions by a pigment dispersion method is effective against light and heat because the pigment is used. And stable.

  In this photolithography method, a colored curable composition is applied onto a substrate by a spin coater, a roll coater, or the like, dried to form a coating film, and the coating film is subjected to pattern exposure and development, whereby colored pixels are formed. obtain. By repeating this operation for the hue, a color filter can be produced. The photolithographic method is widely used as a method suitable for producing a color filter having a large screen and high definition because it forms a pattern with light and has excellent positional accuracy. In particular, this is a very advantageous method for producing a solid-state imaging device that requires higher resolution in recent years.

In recent years, there has been a demand for higher definition of color filters for solid-state imaging devices.
However, with the conventional pigment dispersion method, it is difficult to further improve the resolution from the viewpoint of color unevenness due to coarse pigment particles. Therefore, in applications where a fine pattern is required, such as a solid-state imaging device, it is becoming difficult to apply a photolithography method using a pigment dispersion method in the future. On the other hand, in a liquid crystal display device and an organic EL display device, a color filter manufactured by a photolithography method using a pigment dispersion method is excellent in light resistance and heat resistance, but the contrast is reduced due to light scattering by pigment particles. And has the problem of increased haze.

  By using dyes instead of the pigment dispersion method, the color filters for solid-state image sensors can solve the problem of uneven color and roughness, and high resolution can be achieved, while the color filters for liquid crystal display devices and organic EL display devices can achieve contrast and Improvements in optical properties such as haze are expected.

  Based on the above background, the use of dyes as colorants has been studied (for example, see Patent Document 1). However, the dye-containing curable composition has the following new problems.

(1) Dyes are generally inferior in light resistance and heat resistance compared to pigments. In particular, there is a problem in that the optical characteristics change due to the high temperature at the time of film formation of ITO (indium tin oxide), which is frequently used as an electrode for FPD (flat panel display) such as a liquid crystal display (LCD).
(2) Since dyes tend to suppress radical polymerization reactions, it is difficult to design colored curable compositions in systems that use radical polymerization as a curing means.
Especially in photolithography,
(3) Since ordinary dyes have low solubility in an alkaline aqueous solution or an organic solvent (hereinafter also simply referred to as a solvent), it is difficult to obtain a curable composition having a desired spectrum.
(4) The dye often exhibits an interaction with other components in the colored curable composition, and it is difficult to adjust the solubility (developability) of the cured part and the non-cured part.
(5) When the molar extinction coefficient (ε) of the dye is low, a large amount of dye must be added. For that purpose, a polymerizable compound (monomer), a binder, a photopolymerization initiator, etc. in the colored curable composition Other components must be reduced, and the curability of the composition, the heat resistance after curing, the developability of the (non-) cured portion, and the like are reduced.

Due to these problems of dyes, it has been difficult to form a colored pattern of a color filter with high definition, thin film and excellent fastness by using dyes.
In addition, since a color filter for a solid-state imaging device requires a thin film (for example, 1 μm or less), it is necessary to add a large amount of dye to the curable composition in order to obtain a desired absorption. , To further exacerbate the aforementioned problems.

In relation to such problems, various methods have been proposed in the past, such as selecting the type of initiator or increasing the amount of initiator added (for example, see Patent Document 2).
In addition, there is a method for producing a color filter that performs polymerization in a state where the exposure temperature is increased by irradiating the colored pattern with light while heating the substrate after forming the colored pattern, thereby increasing the polymerization rate of the colored curable composition. It is disclosed (for example, see Patent Document 3).
Furthermore, a method for producing a color filter is disclosed in which light irradiation is performed between the development process and the heat treatment to prevent shape deformation of the color filter (see, for example, Patent Document 4).

Further, focusing on spectral characteristics suitable for color filters, colored curable compositions and pigment compounds using dipyrromethene dyes have been studied (see, for example, Patent Documents 5 and 6).
However, when the dipyrromethene dye is used, the problem of uneven color and roughness, and the problem of contrast are solved, but there is still room for improvement in developability, and further technical development has been awaited.

JP-A-6-75375 Japanese Patent Laying-Open No. 2005-316012 Japanese Patent No. 3309514 JP 2006-258916 A JP 2008-292970 A JP 2010-18788 A

In the colored curable composition for a color filter containing a dye, there are essential problems specific to the following dyes (6) to (8) in addition to the problems described above.
(6) Dye soaking at the time of applying the next color Dye soaking means that when a colored pattern is formed by using a colored curable composition containing a dye, the pattern (or layer) of the other color previously formed is When the colored curable composition of color is applied, the dye contained in the colored curable composition penetrates, and color mixing occurs in the colored pixels.
(7) Elution of dye during alkali development In a colored curable composition using a dye, a large amount of dye needs to be added, and as a result, the relative content of components contributing to photolithographic properties is reduced. For this reason, a pattern is likely to be peeled off in a low exposure area due to a decrease in sensitivity, or a pattern formation failure such as a desired shape and color density not being obtained due to elution of a dye during alkali development or the like is likely to occur.
(8) Thermal diffusion (color transfer) by heat treatment
In a colored curable composition using a dye, when heat treatment is performed after film formation, color transfer tends to occur between adjacent pixels or between layers in a stacked state. Color migration causes color mixing.
In addition to the above problem, there is the following problem (9).
(9) Development residue after development (development residue on the substrate and other colors)
The development residue includes a development residue remaining on the substrate and a development residue remaining in the previously formed other color pattern (or layer), both of which cause color mixing.
Among the above (6) to (9), (6), (8), and (9) are particularly causes of color mixing, and are factors that greatly hinder the sensitivity improvement in the recent increase in the number of pixels of the solid-state imaging device.

  Patent Document 8 discloses a spectral characteristic derived from the light absorption characteristic unique to the dipyrromethene dye, but elution of the colorant during alkali development, penetration of the colorant, and thermal diffusion of the colorant by heat treatment (color transfer). No mention is made of development residues.

This invention is made | formed in view of the said condition, and makes it a subject to achieve the following objectives.
That is, an object of the present invention is to provide a colored curable composition capable of forming a colored film in which elution of the colorant during alkali development is suppressed. The present invention also provides a color filter having a colored pixel having a desired hue using the colored curable composition, a method for producing the color filter, a solid-state imaging device including the color filter, a liquid crystal display device, and an organic EL display device. The purpose is to provide.

That is, specific means for solving the above problems are as follows.
<1> (A) a phthalocyanine pigment, (B) a dye multimer containing a dipyrromethene structure, (C) a polymerization initiator, (D) a polymerizable compound, and (E) a solvent, wherein (D) the polymerizable compound is A colored curable composition which is an ethylenically unsaturated polymerizable compound containing at least one of an epoxy group and an isocyanate group.

<2> The ethylenically unsaturated polymerizable compound containing at least one of the epoxy group and the isocyanate group is glycidyl (meth) acrylate or 2- (meth) acryloylethyloxyethyl isocyanate. Colored curable composition.

<3> The dye moiety in the dye multimer containing the dipyrromethene structure is derived from a dipyrromethene metal complex compound obtained from a dipyrromethene compound represented by the following general formula (M) and a metal or a metal compound, or a tautomer thereof. The colored curable composition according to <1> or <2>, which is a structure.

[In General Formula (M), R ^{4 to} R ¹⁰ each independently represents a hydrogen atom or a monovalent substituent. However, R ⁴ and R ⁹ are not bonded to each other to form a ring. ]

<4> A colored curable composition in which the colored curable composition according to any one of <1> to <3> is used for forming a colored pixel by a photolithography method.
<5> A color filter using the colored curable composition according to any one of <1> to <4>.

<6> A colored layer forming step of forming a colored layer by applying the colored curable composition according to any one of <1> to <4> on a support, and pattern-like with respect to the colored layer A method for producing a color filter, comprising: an exposure step of forming a latent image by exposing the substrate and a developing step of developing a colored layer on which the latent image is formed to form a pattern.

<7> A solid-state imaging device comprising the color filter according to <5>.
<8> A liquid crystal display device comprising the color filter according to <5>.
<9> An organic EL display device comprising the color filter according to <5>.

In the present invention, since an ethylenically unsaturated polymerizable compound containing at least one of an epoxy group and an isocyanate group is used as the polymerizable compound (D), (B) a large amount of dye containing a dipyrromethene structure which is a colorant It is considered that the active group hydrogen, especially when the dye multimer has a carboxyl group, the carboxyl group reacts with the epoxy group or isocyanate group of the polymerizable compound, and is an alkali-soluble group of the dye multimer. It is presumed that the carboxyl group is substituted with an ethylenically unsaturated polymerizable group. As a result, the carboxyl group which is an alkali-soluble group of the dye multimer is blocked, so that the alkali solubility of the dye multimer is lowered. It is presumed that the unsaturated polymerizable group reacts to be further polymerized, so that the solubility in an alkaline solution is reduced, and the elution of the dye multimer in the exposed area is suppressed during alkali development. .
In particular, in a preferred embodiment of the present invention, in the case where glycidyl (meth) acrylate or 2- (meth) acryloylethyloxyethyl isocyanate is used as the polymerizable compound, it is a low molecular weight compound, so that it is a colored layer. In this case, the molecular movement of the polymerizable compound is large, and the effect of the present invention is considered to be further improved.

  The colored curable composition of the present invention is a blue or green colored curable composition containing (A) a phthalocyanine pigment and (B) a dye multimer containing a dipyrromethene structure as a colorant. Or it is used for green pixel formation. The blue or green colored layer absorbs i-line (365 nm) that is particularly effective as exposure light, and the exposure light does not easily penetrate to the lower part of the colored layer, so that the exposed portion is difficult to cure. For this reason, the exposed portion is easily dissolved in the alkaline developer, and the colorant and the like are easily eluted from the blue or green pixel. By using the present invention, in forming a blue or green colored pixel, elution of a colorant or the like from the blue or green pixel is suppressed during alkali development, and a blue or green pixel suitable for the target hue can be designed.

  ADVANTAGE OF THE INVENTION According to this invention, the colored curable composition which can form the colored film in which the elution of the coloring agent at the time of alkali development was suppressed can be provided. Also provided are a color filter having colored pixels of a desired hue using the colored curable composition, a method for producing the same, and a solid-state imaging device, a liquid crystal display device, and an organic EL display device provided with the color filter. Can do.

Hereinafter, the colored curable composition, the color filter and the manufacturing method thereof, the solid-state imaging device, the liquid crystal display device, and the organic EL display device of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

≪Colored curable composition≫
The colored curable composition of the present invention comprises (A) a phthalocyanine pigment, (B) a dye multimer containing a dipyrromethene structure (hereinafter referred to as “specific dye multimer” as appropriate), (C) a polymerization initiator, (D ) A polymerizable compound, and (E) a solvent, and the (D) polymerizable compound contains at least one of an epoxy group and an isocyanate group (hereinafter referred to as “specific polymerizable compound” as appropriate). It is characterized by the above.
Below, each component which comprises the colored curable composition of this invention is demonstrated.

[(A) phthalocyanine pigment]
The (A) phthalocyanine pigment used in the present invention is not particularly limited as long as it is a pigment having a phthalocyanine skeleton. Further, the central metal contained in the phthalocyanine pigment is not particularly limited as long as it is a metal that can form a phthalocyanine skeleton. Among these, magnesium, titanium, iron, cobalt, nickel, copper, zinc, and aluminum are preferably used as the central metal.

  Specific examples of the phthalocyanine pigment in the present invention include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 5, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 16, C.I. I. Pigment blue 17: 1, C.I. I. Pigment blue 75, C.I. I. Pigment blue 79, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 37, chloroaluminum phthalocyanine, hydroxyaluminum phthalocyanine, aluminum phthalocyanine oxide, and zinc phthalocyanine. Among these, from the viewpoint of light resistance and coloring power, C.I. I. Pigment blue 15, C.I. I. Pigment Blue 15: 6, Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 2 is preferable. I. Pigment Blue 15: 6 is preferable.

The (A) phthalocyanine pigment used in the present invention is preferably one having a particle size as small as possible from the viewpoint of high resolution and high transmittance. The average primary particle diameter is preferably 0.01 μm to 0.1 μm, more preferably 0.01 μm to 0.05 μm.
The phthalocyanine pigment having the above average primary particle diameter can be obtained by making the pigment particles fine by a method such as salt milling.

  Moreover, an average primary particle diameter can be measured using TEM (transmission electron microscope). That is, the TEM photograph is subjected to image analysis to examine the particle size distribution. More specifically, the pigment powder is observed with a TEM at a magnification of 3 to 100,000 times, a photograph is taken, and the major axis of 1000 primary particles is measured. Perform on points and average the results.

  The phthalocyanine pigment is preferably prepared in advance as a pigment dispersion together with a dispersant, a solvent and the like described later and used in the colored curable composition.

(Dispersant)
As the dispersant, a known pigment dispersant or surfactant is used.
As the dispersant, many kinds of compounds are used. For example, a phthalocyanine pigment derivative (commercial product EFKA-745 (manufactured by Efka)), Solsperse 5000 (manufactured by Nippon Lubrizol Co., Ltd.); organosiloxane polymer KP341 ( Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. 95 (above, manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, poly Nonionic surfactants such as oxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; W004, W005, W017 (above, manufactured by Yusho Co., Ltd.), etc. Anionic surfactants; EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), D Polymer dispersing agents such as Perth Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (Sannopco Co., Ltd.); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000 , 26000, 28000, etc. (manufactured by Nippon Lubrizol Co., Ltd.); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (above, manufactured by ADEKA Corporation), and ISONET S-20 (manufactured by Sanyo Chemical Co., Ltd.) are included. In addition, amphoteric dispersants such as Hinoact T-8000E manufactured by Kawaken Fine Chemical Co., Ltd. are also included.

  The content of the dispersant in the colored curable composition of the present invention is preferably 1% by mass to 80% by mass, more preferably 5% by mass to 70% by mass with respect to the pigment, and 10% by mass to 60% by mass. Is most preferred.

The content of the phthalocyanine pigment in the colored curable composition in the present invention is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass with respect to the total solid content of the colored curable composition. 35 mass% to 50 mass% is most preferable.
In the present invention, the total solid content of the colored curable composition indicates the total content of components excluding the solvent among the components constituting the colored curable composition.
The content ratio of the phthalocyanine pigment to the specific dye multimer is preferably phthalocyanine pigment: specific dye multimer = 100: 10 to 100: 200, more preferably 100: 20 to 100: 100, and 100: More preferably, it is 25-100: 75.

[(B) Dye multimer containing dipyrromethene structure = specific dye multimer]
The specific dye multimer in the present invention includes a dipyrromethene structure.
The dye moiety in the dye multimer containing the dipyrromethene structure is a structure derived from a dipyrromethene metal complex compound obtained from a dipyrromethene compound represented by the following general formula (M) and a metal or a metal compound, or a tautomer thereof. Preferably there is.

[In General Formula (M), R ^{4 to} R ¹⁰ each independently represents a hydrogen atom or a monovalent substituent. However, R ⁴ and R ⁹ are not bonded to each other to form a ring. ]

Specific examples of the dipyrromethene metal complex compound obtained from the dipyrromethene compound represented by the general formula (M) and a metal or a metal compound or a tautomer thereof include the following general formula (5) or the following general formula ( The dipyrromethene metal complex compound represented by 6) is mentioned.
However, the present invention is not limited to these.

(Dipyrromethene metal complex compound represented by the general formula (5))

In the general formula (5), R ^{4 to} R ⁹ each independently represents a hydrogen atom or a substituent, and R ¹⁰ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound. X ¹ represents a group capable of binding to Ma, X ² represents a group that neutralizes the charge of Ma, and X ¹ and X ² are bonded to each other to form a 5-membered, 6-membered, or 7-membered member together with Ma. The ring may be formed. However, R ⁴ and R ⁹ are not bonded to each other to form a ring. In addition, the dipyrromethene metal complex compound represented by the general formula (5) includes a tautomer.

There is no particular limitation on the site where one or two hydrogen atoms are removed from the dipyrromethene metal complex compound represented by the general formula (5) in order to form a dye residue, but in terms of synthesis compatibility, R ⁴ preferably any one or two sites to R ^9, R ^4, R 6, either one or two sites of ^{R 7} and ^{R 9} are more preferred, any one of ^{R 4} and ^{R 9} or Two sites are more preferred.

The specific dye multimer in the present invention preferably has an alkali-soluble group.
As a method for introducing an alkali-soluble group into a specific dye multimer, when a dye monomer or a structural unit having an alkali-soluble group is used, R ^{4 to} R ¹⁰ of the dipyrromethene metal complex compound represented by the general formula (5). , X ¹ , X ² , or one or more substituents may have an alkali-soluble group. Among these substituents, any of R ^{4 to} R ⁹ and X ¹ is preferable, any of R ⁴ , R ⁶ , R ⁷ and R ⁹ is more preferable, and any of R ⁴ and R ⁹ is still more preferable.

  The dipyrromethene metal complex compound represented by the general formula (5) may have a functional group other than the alkali-soluble group as long as the effects of the present invention are not impaired.

As said R < ⁴ > -R < ⁹ >, a halogen atom (for example, fluorine, chlorine, bromine), an alkyl group (preferably C1-C48, More preferably, C1-C24 linear, branched chain, Or a cyclic alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl), an alkenyl group (preferably an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms, such as vinyl, allyl, 3-buten-1-yl), an aryl group (preferably carbon An aryl group having 6 to 48, more preferably 6 to 24 carbon atoms, such as phenyl and naphthyl A heterocyclic group (preferably a heterocyclic group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2 -Benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), a silyl group (preferably a silyl group having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms, such as trimethylsilyl, triethylsilyl, Tributylsilyl, t-butyldimethylsilyl, t-hexyldimethylsilyl), hydroxy group, cyano group, nitro group, alkoxy group (preferably an alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, , Methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecylo A cycloalkyloxy group such as cyclopentyloxy or cyclohexyloxy) or an aryloxy group (preferably an aryloxy group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms such as phenoxy or 1-naphthoxy ), A heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), silyloxy A group (preferably a silyloxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy), an acyloxy group (preferably having 2 to 2 carbon atoms). 48, more preferably an acyloxy group having 2 to 24 carbon atoms, For example, acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy), an alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as ethoxycarbonyloxy, t- Butoxycarbonyloxy, cycloalkyloxycarbonyloxy (for example, cyclohexyloxycarbonyloxy)), aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, , Phenoxycarbonyloxy), a carbamoyloxy group (preferably a carbamoyloxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dimethylcarbamoyloxy, N- Tilcarbamoyloxy, N-phenylcarbamoyloxy, N-ethyl-N-phenylcarbamoyloxy), a sulfamoyloxy group (preferably having 1 to 32 carbon atoms, more preferably having 1 to 24 carbon atoms). , For example, N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy), an alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms, For example, methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexylsulfonyloxy),

An arylsulfonyloxy group (preferably an arylsulfonyloxy group having 6 to 32 carbon atoms, more preferably an arylsulfonyloxy group having 6 to 24 carbon atoms, such as phenylsulfonyloxy), an acyl group (preferably having 1 to 48 carbon atoms, more preferably carbon An acyl group having 1 to 24, for example, formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl, cyclohexanoyl), an alkoxycarbonyl group (preferably having 2 to 48 carbon atoms, more preferably an alkoxy having 2 to 24 carbon atoms) Examples of carbonyl groups include methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl, 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl), and aryloxycarbonyl groups (preferably having 7 to 32 carbon atoms). , Yo Preferably, it is an aryloxycarbonyl group having 7 to 24 carbon atoms, such as phenoxycarbonyl, and a carbamoyl group (preferably having 1 to 48 carbon atoms, more preferably a carbamoyl group having 1 to 24 carbon atoms, such as carbamoyl, N, N-diethylcarbamoyl, N-ethyl-N-octylcarbamoyl, N, N-dibutylcarbamoyl, N-propylcarbamoyl, N-phenylcarbamoyl, N-methylN-phenylcarbamoyl, N, N-dicyclohexylcarbamoyl), amino A group (preferably an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as amino, methylamino, N, N-dibutylamino, tetradecylamino, 2-ethylhexylamino, cyclohexylamino), anilino Group (preferably having 6 to 32 carbon atoms) More preferably, it is an anilino group having 6 to 24 carbon atoms, such as anilino or N-methylanilino), a heterocyclic amino group (preferably having 1 to 32 carbon atoms, more preferably a heterocyclic amino group having 1 to 18 carbon atoms, For example, 4-pyridylamino), carbonamido group (preferably a carbonamido group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, acetamido, benzamido, tetradecanamido, pivaloylamide, cyclohexaneamido), ureido group (Preferably a ureido group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as ureido, N, N-dimethylureido, N-phenylureido), an imide group (preferably having 36 or less carbon atoms, more Preferably it is an imide group having 24 or less carbon atoms, such as N-succinimide and N-phthalate. Imide), alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonyl Amino, cyclohexyloxycarbonylamino), aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as phenoxycarbonylamino), sulfonamide group (preferably Is a sulfonamide group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methanesulfonamide, butanesulfonamide, benzenesulfonamide, hexadecanesulfonamide, cyclohexane. Sulfonamides), sulfamoylamino groups (preferably sulfamoylamino groups having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dipropylsulfamoylamino, N-ethyl). -N-dodecylsulfamoylamino), an azo group (preferably an azo group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as phenylazo, 3-pyrazolylazo),

An alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably an alkylthio group having 1 to 24 carbon atoms, for example, methylthio, ethylthio, octylthio, cyclohexylthio), an arylthio group (preferably having 6 to 48 carbon atoms, more preferably An arylthio group having 6 to 24 carbon atoms, such as phenylthio, and a heterocyclic thio group (preferably having 1 to 32 carbon atoms, more preferably a heterocyclic thio group having 1 to 18 carbon atoms, such as 2-benzothiazoli Ruthio, 2-pyridylthio, 1-phenyltetrazolylthio), an alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, more preferably an alkylsulfinyl group having 1 to 24 carbon atoms, such as dodecanesulfinyl group), an arylsulfinyl group ( Preferably it has 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms. An arylsulfonyl group (for example, phenylsulfinyl), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, Isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecylsulfonyl, octylsulfonyl, cyclohexylsulfonyl), an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, such as phenylsulfonyl, 1-naphthylsulfonyl), a sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as sulfamoyl, N, N-dipropylsulfa , N-ethyl-N-dodecylsulfamoyl, N-ethyl-N-phenylsulfamoyl, N-cyclohexylsulfamoyl), sulfo group, phosphonyl group (preferably having 1 to 32 carbon atoms, more preferably carbon A phosphonyl group having 1 to 24 carbon atoms, for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), phosphinoylamino group (preferably having 1 to 32 carbon atoms, more preferably phosphino having 1 to 24 carbon atoms) Ilylamino group includes, for example, diethoxyphosphinoylamino, dioctyloxyphosphinoylamino).

Among the above, R ⁴ and R ⁹ are preferably an alkylamino group, an arylamino group, a carbonamido group, a ureido group, an imide group, an alkoxycarbonylamino group, and a sulfonamido group, and a carbonamido group, a ureido group, an alkoxy group. A carbonylamino group and a sulfonamide group are more preferable, a carbonamide group, a ureido group, an alkoxycarbonylamino group, and a sulfonamide group are further preferable, and a carbonamide group and a ureido group are particularly preferable.
Among the above, R ⁵ and R ⁸ are preferably an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitrile group, an imide group, and a carbamoylsulfonyl group, and an alkoxycarbonyl group, aryl Oxycarbonyl group, carbamoyl group, alkylsulfonyl group, nitrile group, imide group, carbamoylsulfonyl group are more preferable, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, nitrile group, imide group, carbamoylsulfonyl group are more preferable, alkoxy A carbonyl group, an aryloxycarbonyl group, and a carbamoyl group are particularly preferable.
Among the above, R ⁶ and R ⁷ are preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and more preferably a substituted or unsubstituted alkyl group. , A substituted or unsubstituted aryl group.

When R ⁶ and R ⁷ represent an alkyl group, the alkyl group is preferably a linear, branched, or cyclic substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, more specifically. For example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, i-butyl group, t-butyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and benzyl Group, more preferably a branched chain having 1 to 12 carbon atoms, or a cyclic substituted or unsubstituted alkyl group, and more specifically, for example, isopropyl group, cyclopropyl group, i-butyl group, A t-butyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group are mentioned, More preferably, it is a C1-C12 secondary or tertiary substituted or unsubstituted alkyl group. More specifically, examples include isopropyl group, cyclopropyl group, i-butyl group, t-butyl group, cyclobutyl group, and cyclohexyl group.

When R ⁶ and R ⁷ represent an aryl group, the aryl group preferably includes a substituted or unsubstituted phenyl group and a substituted or unsubstituted naphthyl group, and more preferably a substituted or unsubstituted phenyl group. It is a group.
When R ⁶ and R ⁷ represent a heterocyclic group, the heterocyclic group is preferably a substituted or unsubstituted 2-thienyl group, a substituted or unsubstituted 4-pyridyl group, a substituted or unsubstituted 3 -Pyridyl group, substituted or unsubstituted 2-pyridyl group, substituted or unsubstituted 2-furyl group, substituted or unsubstituted 2-pyrimidinyl group, substituted or unsubstituted 2-benzothiazolyl group, substituted or unsubstituted 1 -Imidazolyl group, substituted or unsubstituted 1-pyrazolyl group, substituted or unsubstituted benzotriazol-1-yl group, more preferably substituted or unsubstituted 2-thienyl group, substituted or unsubstituted 4- Examples include a pyridyl group, a substituted or unsubstituted 2-furyl group, a substituted or unsubstituted 2-pyrimidinyl group, and a substituted or unsubstituted 1-pyridyl group.

In the general formula (5), Ma represents a metal atom or a metal compound. The metal atom or metal compound may be any metal atom or metal compound capable of forming a complex, and may be any divalent metal atom, divalent metal oxide, divalent metal hydroxide, or Divalent metal chlorides are included.
For example, Zn, Mg, Si, Sn , Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe , etc., and _{AlCl, InCl, FeCl, TiCl 2} , SnCl 2, SiCl 2, GeCl 2 , etc. Metal chlorides, metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂ are included.

  Among these, from the viewpoints of the stability, spectral characteristics, heat resistance, light resistance, and production suitability of the complex, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, and VO are preferred, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, and VO are more preferred, Zn, Cu, Co, and VO are particularly preferred, and Zn is most preferred.

In the general formula (5), R ¹⁰ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, preferably a hydrogen atom.

In the general formula (5), X ¹ may be any group as long as it is a group capable of binding to Ma. Specifically, water, alcohols (for example, methanol, ethanol, propanol), etc. The compounds described in “Metal Chelate” ([1] Takeichi Sakaguchi / Keihei Ueno (1995 Nanedo), [2] (1996), [3] (1997), etc.) can be mentioned. Among these, from the viewpoint of production, water, carboxylic acid compounds and alcohols are preferable, and water and carboxylic acid compounds are more preferable.

In the general formula (5), examples of the “group that neutralizes the charge of Ma” represented by X ² include a halogen atom, a hydroxyl group, a carboxylic acid group, a phosphoric acid group, and a sulfonic acid group. From the viewpoint of production, a halogen atom, a hydroxyl group, a carboxylic acid group, and a sulfonic acid group are preferable, and a hydroxyl group and a carboxylic acid group are more preferable.

In the general formula (5), X ¹ and X ² may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring together with Ma. The 5-membered, 6-membered and 7-membered rings formed may be saturated or unsaturated. The 5-membered, 6-membered, and 7-membered rings may be composed of only carbon atoms, and form a heterocycle having at least one atom selected from a nitrogen atom, an oxygen atom, and / or a sulfur atom. You may do it.

As a preferred embodiment of the compound represented by the general formula (5), R ^{4 to} R ⁹ are each independently a preferred embodiment described in the description of R ^{4 to} R ⁹ , and R ¹⁰ is a description of R ¹⁰ . In the preferred embodiment described, Ma is Zn, Cu, Co, or VO, X ¹ is water or a carboxylic acid compound, X ² is a hydroxyl group or a carboxylic acid group, and X ¹ and X ² May be bonded to each other to form a 5-membered or 6-membered ring.

(Dipyrromethene metal complex compound represented by the general formula (6))

In the general formula (6), R ¹¹ and R ¹⁶ are each independently an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. Represents a group. R ^{12 to} R ¹⁵ each independently represents a hydrogen atom or a substituent. R ¹⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound. X ² and X ³ are NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), a nitrogen atom, an oxygen atom, or Represents a sulfur atom. Y ¹ and Y ² represent NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), a nitrogen atom, or a carbon atom. Represent. R ¹¹ and Y ¹ may be bonded to each other to form a 5-, 6-, or 7-membered ring, and R ¹⁶ and Y ² are bonded to each other to form a 5-, 6-, or 7-membered ring. The ring may be formed. X ¹ represents a group capable of binding to Ma, and a represents 0, 1, or 2. In addition, the dipyrromethene metal complex compound represented by the general formula (6) includes a tautomer.

Although there is no particular limitation as a site where one or two hydrogen atoms are removed from the dipyrromethene metal complex compound represented by the general formula (6) in order to form a dye residue, R ^{11 to} R ¹⁷ , X ¹ , It is any one or two sites of Y ^{1 to} Y ² .
Among these, from the point of synthetic compatibility, any one or two sites of R ^{11 to} R ¹⁶ and X ¹ are preferable, and more preferably any one of R ¹¹ , R ¹³ , R ¹⁴ and R ^16. One or two sites, and more preferably one or two sites out of R ¹¹ and R ¹⁶ .

As a method for introducing an alkali-soluble group into the specific dye multimer in the present invention, when a dye monomer or a structural unit having an alkali-soluble group is used, R ¹¹ of the dipyrromethene metal complex compound represented by the general formula (6) is used. Any one or two or more substituents of ˜R ¹⁷ , X ¹ , Y ¹ ˜Y ² can have an alkali-soluble group. Among these ^{substituents,} one of R 11 ^{～～R 16} and ^{X 1} are ^preferred, more preferably one of R ^11, R ^{13, R 14} and ^{R 16,} any one of ^{R 11} and ^{R 16} are more preferably .

  The dipyrromethene metal complex compound represented by the general formula (6) may have a functional group other than the alkali-soluble group as long as the effects of the present invention are not impaired.

Said R < ¹² > -R < ¹⁵ > is synonymous with R < ⁵ > -R < ⁸ > in the said General formula (5), and its preferable aspect is also the same. R ¹⁷ has the same meaning as R ¹⁰ in the general formula (5), and the preferred embodiment is also the same. Said Ma is synonymous with Ma in the said General formula (5), and its preferable range is also the same.

More specifically, in the general formula (6), among R ^{12 to} R ¹⁵ , the R ¹² and R ¹⁵ include an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, Nitrile group, imide group or carbamoylsulfonyl group is preferable, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, nitrile group, imide group and carbamoylsulfonyl group are more preferable, alkoxycarbonyl group, aryloxycarbonyl Group, carbamoyl group, nitrile group, imide group and carbamoylsulfonyl group are more preferred, and alkoxycarbonyl group, aryloxycarbonyl group and carbamoyl group are particularly preferred.
R ¹³ and R ¹⁴ are preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, more preferably a substituted or unsubstituted alkyl group, substituted or unsubstituted. A substituted aryl group. Here, specific examples of more preferable alkyl groups, aryl groups, and heterocyclic groups can be the same as specific examples listed in R ⁶ and R ⁷ of the general formula (5).

In the general formula (6), R ¹¹ and R ¹⁶ are alkyl groups (preferably a linear, branched, or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms. Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl), alkenyl group (preferably having 2 to 24 carbon atoms, more preferably An alkenyl group having 2 to 12 carbon atoms, for example, vinyl, allyl, 3-buten-1-yl), an aryl group (preferably an aryl group having 6 to 36 carbon atoms, more preferably 6 to 18 carbon atoms, , Phenyl, naphthyl), a heterocyclic group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, For example, 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 2-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), an alkoxy group (preferably having 1 carbon atom) To 36, more preferably an alkoxy group having 1 to 18 carbon atoms, such as methoxy, ethoxy, propyloxy, butoxy, hexyloxy, 2-ethylhexyloxy, dodecyloxy, cyclohexyloxy), an aryloxy group (preferably having a carbon number) An aryloxy group having 6 to 24, more preferably 1 to 18 carbon atoms, such as phenoxy or naphthyloxy, an alkylamino group (preferably having 1 to 36 carbon atoms, more preferably an alkylamino group having 1 to 18 carbon atoms) For example, methylamino, ethylamino, propylamino, Tylamino, hexylamino, 2-ethylhexylamino, isopropylamino, t-butylamino, t-octylamino, cyclohexylamino, N, N-diethylamino, N, N-dipropylamino, N, N-dibutylamino, N-methyl -N-ethylamino), an arylamino group (preferably an arylamino group having 6 to 36 carbon atoms, more preferably 6 to 18 carbon atoms, such as phenylamino, naphthylamino, N, N-diphenylamino, N- Ethyl-N-phenylamino) or a heterocyclic amino group (preferably a heterocyclic amino group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms such as 2-aminopyrrole, 3-aminopyrazole, 2 -Aminopyridine, 3-aminopyridine).

Among the above, R ¹¹ and R ¹⁶ are preferably an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylamino group, an arylamino group, and a heterocyclic amino group, and an alkyl group, an alkenyl group, an aryl group, Heterocyclic groups are more preferred, alkyl groups, alkenyl groups, and aryl groups are more preferred, and alkyl groups are particularly preferred.

In the general formula (6), an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group represented by R ¹¹ and R ¹⁶ When it is a substitutable group, it may be substituted with the substituent explained in the substituent of R ^{1 in} the general formula (1) described later, and when it is substituted with two or more substituents These substituents may be the same or different.

In the general formula (6), X ² and X ³ represent NR, a nitrogen atom, an oxygen atom, or a sulfur atom. Here, R is a hydrogen atom, an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, such as methyl, ethyl, propyl, Isopropyl, butyl, isobutyl, t-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl), alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms) An alkenyl group, for example, vinyl, allyl, 3-buten-1-yl), an aryl group (preferably an aryl group having 6 to 36 carbon atoms, more preferably an aryl group having 6 to 18 carbon atoms, for example, phenyl, naphthyl), A heterocyclic group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, such as 2-thienyl; 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), acyl group (preferably having 1 to 24 carbon atoms, more preferably An acyl group having 2 to 18 carbon atoms, for example, acetyl, pivaloyl, 2-ethylhexyl, benzoyl, cyclohexanoyl), an alkylsulfonyl group (preferably having 1 to 24 carbon atoms, more preferably an alkylsulfonyl having 1 to 18 carbon atoms) A group such as methylsulfonyl, ethylsulfonyl, isopropylsulfonyl, cyclohexylsulfonyl), an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms, such as phenylsulfonyl, naphthyl) Sulfonyl).

The alkyl group, alkenyl group, aryl group, heterocyclic group, acyl group, alkylsulfonyl group, and arylsulfonyl group of R are substituted with the substituent explained in the substituent of R ^{1 in} the general formula (1) described later. In the case where it is substituted with a plurality of substituents, these substituents may be the same or different.

In General Formula (6), Y ¹ and Y ² represent NR, a nitrogen atom, or a carbon atom, R has the same meaning as R in X ² and X ³ , and the preferred embodiment is also the same.

In the general formula (6), R ¹¹ and Y ¹ are bonded to each other to form a 5-membered ring with a carbon atom (for example, cyclopentane, pyrrolidine, tetrahydrofuran, dioxolane, tetrahydrothiophene, pyrrole, furan, thiophene, indole, benzofuran, Benzothiophene), 6-membered ring (eg, cyclohexane, piperidine, piperazine, morpholine, tetrahydropyran, dioxane, pentamethylene sulfide, dithiane, benzene, piperidine, piperazine, pyridazine, quinoline, quinazoline), or 7-membered ring (eg, cyclo Heptane, hexamethyleneimine).

In the general formula (6), R ¹⁶ and Y ² are bonded to each other to form a 5-membered ring with a carbon atom (for example, cyclopentane, pyrrolidine, tetrahydrofuran, dioxolane, tetrahydrothiophene, pyrrole, furan, thiophene, indole, benzofuran, Benzothiophene), 6-membered ring (eg, cyclohexane, piperidine, piperazine, morpholine, tetrahydropyran, dioxane, pentamethylene sulfide, dithiane, benzene, piperidine, piperazine, pyridazine, quinoline, quinazoline), or 7-membered ring (eg, cyclo Heptane, hexamethyleneimine).

In the general formula (6), when the 5-membered, 6-membered, and 7-membered rings formed by combining R ¹¹ and Y ¹ and R ¹⁶ and Y ² are substitutable rings, It may be substituted with the substituent described in the substituent of R ^{1 in} the general formula (1) described later, and when it is substituted with two or more substituents, the substituents are the same. May be different.

In the general formula (6), X ¹ represents a group capable of binding to Ma, and specific examples thereof include the same group as X ¹ in the general formula (5), and preferred embodiments are also the same. a represents 0, 1, or 2.

As a preferable aspect of the compound represented by the general formula (6), R ^{12 to} R ¹⁵ are each preferably a preferable aspect described in the description of R ^{5 to} R ^{8 in} the general formula (5). R ¹⁷ is a preferred embodiment described in the description of R ^{10 in} the general formula (5), Ma is Zn, Cu, Co, or VO, X ² is NR (R is a hydrogen atom, an alkyl group), A nitrogen atom or an oxygen atom, X ³ is NR (R is a hydrogen atom, an alkyl group), or an oxygen atom; Y ¹ is NR (R is a hydrogen atom, an alkyl group), a nitrogen atom, or a carbon atom; Y ² represents a nitrogen atom or a carbon atom, R ¹¹ and R ¹⁶ each independently represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group, and X ¹ represents an oxygen atom. A is 0 or 1 A. R ¹¹ and Y ¹ may be bonded to each other to form a 5- or 6-membered ring, or R ¹⁶ and Y ² may be bonded to each other to form a 5- or 6-membered ring.

As a more preferable embodiment of the compound represented by the general formula (6), R ^{12 to} R ¹⁵ are each preferably independently described in the description of R ^{5 to} R ⁸ in the compound represented by the general formula (5). R ¹⁷ is a preferred embodiment described in the description of R ^{10 in} the general formula (5), Ma is Zn, X ² and X ³ are oxygen atoms, and Y ¹ is NH. Y ² is a nitrogen atom, R ¹¹ and R ¹⁶ are each independently an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group, and X ¹ is bonded through an oxygen atom. And a is 0 or 1. R ¹¹ and Y ¹ may be bonded to each other to form a 5- or 6-membered ring, or R ¹⁶ and Y ² may be bonded to each other to form a 5- or 6-membered ring.

The molar extinction coefficient of the dipyrromethene metal complex compound represented by the general formulas (5) and (6) is preferably as high as possible from the viewpoint of film thickness. The maximum absorption wavelength λmax is preferably 520 nm to 580 nm, more preferably 530 nm to 570 nm, from the viewpoint of improving color purity. The maximum absorption wavelength and molar extinction coefficient are measured with a spectrophotometer UV-2400PC (manufactured by Shimadzu Corporation).
The melting point of the dipyrromethene metal complex compound represented by the general formula (5) and the general formula (6) is preferably not too high from the viewpoint of solubility.

  The dipyrromethene metal complex compounds represented by the general formula (5) and the general formula (6) are disclosed in U.S. Pat. Nos. 4,774,339, 5,433,896, and JP-A-2001-240761. 2002-155052 gazette, Japanese Patent No. 3614586 gazette, Aust. J. et al. Chem, 1965, 11, 1835-1845, J. Am. H. Boger et al, Heteroatom Chemistry, Vol. 1, No. 1 5,389 (1990) and the like. Specifically, the method described in paragraphs 0131 to 0157 of JP-A-2008-292970 can be applied.

The specific dye multimer in the present invention is a dye multimer containing a dipyrromethene structure, and the dye part in the dye multimer containing a dipyrromethene structure is composed of a dipyrromethene compound represented by the general formula (M) and a metal or a metal compound. A structure derived from the obtained dipyrromethene metal complex compound or a tautomer thereof is preferable.
Furthermore, as the dipyrromethene metal complex compound obtained from the dipyrromethene compound represented by the general formula (M) and a metal or a metal compound or a tautomer thereof, the general formula (5) or the general formula (6) may be used. The dipyrromethene metal complex compound represented is preferred.
Next, the dye multimer will be described.

The specific dye multimer in the present invention is a dye multimer containing a dipyrromethene structure, and preferably has a weight average molecular weight (Mw) of 5,000 or more and 20,000 or less, more preferably 5,000 or more and 16, 000 or less, more preferably 6,000 or more and 12,000 or less.
When the weight average molecular weight (Mw) is less than 5,000, when a colored film is formed, the thermal diffusion (color transfer) of the colorant by heat treatment, the soaking of the colorant, the alkali elution resistance, and the solvent resistance deteriorate. Tend. When the weight average molecular weight exceeds 20,000, the development residue tends to deteriorate.

Further, the dispersity (Mw / Mn) is preferably 1.00 or more and 2.50 or less.
When the dispersity (Mw / Mn) exceeds 2.50, when a colored film is formed, the thermal diffusion (color transfer) of the colorant by heat treatment, the soaking of the colorant, the alkali elution resistance, and the solvent resistance deteriorate. Tend. The dispersity (Mw / Mn) needs to be 1.00 or more and 2.50 or less, preferably 1.00 or more and 2.20 or less, more preferably 1.00 or more and 2.00 or less. is there.

  In addition, a weight average molecular weight and molecular weight distribution refer to the value measured by gel permeation chromatography (GPC) using HLC-8220GPC (developing solvent NMP, detection RI, conversion value by polystyrene) manufactured by Tosoh Corporation.

The dye multimer in the present invention preferably has an alkali-soluble group.
Examples of the alkali-soluble group include a carboxyl group, a phosphono group, and a sulfo group. Among these, a carboxyl group is preferable.
The acid value of the specific dye multimer is preferably 0.5 mmol / g or more and 3.0 mmol / g or less, and preferably 0.6 mmol / g or more and 2.5 mmol / g from the viewpoint of being suitably used in the photolithography method described later. Or less, more preferably 0.7 mmol / g or more and 2.0 mmol / g or less.

  Examples of the specific dye multimer in the present invention include dimers, trimers, oligomers, and polymers.

When the dye multimer used in the present invention is synthesized by a copolymerization reaction, the other polymerizable monomer (comonomer) is not particularly limited as long as it can be polymerized with the polymerizable dye monomer.
These comonomers include styrenic compounds, carboxylic acid monomers, and their esters, amides, imides or anhydrides, and vinyl compounds.
Examples of styrenic compounds are styrene, α-methylstyrene, hydroxystyrene, p-chloromethylstyrene, and m-chloromethylstyrene.
Examples of α, β-unsaturated carboxylic acids are acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and 1-butyne-2,3,4-tricarboxylic acid.

Examples of unsaturated carboxylic acid esters include the above-mentioned α, β-unsaturated carboxylic acid methyl ester, ethyl ester, 2-hydroxyethyl ester, propyl ester, butyl ester, octyl ester, dodecyl ester, 2,2, 6,6-tetramethyl-4-piperidyl ester, 1,2,2,6,6-pentamethyl-4-piperidyl ester, 2- [3- (2-benzotriazolyl) -4-hydroxyphenyl] ethyl ester It is.
Examples of unsaturated carboxylic acid amides include methyl amide, dimethyl amide, ethyl amide, diethyl amide, propyl amide, dipropyl amide, butyl amide, dibutyl amide, hexyl amide, octyl amide, phenyl of the above α, β-unsaturated carboxylic acid. Amides and the like.
Examples of unsaturated carboxylic acid imides are maleimide, itaconimide, N-butylmaleimide, N-octylmaleimide, and N-phenylmaleimide. Examples of vinyl compounds are vinyl acetate, N-vinyl carbazole, and N-vinyl pyrrolidone.

  Although the copolymerization ratio of the polymerizable dye monomer and the comonomer varies depending on the type of the polymerizable dye monomer, it is usually preferably in a ratio of 5 to 10,000 g of the comonomer with respect to 100 g of the polymerizable dye monomer. A ratio is more preferable, and a ratio of 5 to 100 g of comonomer is particularly preferable.

  The specific dye multimer in the present invention has at least one of structural units represented by the following general formula (A), general formula (B), and general formula (C), or the general formula (D And a dye multimer containing a dipyrromethene structure represented by

(Structural unit represented by formula (A))

In general formula (A), X ^A1 represents a linking group formed by polymerization, L ^A1 represents a single bond or a divalent linking group, and Dye represents one arbitrary hydrogen atom from a dye compound containing a dipyrromethene structure. Represents ˜1 + m pigment residues removed. X ^A2 represents a linking group formed by polymerization, L ^A2 represents a single bond or a divalent linking group, m represents an integer of 0 to 3, and when m is 2 or more, the structure in [] May be the same or different. Dye and LA ² may be linked by any of a covalent bond, an ionic bond, and a coordination bond.

In the general formula (A), X ^A1 and X ^A2 each independently represent a linking group formed by polymerization. That is, it refers to a portion that forms a repeating unit corresponding to the main chain formed by the polymerization reaction. Two sites represented by * are repeating units.
X ^A1 and X ^A2 each independently include a linking group formed by polymerizing a substituted or unsubstituted unsaturated ethylene group, a linking group formed by ring-opening polymerization of a cyclic ether, and the like. Is a linking group formed by polymerizing an unsaturated ethylene group. Specific examples include the following linking groups, but the linking groups formed by polymerization in the present invention are not limited to these.
In the following (X-1) to (X-15), it is connected to L ^A1 or L ^A2 at the site indicated by *.

In general formula (A), L ^A1 and L ^A2 each independently represent a single bond or a divalent linking group. L ^A1 and L ^A2 are each independently a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 30 carbon atoms (for example, methylene group, ethylene group, trimethylene group, propylene group, butylene group, etc.) A substituted or unsubstituted arylene group having 6 to 30 carbon atoms (for example, a phenylene group, a naphthalene group, etc.), a substituted or unsubstituted heterocyclic linking group, —CH ₂ ═CH ₂ —, —O—, —S—. , —NR—, —C (═O) —, —SO—, —SO ₂ —, a linking group represented by the following general formula (2), a linking group represented by the following general formula (3), or the following And a linking group formed by linking two or more of these (for example, —N (R) C (═O) —, —OC (═O) —). , -C (= O) N (R)-, -C (= O) O-). R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
The divalent linking group of the present invention is not limited at all as long as the effects of the present invention can be obtained.

Here, R ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ³ represents a hydrogen atom or a substituent. k represents an integer of 0 to 4, and when k is 2 or more, R ³ may be the same or different.
In the general formula (2) to the general formula (4), * represents a position bonded to the —C (R ¹ ) ═CH ₂ group in the general formula (1), and ** represents the general formula (1). It represents a position bonded with the (case of n = 0) ^{L 2} or Dye in.

In general formula (A), m represents an integer of 0 to 3. When m is 2 or more, a plurality of X ^A2 may be the same or different. Similarly, when m is 2 or more, a plurality of L ^A2 may be the same or different.
M is preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

In the general formula (A), Dye represents a dye residue obtained by removing 1 to 1 + m of arbitrary hydrogen atoms of a dye compound having a dipyrromethene structure.
In General Formula (A), Dye and L ^A2 may be linked by any of a covalent bond, an ionic bond, and a coordination bond, but are preferably linked by an ionic bond or a coordination bond.

(Structural unit represented by general formula (B))

In the general formula (B), X ^B1 represents a linking group formed by polymerization, L ^B1 represents a single bond or a divalent linking group, and A represents a group capable of ionic bonding or coordination bonding with Dye. Dye represents a dye compound having a dipyrromethene structure having a group capable of ionic bonding or coordination bond with A, or a dye residue obtained by removing 1 to m arbitrary hydrogen atoms from the dye compound. X ^B2 represents a linking group formed by polymerization, L ^B2 represents a single bond or a divalent linking group, m represents an integer of 0 to 3, and when m is 2 or more, the structure in [] May be the same or different. Dye and the L ^B2, covalent bonding, ionic bonding, and may be connected at any coordination bonds.

X ^B1 , L ^B1 , and m in the general formula (B) have the same meanings as X ^A1 , L ^A1 , and m in the general formula (A), respectively, and the preferred ranges are also the same.
X ^B2 and L ^B2 in the general formula (B) have the same ^meanings as X ^A2 and L ^A2 in the general formula (A), respectively, and the preferred ranges are also the same.
The group represented by A in the general formula (B) may be any group capable of ionic bonding or coordination bonding with Dye, and the group capable of ionic bonding may be either an anionic group or a cationic group. . The anionic group is preferably an anionic group having a pKa of 12 or less, such as a carboxyl group, a phospho group, a sulfo group, an acylsulfonamide group, or a sulfonimide group, more preferably a pKa of 7 or less, still more preferably 5 or less. The anionic group may form an ionic bond or a coordinate bond with Ma or a heterocyclic group in Dye, but it is more preferable to form an ionic bond with Ma. Specific examples of preferred anionic groups are shown below, but the present invention is not limited thereto. In the following specific examples, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

  As the cationic group represented by A in the general formula (B), a substituted or unsubstituted onium cation (for example, a substituted or unsubstituted ammonium group, pyridinium group, imidazolium group, sulfonium group, phosphonium group, etc.) Are preferable, and a substituted ammonium group is particularly preferable.

In general formula (B), m represents an integer of 0 to 3. When m is 2 or more, a plurality of ^XB2 may be the same or different. Similarly, when m is 2 or more, a plurality of L ^B2 may be the same or different.
M is preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

Dye in the general formula (B) is a dye compound containing a dipyrromethene structure, or a dye residue obtained by removing 1 to m arbitrary hydrogen atoms from the dye compound.
In General Formula (B), Dye and L ^B2 may be connected by any of a covalent bond, an ionic bond, and a coordinate bond, but are preferably connected by an ionic bond or a coordinate bond.

(Structural unit represented by general formula (C))

In the general formula (C), L ^C1 represents a single bond or a divalent linking group, and Dye represents a divalent dye residue obtained by removing two arbitrary hydrogen atoms from a dye compound containing a dipyrromethene structure.
L ^C1 in the general formula (C) has the same meaning as L ^A1 in the general formula (A), and the preferred range is also the same.

  The structural units containing the dipyrromethene structure constituting the specific dye multimer of the present invention are shown below.

(Copolymerization component)
The specific dye multimer of the present invention may be composed of only the structural units represented by the general formula (A), the general formula (B), and the general formula (C). ), At least one of the structural units represented by the general formula (B) and the general formula (C), and other structural units (in this case, the general formula (A) ), At least one of the structural units represented by the general formula (B) and the general formula (C) and the other structural units preferably include an alkali-soluble group.
The other structural unit is preferably a structural unit having an alkali-soluble group (carboxyl group, phosphono group, sulfo group, etc.) in the side chain.
Hereinafter, although the specific example of another structural unit is shown, this invention is not limited to these.

  Moreover, the following structural unit which has an unsaturated group in a side chain is also preferable as a copolymerization component. For example, an ethylenically unsaturated group (for example, a methacryl group, an acryl group, a styryl group, etc.) is mentioned, and heat resistance and solvent resistance are improved by including these structural units.

(Dye multimer represented by formula (D))

In General Formula (D), L ^D1 represents an m-valent linking group, m represents an integer of 2 to 100, and when m is 2 or more, the structures of Dye may be the same or different. . Dye represents a dye residue obtained by removing one arbitrary hydrogen atom from a dye compound containing a dipyrromethene structure.
m is preferably 2 to 80, more preferably 2 to 40, and particularly preferably 2 to 10.

When m is 2, the divalent linking group represented by L ^D1 is a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 30 carbon atoms (for example, methylene group, ethylene group, trimethylene group). , Propylene group, butylene group, etc.), substituted or unsubstituted arylene group having 6 to 30 carbon atoms (eg, phenylene group, naphthalene group, etc.), substituted or unsubstituted heterocyclic linking group, —CH ₂ ═CH ₂ — , —O—, —S—, —NR—, —C (═O) —, —SO—, —SO ₂ —, and a linking group formed by linking two or more thereof (for example, —N (R) C (= O)-, -OC (= O)-, -C (= O) N (R)-, -C (= O) O-, -N (R) C (= O) N (R)-etc.) are preferred. R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
The m-valent linking group in which m is 3 or more is a substituted or unsubstituted arylene group (1,3,5-phenylene group, 1,2,4-phenylene group, 1,4,5,8-naphthalene group, etc.) And a linking group formed by substituting the divalent linking group with a heterocyclic linking group (for example, 1,3,5-triazine group, etc.), an alkylene linking group or the like as a central mother nucleus.

(Dye monomer represented by general formula (1))
The specific dye monomer in the present invention is also preferably obtained by polymerizing a dye monomer containing a dipyrromethene structure represented by the following general formula (1).

In the general formula (1), R ¹ represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group. L ¹ is —N (R ² ) C (═O) —, —OC (═O) —, —C (═O) N (R ² ) —, —C (═O) O—, The group represented by (2), the group represented by the following general formula (3), or the group represented by the following general formula (4) is represented. L ² represents a divalent linking group. m and n each independently represents 0 or 1. Dye represents a dye residue containing a dipyrromethene structure. R ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

Here, R ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ³ represents a hydrogen atom or a substituent. k represents an integer of 0 to 4, and when k is 2 or more, R ³ may be the same or different. In the general formula (2) to the general formula (4), * represents a position bonded to the —C (R ¹ ) ═CH ₂ group in the general formula (1), and ** represents the general formula (1). It represents a position bonded with the (case of n = 0) ^{L 2} or Dye in.

That is, the dye monomer comprising a dipyrromethene structure represented by the general formula (1) is a dye compound containing a dipyrromethene ^{_{structure, - (L 2) n -}} (L 1) m -C (R 1) = CH ₂ is a compound into which a polymerizable group represented by ₂ is introduced.
When both m and n are 0, a -C (R ¹ ) = CH ₂ group is directly introduced into a dye compound containing a dipyrromethene structure.

In the general formula (1), R ¹ represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group. When R ¹ is an alkyl group or an aryl group, it may be unsubstituted or substituted.

When R ¹ is an alkyl group, a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 6 carbon atoms is preferable. Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, octyl group, isopropyl group, cyclohexyl group and the like.
When R ¹ is an aryl group, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and still more preferably 6 to 12 carbon atoms is preferable. Examples of the aryl group include a phenyl group and a naphthyl group.

When R ¹ is a substituted alkyl group or a substituted aryl group, the substituent is a halogen atom (for example, fluorine, chlorine, bromine, iodine), an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 1 carbon atoms). 12 alkyl groups, for example, methyl, ethyl, propyl, butyl, isopropyl, t-butyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, adamantyl), aryl groups (preferably having 6 to 24 carbon atoms, more Preferably it is a C6-C12 aryl group, for example, phenyl, naphthyl), a heterocyclic group (preferably C1-C24, more preferably a C1-C12 heterocyclic group, for example, 2-thienyl. 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazoli , 1-pyrazolyl, benzotriazol-1-yl), silyl group (preferably a silyl group having 3 to 24 carbon atoms, more preferably 3 to 12 carbon atoms, such as trimethylsilyl, triethylsilyl, tributylsilyl, t- (Butyldimethylsilyl, t-hexyldimethylsilyl), hydroxyl group, cyano group, nitro group, sulfonic acid group, phosphonic acid group, carboxyl group, alkoxy group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms) And more preferably an alkoxy group having 1 to 6 carbon atoms such as methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecyloxy, cycloalkyloxy group such as cyclopentyloxy, cyclohexyl Oxy), an aryloxy group (preferably having 6 to 24 carbon atoms) More preferably, it is an aryloxy group having 6 to 12 carbon atoms, such as phenoxy or 1-naphthoxy, and a heterocyclic oxy group (preferably having 1 to 24 carbon atoms, more preferably a heterocyclic oxy group having 1 to 12 carbon atoms). , For example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), a silyloxy group (preferably a silyloxy group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, for example, trimethylsilyloxy, t -Butyldimethylsilyloxy, diphenylmethylsilyloxy), an acyloxy group (preferably an acyloxy group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, for example, acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy), Alkoxycarbonyloxy group (preferably having 2 carbon atoms) 24, more preferably an alkoxycarbonyloxy group having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, such as ethoxycarbonyloxy, t-butoxycarbonyloxy), cycloalkyloxycarbonyloxy (for example, cyclohexyloxycarbonyl) Oxy)), aryloxycarbonyloxy group (preferably aryloxycarbonyloxy group having 7 to 24 carbon atoms, more preferably 7 to 12 carbon atoms, such as phenoxycarbonyloxy), carbamoyloxy group (preferably having 1 carbon atom) To 24, more preferably a carbamoyloxy group having 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms, such as N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy, N- Ethyl-N- Phenylcarbamoyloxy), a sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms, for example, N, N- Diethylsulfamoyloxy, N-propylsulfamoyloxy), an alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms). And, for example, methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexylsulfonyloxy), arylsulfonyloxy groups (preferably arylsulfonyloxy groups having 6 to 24 carbon atoms, more preferably 6 to 12 carbon atoms, such as phenylsulfonyl Oxy), an acyl group (preferably having 1 to 2 carbon atoms) , More preferably an acyl group having 1 to 12 carbon atoms, such as formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl, cyclohexanoyl)

An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl ), An aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 24 carbon atoms, more preferably an aryloxycarbonyl group having 7 to 12 carbon atoms, such as phenoxycarbonyl), a carbamoyl group (preferably having 1 to 24 carbon atoms, more preferably A carbamoyl group having 1 to 12 carbon atoms such as carbamoyl, N, N-diethylcarbamoyl, N-ethyl-N-octylcarbamoyl, N, N-dibutylcarbamoyl, N-propylcarbamoyl, N-phenylcarbamoyl, N-methyl − -Phenylcarbamoyl, N, N-dicyclohexylcarbamoyl), an amino group (preferably an amino group having 24 or less carbon atoms, more preferably 12 or less carbon atoms, such as amino, methylamino, N, N-dibutylamino, Tetradecylamino, 2-ethylhexylamino, cyclohexylamino), anilino group (preferably an anilino group having 6 to 24 carbon atoms, more preferably 6 to 12 carbon atoms, such as anilino, N-methylanilino), heterocyclic amino A group (preferably a C1-C24, more preferably a C1-C12 heterocyclic amino group such as 4-pyridylamino), a carbonamido group (preferably C2-C24, more preferably C2 ~ 12 carbonamido groups such as acetamide, benzamide, tetradecanamide, (Roylamide, cyclohexaneamide), ureido group (preferably a ureido group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, such as ureido, N, N-dimethylureido, N-phenylureido), imide group ( Preferably, it is an imide group having 20 or less carbon atoms, more preferably 12 or less carbon atoms, for example, N-succinimide, N-phthalimide), alkoxycarbonylamino group (preferably having 2 to 24 carbon atoms, more preferably 2 carbon atoms). -12 alkoxycarbonylamino group, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino, cyclohexyloxycarbonylamino), aryloxycarbonylamino group (preferably having 7 to 24 carbon atoms, Better Preferably, it is an aryloxycarbonylamino group having 7 to 12 carbon atoms, such as phenoxycarbonylamino), a sulfonamide group (preferably a sulfonamide group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, Methanesulfonamide, butanesulfonamide, benzenesulfonamide, hexadecanesulfonamide, cyclohexanesulfonamide), sulfamoylamino group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms). And, for example, N, N-dipropylsulfamoylamino, N-ethyl-N-dodecylsulfamoylamino), an azo group (preferably an azo group having 1 to 24 carbon atoms, more preferably 1 to 24 carbon atoms). For example, phenylazo, 3-pyrazolylazo), alkylthio group (preferably Or an alkylthio group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms such as methylthio, ethylthio, octylthio, cyclohexylthio), an arylthio group (preferably having 6 to 24 carbon atoms, more preferably 6 carbon atoms). An arylthio group having ˜12, for example, phenylthio), a heterocyclic thio group (preferably a heterocyclic thio group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, such as 2-benzothiazolylthio, 2 -Pyridylthio, 1-phenyltetrazolylthio), an alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 24 carbon atoms, more preferably an alkylsulfinyl group having 1 to 12 carbon atoms, for example, dodecanesulfinyl),

An arylsulfinyl group (preferably an arylsulfinyl group having 6 to 24 carbon atoms, more preferably an arylsulfinyl group having 6 to 12 carbon atoms, for example, phenylsulfinyl), an alkylsulfonyl group (preferably having 1 to 24 carbon atoms, more preferably 1 carbon atom) -12 alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecylsulfonyl, octylsulfonyl, cyclohexylsulfonyl), arylsulfonyl groups (preferably having 6 carbon atoms) To 24, more preferably an arylsulfonyl group having 6 to 12 carbon atoms, for example, phenylsulfonyl, 1-naphthylsulfonyl), sulfamoyl group (preferably having 24 or less carbon atoms, more preferably carbon 16 or less sulfamoyl groups, for example, sulfamoyl, N, N-dipropylsulfamoyl, N-ethyl-N-dodecylsulfamoyl, N-ethyl-N-phenylsulfamoyl, N-cyclohexylsulfamoyl), A sulfo group, a phosphonyl group (preferably a phosphonyl group having 1 to 24 carbon atoms, more preferably a phosphonyl group having 1 to 12 carbon atoms, such as phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), a phosphinoylamino group (preferably Is a phosphinoylamino group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and examples thereof include diethoxyphosphinoylamino and dioctyloxyphosphinoylamino).

  Among the above substituents, halogen atom, alkyl group, aryl group, hydroxyl group, sulfonic acid group, phosphonic acid group, carboxylic acid group, alkoxy group, aryloxy group, alkoxycarbonyloxy group, cycloalkylcarbonyloxy group, aryl Oxycarbonyloxy group, carbamoyloxy group, sulfamoyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carbonamido group, imide group, sulfonamido group , Sulfamoylamino group, sulfamoyl group are preferable, alkyl group, aryl group, hydroxyl group, sulfonic acid group, phosphonic acid group, carboxylic acid group, alkoxy group, aryloxy group, alkoxycarbonyloxy , Aryloxycarbonyloxy group, carbamoyloxy group, sulfamoyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carbonamido group, sulfonamido group, A sulfamoylamino group and a sulfamoyl group are more preferable, and a hydroxyl group, a sulfonic acid group, a phosphonic acid group, a carboxylic acid group, an alkoxy group, an aryloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, a carbamoyloxy group, a sulfo group. More preferred are a famoyloxy group, an alkylsulfonyloxy group, an arylsulfonyloxy group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. Group, a carboxylic acid group, an alkoxy group, an alkoxycarbonyl group, a carbamoyloxy group, a sulfamoylamino group, an alkylsulfonyloxy group, an acyl group, an alkoxycarbonyl group is particularly preferred.

  Among the above particularly preferred substituents, a sulfonic acid group, a carboxylic acid group, an alkoxy group, an alkoxycarbonyloxy group, an alkylsulfonyloxy group, and an alkoxycarbonyl group are more preferable, and a sulfonic acid group, a carboxylic acid group, an alkoxy group, and an alkoxycarbonyl group. A group is more preferable, and a sulfonic acid group, a carboxylic acid group, and an alkoxy group are particularly preferable.

In the general formula (1), R ¹ is preferably a hydrogen atom, an alkyl group or an aryl group, particularly preferably a hydrogen atom or an alkyl group.

In the general formula (1), when the substituents of the substituted alkyl group and the substituted aryl group of R ¹ are further substitutable groups, the substituents described above may be substituted. When substituted with the above substituents, these substituents may be the same or different.

In the general formula (1), L ¹ represents —N (R ² ) C (═O) —, —OC (═O) —, —C (═O) N (R ² ) —, —C (= O) represents O—, a group represented by the following general formula (2), a group represented by the general formula (3), or a group represented by the general formula (4). Here, R ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

In the general formula (1), the alkyl group, aryl group, and heterocyclic group represented by R ² are the alkyl group, aryl group, and heterocyclic group described above for the substituted alkyl group and substituted aryl group represented by R ^1. Is given as an example, and preferred embodiments are also the same.
The alkyl group, aryl group, and heterocyclic group of R ² may be substituted with the substituent described in the above R ¹ , and when they are substituted with two or more substituents, their substitution The groups may be the same or different.

Below, in the general formula (1), is represented by groups represented by the following formula represented by L ¹ (2), a group represented by the general formula (3), and general formula (4) The group will be described.

Here, R ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, R ³ represents a hydrogen atom or a substituent, k represents an integer of 0 to 4, and k is 2 In these cases, R ³ may be the same or different. * Represents the position bonded to the —C (R ¹ ) ═CH ₂ group in the general formula (1), and ** represents L ² or Dye (in the case of n = 0) in the general formula (1). Represents the position to join.

R ² has the same meaning as R ² described in the general formula (1), and the preferred embodiment is also the same.

R ³ represents a hydrogen atom or a substituent, and examples of the substituent represented by R ³ include the substituents described for the substituted alkyl group and substituted aryl group of R ¹ , and preferred embodiments are also the same. It is. k represents 0, 1, 2, 3, 4; When k is 2, 3, or 4, R ³ may be the same or different.
When the substituent of R ³ is a further substitutable group, it may be substituted with the substituent described in the above R ¹ , and when it is substituted with two or more substituents These substituents may be the same or different.

As L ¹ , from the viewpoint of synthesis, —N (R ² ) C (═O) —, —OC (═O) —, —C (═O) N (R ² ) —, —C (= O) O- are preferable, -OC (= O) -, - C (= O) N (R 2) -, - C (= O) O- , more preferably, -C (= O) N ( R 2 )-And -C (= O) O- are more preferable.

Next, L ² in the general formula (1) will be described.
L ² represents a divalent linking group that links L ¹ or —C (R ¹ ) ═CH ₂ group (when m = 0) and Dye.
L ² is preferably an alkylene group, an aralkylene group, an arylene group, —O—, —C (═O) —, —OC (═O) —, OC (═O) O—, —OSO ₂ —, ^{-OC (= O) N (R} 50) -, - N (R 50) -, - N (R 50) C (= O) -, - N (R 50) C (= O) O -, - N (R ⁵⁰ ) C (═O) N (R ⁵¹ ) —, —N (R ⁵⁰ ) SO ₂ —, —N (R ⁵⁰ ) SO ₂ N (R ⁵¹ ) —, —S—, —S—S— _{, -SO -, - SO 2 -} , - SO 2 N (R 50) -, - SO 2 O- and the like. In addition, a plurality of the above divalent linking groups may be bonded to form a new divalent linking group.

R ⁵⁰ and R ⁵¹ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Examples of the alkyl group, aryl group, and heterocyclic group of R ⁵⁰ and R ⁵¹ include the alkyl group, aryl group, and heterocyclic group described above for the substituent of R ¹ , and preferred embodiments are also the same. The alkyl group, aryl group, and heterocyclic group of R ⁵⁰ and R ⁵¹ may be substituted with the substituents described for the substituent of R ¹ , or may be substituted with two or more substituents. These substituents may be the same or different.

When L ² is an alkylene group, an aralkylene group, or an arylene group, it may be unsubstituted or substituted, and when it is substituted, it is substituted with the substituent described for the substituent of R ^1. When it is substituted with two or more substituents, these substituents may be the same or different.
When L ² is an alkylene group, an aralkylene group, or an arylene group, an alkylene group having 1 to 12 carbon atoms, an aralkylene group having 6 to 18 carbon atoms, or an arylene group having 6 to 18 carbon atoms is preferable. An alkylene group having 8 to 8 carbon atoms, an aralkylene group having 6 to 16 carbon atoms, and an arylene group having 6 to 12 carbon atoms are more preferable, and an alkylene group having 1 to 6 carbon atoms and an aralkylene group having 6 to 12 carbon atoms are still more preferable.

As the combination of L ¹ and L ² , L ¹ is —N (R ² ) C (═O) —, —OC (═O) —, —C (═O) N (R ² ) —, — C (= O) O-, L ² is an alkylene group having 1 to 12 carbon atoms, an aralkylene group having 6 to 18 carbon atoms, an arylene group having 6 to 18 carbon atoms, an alkylthioether having 2 to 18 carbon atoms, a carbon number Preferred are an alkylcarbonamide group having 2 to 18 carbon atoms and an alkylaminocarbonyl group having 2 to 18 carbon atoms. More preferably, L ¹ is —OC (═O) —, —C (═O) N (R ² ) —, —C (═O) O—, and L ² is an alkylene group having 1 to 8 carbon atoms, Embodiments of an aralkylene group having 6 to 16 carbon atoms, an arylene group having 6 to 12 carbon atoms, an alkylthioether having 2 to 12 carbon atoms, an alkylcarbonamide group having 2 to 12 carbon atoms, and an alkylaminocarbonyl group having 2 to 12 carbon atoms More preferably, L ¹ is —C (═O) N (R ² ) — or —C (═O) O—, L ² is an alkylene group having 1 to 6 carbon atoms, or 6 to 12 carbon atoms. Are an aralkylene group, an alkylthioether having 2 to 6 carbon atoms, an alkylcarbonamide group having 2 to 6 carbon atoms, and an alkylaminocarbonyl group having 2 to 6 carbon atoms.

Below, in the general formula (1) in ^{_{- (L 2) n - (}} L 1) m -C (R 1) = examples of the polymerizable group represented by CH _2. However, the present invention is not limited to these.

(Example compounds of specific dye multimers)
Hereinafter, although the exemplary compound of the specific dye multimer in this invention is shown, this invention is not limited to the following exemplary compounds at all.
In the following exemplary compounds, “wt-%” is based on mass.
Moreover, in exemplary compound 2-1 to 2-5, it superposes | polymerizes according to the ratio which shows the structural component which comprises the composition ratio a, and the methacrylic acid component corresponded to composition ratio (b + c) in a table | surface. A part of the methacrylic acid component of the dye multimer generated by polymerization is coordinated with Zn by an equimolar amount with respect to the component constituting the composition ratio a.

(Synthesis example of specific dye multimer)
Hereinafter, examples of the synthesis method will be shown for some specific examples of the specific dye multimer, but the present invention is not limited thereto.

-Synthesis of Exemplified Compound 1-4-
The following dye monomer 1 (5.0 g), methacrylic acid (0.68 g) and 240 mg of n-dodecanethiol as a chain transfer agent were dissolved in 32 ml of propylene glycol monomethyl ether acetate (PGMEA) and stirred at 85 ° C. under nitrogen. Then, 542 mg of dimethyl 2,2′-azobis (2-methylpropionate) was added. Thereafter, 240 mg of dimethyl 2,2′-azobis (2-methylpropionate) was additionally added twice every 2 hours, the temperature was raised to 90 ° C., and the mixture was further stirred for 2 hours. After completion of the reaction, the reaction solution was dropped into 400 ml of acetonitrile, and the resulting crystal was filtered to obtain Exemplified Compound 1-4 (4.8 g).
The following dye monomer 1 can be synthesized, for example, according to the synthesis method described in JP-A-2008-292970.
In addition, the weight average molecular weight can be adjusted by increasing / decreasing the amount of chain transfer agent and the reaction temperature, and the degree of dispersion can be adjusted by changing the type / amount of reprecipitation solvent.

-Synthesis of Exemplified Compound 2-3-
The following dye monomer 2 (20 g), methacrylic acid (5.88 g) and 520 mg of thiomalic acid as a chain transfer agent were dissolved in 150 ml of propylene glycol monomethyl ether (PGME), stirred at 85 ° C. under nitrogen, dimethyl 2, 1.2 g of 2′-azobis (2-methylpropionate) was added. Thereafter, 1.2 g of dimethyl 2,2′-azobis (2-methylpropionate) was additionally added twice every 2 hours, the temperature was raised to 90 ° C., and the mixture was further stirred for 2 hours. After completion of the reaction, the reaction solution was dropped into 2000 ml of acetonitrile, and the resulting crystal was filtered to obtain Exemplary Compound 2-3 (21.2 g). ^{Since the} AcO proton peak disappeared from the ¹ H NMR spectrum, it was confirmed that the main chain carboxylic acid was coordinated as in Example Compound 2-3.
The following dye monomer 2 can also be synthesized according to, for example, the synthesis method described in JP-A-2008-292970. In addition, the weight average molecular weight can be adjusted by increasing / decreasing the amount of chain transfer agent and the reaction temperature, and the degree of dispersion can be adjusted by changing the type / amount of reprecipitation solvent.

As mentioned above, although the specific dye multimer in this invention was demonstrated, in the colored curable composition of this invention, a specific dye multimer may be used individually by 1 type, and may use 2 or more types together. Moreover, in the colored curable composition of this invention, you may use together other coloring agents other than (A) phthalocyanine pigment and (B) specific dye multimer. Examples of other colorants will be described later.
The total content of (A) phthalocyanine pigment and (B) specific dye multimer in the total solid content of the colored curable composition of the present invention is preferably 0.1 to 70% by mass, and 1 to 65% by mass. % Is more preferable, and 5 to 60% by mass is particularly preferable.
1-70 mass% is preferable, and, as for content of the total colorant in the total solid of the colored curable composition which used another colorant together with the colored curable composition of this invention, 20-65 mass% is preferable. More preferably, 40-60 mass% is especially preferable.

  The colored curable composition of the present invention may be used in combination with other colorants (pigments and dyes) in order to further improve the spectral properties of the resulting colored film.

  Specific examples of the pigment that may be used in combination include Color Index Pigment Red 9, 19, 38, 43, 97, 122, 123, 144, 149, 166, 168, 177, 179, 180, 192, 215, 216, 208, 217, 220, 223, 224, 226, 227, 228, 240, 254, Pigment Yellow 20, 24, 86, 81, 83, 93, 108, 109, 110, 117, 125, 137, 138 139, 147, 148, 150, 153, 154, 166, 168, 185, Pigment Orange 36, Pigment Violet 23, and the like, but are not limited thereto.

Specific examples of the dye include Color Index Acid Red 52, 87, 92, 122, 486, Solvent Red 8, 24, 83, 109, 125, 132, Disperse Red 60, 72, 88, 206. Basic Red 12, 27, Acid Blue 9, 40, 83, 129, 249, Solvent Blue 25, 35, 36, 55, 67, 70, Disperse Blue 56, 81, 60, 87, 149, 197, 211, 214, Basic Blue 1, 7, 26, 77, Acid Green 18, Solvent Green 3, Basic Green 1, Acid Yellow 38, 99, Solvent Yellow 25, 88, 89, 146, Disperse Yellow 42, 60, 87, 198, Basic Yellow 21 , But it is not limited thereto.
Furthermore, in order to obtain a desired hue, these dyes and pigments may be used by mixing two or more kinds in the colored curable composition of the present invention.

[(D) Polymerizable compound]
The colored curable composition of the present invention contains (D) a polymerizable compound.
The (D) polymerizable compound is an ethylenically unsaturated polymerizable compound containing at least one of an epoxy group and an isocyanate group.
The colored curable composition of the present invention may contain a polymerizable compound other than the ethylenically unsaturated polymerizable compound containing at least one of an epoxy group and an isocyanate group as the polymerizable compound (D).

Examples of the ethylenically unsaturated polymerizable compound containing at least one of the epoxy group and isocyanate group described above include glycidyl (meth) acrylate, 2- (meth) acryloylethyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate (Showa) Preference is given to Denko Corporation, Karenz MOI), 1,1-bis- (acryloyloxymethyl) ethyl isocyanate (Showa Denko, Karenz BOI). By using these compounds as the polymerizable compound, the suppression of the elution of the dye into the developer that can be placed during development is improved.
Among these, glycidyl (meth) acrylate, 2-methacryloyloxyethyl isocyanate, and 1,1-bis- (acryloyloxymethyl) ethyl isocyanate are particularly preferable.

Further, the colored curable composition of the present invention includes a polymerizable compound having a structure other than an ethylenically unsaturated polymerizable compound containing at least one of an epoxy group and an isocyanate group (hereinafter referred to as “other polymerizable compound” as appropriate). Can be included).
The other polymerizable compound that can be used in the colored curable composition of the present invention is a polymerizable compound that does not contain an epoxy group or an isocyanate group and has at least one ethylenically unsaturated double bond. That's fine.
Other polymerizable compounds are widely known in the industrial field, and these can be used without particular limitation in the present invention.

Other polymerizable compounds have chemical forms such as monomers, prepolymers (ie, dimers, trimers, and oligomers), or mixtures or copolymers thereof. Examples of monomers and copolymers thereof include, for example, unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters or amides thereof. Preferably, 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. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group, or a mercapto group, and a monofunctional or polyfunctional isocyanate or epoxy, and a hydroxyl group A dehydration condensation reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as an amino group or a mercapto group and a monofunctional or polyfunctional carboxylic acid is also preferably used.
Furthermore, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a halogen group or 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 compound group in which an unsaturated phosphonic acid, styrene, vinyl ether or the like is substituted for 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 ester, methacrylic acid ester, itaconic acid ester, and the like.
Examples of acrylic esters include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, and trimethylolpropane triacrylate. , Trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaerythritol diacryl Over DOO, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomers, and isocyanuric acid EO-modified triacrylate.

  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 tetracrotonate. 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, for example, aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, and JP-A-59-5241. Those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Furthermore, monomers containing acid groups can also be used, such as (meth) acrylic acid, pentaerythritol triacrylate succinic acid monoester, dipentaerythritol pentaacrylate succinic acid monoester, dipentaerythritol tetraacrylate succinic acid diester, penta Erythritol triacrylate maleic acid monoester, dipentaerythritol pentaacrylate maleic acid monoester, pentaerythritol triacrylate phthalic acid monoester, dipentaerythritol pentaacrylate phthalic acid monoester, pentaerythritol triacrylate tetrahydrophthalic acid monoester, dipentaerythritol Examples include pentaacrylate tetrahydrophthalic acid monoester. In particular, pentaerythritol triacrylate succinic acid monoester is preferable from the viewpoint of developability and sensitivity.

  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-54-21726.

  In addition, urethane-based addition-polymerizable compounds produced by using an addition reaction between isocyanate and hydroxyl group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. 2 or more polymerizable vinyl groups are contained in one molecule obtained by adding a vinyl monomer containing a hydroxyl group in a compound represented by the following general formula to a polyisocyanate compound having two or more isocyanate groups. A vinyl urethane compound etc. are mentioned.

Formula ^{_{CH 2 = C (R 10)}} COOCH 2 CH (R 11) OH
(However, R ¹⁰ and R ¹¹ represent H or CH _3. )

  Further, 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-56-17654 Urethane compounds having an ethylene oxide skeleton described in 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, JP-A-1-105238 Can obtain a photopolymerizable composition having an excellent photosensitive speed.

Other examples include reacting polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490. And polyfunctional acrylates and methacrylates such as epoxy acrylates. 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 are also included. be able to. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

  For these polymerizable compounds, a structure having a high unsaturated group content per molecule is preferable in terms of sensitivity, and in many cases, a bifunctional or more functional group is preferable. Further, in order to increase the strength of the image area, that is, the cured film, those having three or more functionalities are preferable. Further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrenic compound, vinyl ether type). A method of adjusting both sensitivity and strength by using a compound) is also effective. 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, the compound containing a carboxylic acid group or EO modified body structure is preferable 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 and use of the polymerizable compound is an important factor for the compatibility and dispersibility with other components (for example, resin, polymerization initiator, colorant) in the colored curable 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 with a substrate or the like.

  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 tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxy D (I) Isocyanurate, pentaerythritol tetraacrylate modified EO, dipentaerythritol hexaacrylate EO modified, pentaerythritol triacrylate succinic acid monoester and the like are preferred, and commercially available products include urethane oligomer UAS-10. , UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.) is preferable.

  Among them, bisphenol A diacrylate EO modified, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modified, di Pentaerythritol hexaacrylate EO modified product, pentaerythritol triacrylate succinic acid monoester, etc. are commercially available products such as DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600 T-600 and AI-600 (manufactured by Kyoeisha) are more preferred.

The content of the polymerizable compound (D) in the total solid content of the colored curable composition of the present invention is preferably 1% by mass to 90% by mass, and more preferably 5% by mass to 80% by mass. Preferably, it is 10 mass%-70 mass%.
By setting it as this range, sclerosis | hardenability improves and pattern moldability becomes favorable.
The content of the ethylenically unsaturated polymerizable compound containing at least one of an epoxy group and an isocyanate group is 0.5 parts to 10 parts on a mass basis with respect to 100 parts of the total solid content of the colored curable composition. It is preferable that
By setting this range, curability is improved and elution of the colorant with respect to the alkaline developer is suppressed.

[(C) Polymerization initiator]
The colored curable composition of the present invention can contain (C) a polymerization initiator.
As a polymerization initiator, it is preferable to contain the photoinitiator which is a radiation sensitive compound.
The photopolymerization initiator is a compound that is decomposed by light and initiates and accelerates polymerization of a polymerizable component such as the above-described polymerizable compound, and in particular, is a compound having absorption in a wavelength region of 300 nm to 500 nm. Is preferred.
The photopolymerization initiator may have a property of initiating polymerization by heat in addition to the property of initiating polymerization by light as described above.
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, oxocidiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, Examples thereof include metallocene compounds, hexaarylbiimidazole compounds, organic borate compounds, disulfonic acid compounds, oxime compounds, onium salt compounds, acylphosphine (oxide) compounds, alkylamino compounds, and the like.
Hereinafter, each of these compounds will be described in detail.

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

  As the s-triazine compound, more preferably, an s-triazine derivative in which at least one mono-, di-, or trihalogen-substituted methyl group is bonded to the s-triazine ring, specifically, for example, 2,4,6- Tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6- Bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloro Methyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl)- s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) ) -S-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6- Bis (tribromomethyl) -s-triazine and the like can be mentioned.

  Examples of the oxodiazole compound include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2- Examples include trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, and the like. .

  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- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) , Acetophenone derivatives such as 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone Thioxanthone derivatives such as 2,4-diisopropylthioxanthone, and benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

Examples of the ketal compound include benzyl methyl ketal and benzyl-β-methoxyethyl ethyl acetal.
Examples of the benzoin compound include m-benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, and methyl-o-benzoylbenzoate.

  Examples of the acridine compound include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the organic peroxide compound include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxide). Oxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroper Oxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2 , -Oxanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate , Dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert- Butyl peroxyoctanoate, tert-butyl peroxylaurate, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- ( t-he Sylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate), carbonyldi (t-hexylper) Oxydihydrogen diphthalate) and the like.

  Examples of the azo compound include azo compounds described in JP-A-8-108621.

  Examples of the coumarin compound include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl). ) Amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like.

  Examples of the azide compound include organic azide compounds described in U.S. Pat. No. 2,848,328, U.S. Pat. No. 2,852,379 and U.S. Pat. No. 2,940,553, 2,6-bis (4-azidobenzylidene) -4-ethyl. And cyclohexanone (BAC-E).

  Examples of the metallocene compound include JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, JP-A-2-4705, Various titanocene compounds described in JP-A-5-83588, such as di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di -Cyclopentadienyl-Ti-bis-2,4-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, di- Cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentaful Lophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4,6-trifluoropheny -1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4 , 5,6-pentafluorophen-1-yl, iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109, and the like.

  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 the organic borate compound include JP-A-62-143044, JP-A-62-1050242, JP-A-9-188585, JP-A-9-188686, JP-A-9-188710, JP-A-2000. -131837, Japanese Patent Application Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application Laid-Open No. 2002-116539, and the like, and Kunz, Martin “Rad Tech'98. Proceeding April 19-22, 1998, Chicago”. Organoboron salts described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, JP-A-6-175554 In Japanese Patent Laid-Open No. 6-175553 Organoboron iodonium complexes, organoboron phosphonium complexes described in JP-A-9-188710, JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7- Specific examples include organoboron transition metal coordination complexes such as those described in Japanese Patent No. 306527 and Japanese Patent Laid-Open No. 7-292014.

  Examples of the disulfonic acid compound include compounds described in JP-A Nos. 61-166544 and 2002-328465.

  Examples of oxime 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, Japanese Patent Application Laid-Open No. 2000-66385, Japanese Patent Application Laid-Open No. 2000-80068, Japanese Patent Application Publication No. 2004-534797 Compounds and the like.

  Examples of the onium salt compounds include S.I. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Diazonium salts described in Bal et al, Polymer, 21, 423 (1980), ammonium salts described in US Pat. No. 4,069,055, JP-A-4-365049, etc., US Pat. No. 4,069 , 055, 4,069,056, phosphonium salts described in each specification, European Patent Nos. 104 and 143, JP-A-2-150848, JP-A-2-296514, iodonium salts Etc.

  The iodonium salt that can be used in the present invention is a diaryl iodonium salt, and from the viewpoint of stability, it is preferable that two or more are substituted with an electron donating group such as an alkyl group, an alkoxy group, and an aryloxy group.

Examples of the sulfonium salt that can be used in the present invention include European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, and US Pat. No. 4,933. , 377, 161,811, 4,760,013, 4,734,444, 2,833,827, German Patent Nos. 2,904,626, 3,604 The sulfonium salt described in each specification of 580 and 3,604,581 is mentioned, It is preferable that it is substituted by the electron withdrawing group from the point of stability and a sensitivity. The electron withdrawing group preferably has a Hammett value greater than zero. Preferred electron-withdrawing groups include halogen atoms and carboxylic acids.
Other preferable sulfonium salts include sulfonium salts in which one substituent of the triarylsulfonium salt has a coumarin or anthraquinone structure and absorbs at 300 nm or more. As another preferable sulfonium salt, a sulfonium salt in which the triarylsulfonium salt has an allyloxy group or an arylthio group as a substituent and has absorption at 300 nm or more can be mentioned.

  Moreover, as an onium salt compound, J.M. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt described in C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and onium salts such as arsonium salts.

  Examples of the acylphosphine (oxide) compound include Irgacure 819, Darocur 4265, and Darocur TPO manufactured by BASF.

  Examples of the alkylamino compound include compounds having a dialkylaminophenyl group described in paragraph No. [0047] of JP-A-9-281698, JP-A-6-19240, JP-A-6-19249, and the like. An amine compound is mentioned. Specifically, compounds having a dialkylaminophenyl group include compounds such as ethyl p-dimethylaminobenzoate, and dialkylaminophenyl carbaldehydes such as p-diethylaminobenzcarbaldehyde and 9-julolidylcarbaldehyde. Examples of the amine compound include triethanolamine, diethanolamine, and triethylamine.

  As the photopolymerization initiator, the above-described initiators can be arbitrarily used, but from the viewpoint of exposure sensitivity, more preferably triazine compounds (s-triazine compounds), ketal compounds, benzoins of organic halogenated compounds. Compounds, metallocene compounds, hexaarylbiimidazole compounds, oxime compounds, acylphosphine (oxide) compounds, hexaalkylamino compounds, triazine compounds, oxime compounds, hexaarylbiimidazole compounds, and alkylamino compounds are more preferred, Most preferred are oxime compounds.

  In particular, when the colored curable composition of the present invention is used for forming colored pixels in a color filter for a solid-state imaging device, the amount of the polymerization initiator added is reduced because the pigment concentration in the composition is high due to the formulation. , The sensitivity may decrease. Further, when exposure is performed with a stepper, use of an initiator that generates a halogen-containing compound during exposure, such as a triazine compound, may cause corrosion of the equipment. Taking these into consideration, the photopolymerization initiator that satisfies the sensitivity and various performances is preferably an oxime compound, and most preferably an oxime compound having absorption at 365 nm.

  In the present invention, among the oxime compounds, a compound represented by the following general formula (d) is preferable from the viewpoints of sensitivity, diameter stability, and coloring during post-heating. Moreover, as a commercial item, Irgacure OXE-01, OXE-02, etc. manufactured by BASF are also preferable.

In the general formula (d), R ²² and X ²² each independently represent a monovalent substituent, A ²² represents a divalent organic group, and Ar represents an aryl group. n is an integer of 1-5.

R ²² is preferably an acyl group from the viewpoint of increasing sensitivity, and specifically, an acetyl group, a propionyl group, a benzoyl group, and a toluyl group are preferable.

A ²² is an alkylene group substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloring due to heating. , 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 group) An alkylene group substituted with is preferred.

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

X ²² may have an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region. Alkenyl group, optionally substituted alkynyl group, optionally substituted alkoxy group, optionally substituted aryloxy group, optionally substituted alkylthioxy group, substituted An arylthio group which may have a group and an amino group which may have a substituent are preferable.
Moreover, n in general formula (d) is preferably an integer of 1 to 2.

  Moreover, as a preferable oxime compound other than the compound which has the said structure, what has a structure represented by the following general formula (d-2) or general formula (d-3) is mentioned.

R ²² , A ²² , and Ar in the general formula (d-3), and R ²² , X ²² , A ²² , Ar, and n in the general formula (d-3) are respectively in the general formula (d). ^{R 22, X 22, a 22} , Ar, and is synonymous with n.
Specific examples of oxime compounds suitable for the colored curable composition of the present invention are shown below, but the present invention is not limited thereto.

  The content of the polymerization initiator in the total solid content of the colored curable composition of the present invention is preferably 0.1% by mass to 50% by mass, more preferably 0.5% by mass to 30% by mass, Especially preferably, it is 1 mass%-20 mass%. Within this range, good sensitivity and pattern formability can be obtained.

[(E) solvent]
The colored curable composition of the present invention contains (E) a solvent.
Examples of the solvent include liquids selected from the organic solvents shown below, and are selected in consideration of the solubility of each component contained in the colored curable composition, applicability, and the like. There is no particular limitation as long as these desired physical properties are satisfied, but it is preferably selected in consideration of safety.

  Specific examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl oxyacetate, and ethyl oxyacetate. , Butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, 3-methoxypropion Ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, 2-methoxypropion Ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy-2 -Methyl methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like;

  Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate (ethylene glycol monomethyl ether acetate), ethyl cellosolve acetate (ethylene glycol monoethyl ether acetate), diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol methyl ether, propylene glycol monomethyl ether acetate, propylene glycol ethyl ether acetate, pro Glycol propyl ether acetate; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; and aromatic hydrocarbons, e.g., toluene, xylene and the like; are preferred.

Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, diethylene glycol monoethyl ether acetate, Diethylene glycol monobutyl ether acetate, propylene glycol methyl ether, propylene glycol monomethyl ether acetate and the like are more preferable.
These solvents may be used alone, but it is also preferable to mix two or more kinds from the viewpoints of solubility of each component constituting the colored curable composition, improvement of the coating surface condition, and the like. In this case, particularly preferably, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl It is a mixed solution composed of two or more selected from carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

As content of the (E) solvent in the colored curable composition of this invention, 50-90 mass% is preferable, 60-95 mass% is more preferable, 70-90 mass% is the most preferable. When the content of the solvent is within the above range, it is advantageous in terms of suppressing the generation of foreign matter.
In addition, when using a colored curable composition for manufacture of the color filter by an inkjet method, the one where content of (E) solvent is small is preferable from a sclerosing | hardenable viewpoint, and there may also be a form which does not use (E) solvent.

  The colored curable composition of the present invention uses, in addition to the essential components described above, known components such as an alkali-soluble resin, a crosslinking agent, and a surfactant according to the purpose as long as the effects of the present invention are not impaired. May be. Hereinafter, various components that can be used in the present invention will be described.

(Alkali-soluble resin)
The colored curable composition of the present invention preferably further contains an alkali-soluble resin. By containing an alkali-soluble resin, developability and pattern formation are improved.

  The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility 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 (for example, carboxyl group, phosphoric acid group, sulfonic acid group, etc.). Among these, more preferably, it is soluble in a solvent and can be developed with a weak alkaline aqueous solution.

  For production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

  As the linear organic polymer used as the alkali-soluble resin, a polymer having a carboxylic acid in the side chain is preferable, such as a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, and a crotonic acid copolymer. , Maleic acid copolymers, partially esterified maleic acid copolymers, etc., acidic cellulose derivatives having a carboxylic acid in the side chain, and polymers having a hydroxyl group added with an acid anhydride. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Examples of vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macro Monomers, polymethyl methacrylate macromonomers and the like can be mentioned.

  As the alkali-soluble resin, a polymer (a) obtained by polymerizing a monomer component essentially comprising a compound represented by the following general formula (ED) (hereinafter sometimes referred to as “ether dimer”) may be used. preferable.

In General Formula (ED), R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

In the general formula (ED) showing the ether dimer, the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ₁ and R ₂ is not particularly limited. , Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, t-amyl group, stearyl group, lauryl group, 2-ethylhexyl group, etc. Branched alkyl group; aryl group such as phenyl group; cyclohexyl group, t-butylcyclohexyl group, dicyclopentadienyl group, tricyclodecanyl group, isobornyl group, adamantyl group, 2-methyl-2-adamantyl group, An alicyclic group such as 1-methoxyethyl group, an alkyl group substituted with an alkoxy group such as 1-ethoxyethyl group; an aryl group such as a benzyl group Alkyl group; and the like. Among these, a primary or secondary carbon substituent which is difficult to be removed by an acid or heat, such as a methyl group, an ethyl group, a cyclohexyl group, and a benzyl group, is particularly preferable in terms of heat resistance.

Specific examples of the ether dimer include dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, (N-propyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) ) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2, 2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di Stearyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (2-ethylhexyl) -2 , 2 ′-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (1-ethoxyethyl) -2 , 2 ′-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 ′-[oxybis (methylene)] bis- 2-propenoate, dicyclohexyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-butylcyclohexyl) 2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tricyclodecanyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 '-[oxybis (Methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, and the like. Among these, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2′- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. These ether dimers may be only one kind or two or more kinds.
The structure derived from the compound represented by the general formula (ED) may be copolymerized with other monomers.

  Among these, benzyl (meth) acrylate / (meth) acrylic acid copolymer yabenzyl (meth) acrylate / (meth) acrylic acid / other monomeric calanal multi-component copolymers are particularly suitable. In addition, a copolymer of 2-hydroxyethyl methacrylate, a 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654, 2-hydroxy -3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / Benzyl methacrylate / methacrylic acid copolymer.

Moreover, in order to improve the crosslinking efficiency of the colored curable composition in the present invention, an alkali-soluble resin having a polymerizable group may be used.
As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is useful. As the alkali-soluble resin containing these polymerizable groups, an isocyanate group and an OH group are reacted in advance to leave one unreacted isocyanate group and a compound containing a (meth) acryloyl group and an acrylic containing a carboxyl group. Urethane-modified polymerizable double bond-containing acrylic resin obtained by reaction with resin, unsaturated group obtained by reaction of acrylic resin containing carboxyl group and compound having both epoxy group and polymerizable double bond in the molecule -Containing acrylic resin, acid pendant type epoxy acrylate resin, acrylic resin containing OH group and polymerizable double bond-containing acrylic resin obtained by reacting dibasic acid anhydride having polymerizable double bond, acrylic resin containing OH group, and A resin obtained by reacting an isocyanate with a compound having a polymerizable group, JP 2002-229207 A And a resin obtained by performing a basic treatment on a resin having an ester group having a leaving group such as a halogen atom or a sulfonate group at the α-position or β-position described in JP-A-2003-335814 Etc. are preferable.

The acid value of the alkali-soluble resin is preferably 30 mgKOH / g to 200 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g, and most preferably 70 to 120 mgKOH / g.
Further, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and most preferably 7,000 to 20,000.

  As content in the colored curable composition of alkali-soluble resin, 1-15 mass% is preferable with respect to the total solid of this composition, More preferably, it is 2-12 mass%, Most preferably 3 to 10% by mass.

(Crosslinking agent)
The colored curable composition of the present invention may contain a crosslinking agent.
The crosslinking agent is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, at least one selected from (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. A melamine compound substituted with one group, a guanamine compound, a glycoluril compound, or a urea compound, (c) a phenol compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group, naphthol A compound, or a hydroxyanthracene compound. Of these, polyfunctional epoxy resins are preferred.

  The (a) epoxy resin may be any epoxy resin as long as it has an epoxy group and crosslinkability. For example, bisphenol A glycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol Diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diglycidyl phthalate ester, N, N-diglycidyl aniline and other divalent glycidyl group-containing low molecular weight compounds, as well as trimethylolpropane triglycidyl ether, trimethylolphenol triglycidyl Trivalent glycidyl group-containing low molecular weight compounds typified by ether, TrisP-PA triglycidyl ether, pentaerythritol tetraglycidyl ether, tetramethylol bisphenol And tetravalent glycidyl group-containing low molecular weight compounds typified by RuA tetraglycidyl ether, and similarly, polyvalent glycidyl group-containing low molecular weight compounds such as dipentaerythritol pentaglycidyl ether and dipentaerythritol hexaglycidyl ether. .

  The number of methylol groups, alkoxymethyl groups, and acyloxymethyl groups substituted in the crosslinking agent (b) is 2 to 6 in the case of melamine compounds, in the case of glycoluril compounds, guanamine compounds, and urea compounds. Although it is 2-4, Preferably it is 5-6 in the case of a melamine compound, and 3-4 in the case of a glycoluril compound, a guanamine compound, and a urea compound.

  Hereinafter, the melamine compound, guanamine compound, glycoluril compound and urea compound of (b) are collectively referred to as a compound (methylol group-containing compound, alkoxymethyl group-containing compound, or acyloxymethyl group-containing compound) according to (b). There is.

  The methylol group-containing compound according to (b) can be obtained by heating the alkoxymethyl group-containing compound according to (b) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like. The acyloxymethyl group-containing compound according to (b) can be obtained by mixing and stirring the methylol group-containing compound according to (b) with acyl chloride in the presence of a basic catalyst.

Hereinafter, specific examples of the compound according to (b) having the substituent will be given.
Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 5 methylol groups of hexamethylol melamine are methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, hexamethylol. Examples thereof include compounds in which 1 to 5 methylol groups of melamine are acyloxymethylated, or mixtures thereof.

  Examples of the guanamine compound include, for example, tetramethylolguanamine, tetramethoxymethylguanamine, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolguanamine, or a mixture thereof, tetramethoxyethylguanamine, tetraacyloxymethylguanamine, tetramethylol. Examples thereof include compounds in which 1 to 3 methylol groups of guanamine are acyloxymethylated or a mixture thereof.

  Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxymethylglycoluril, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolglycoluril, or a mixture thereof, or a methylol group of tetramethylolglycoluril. Examples thereof include compounds obtained by acylating 1 to 3 or a mixture thereof.

Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol urea, a mixture thereof, and tetramethoxyethyl urea.
The compounds according to (b) may be used alone or in combination.

The crosslinking agent (c), that is, a phenol compound, a naphthol compound, or a hydroxyanthracene compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group is the crosslinking agent (b). As in the case of), intermixing with the overcoated photoresist is suppressed by thermal crosslinking, and the film strength is further increased.
Hereinafter, these compounds may be collectively referred to as a compound according to (c) (a methylol group-containing compound, an alkoxymethyl group-containing compound, or an acyloxymethyl group-containing compound).

  The number of methylol groups, acyloxymethyl groups, and alkoxymethyl groups contained in the cross-linking agent (c) is at least two per molecule, and from the viewpoint of thermal crosslinkability and storage stability, phenol as a skeleton Compounds in which the 2nd and 4th positions of the compound are all substituted are preferred. In addition, the naphthol compound and hydroxyanthracene compound as the skeleton are preferably compounds in which all of the ortho-position and para-position of the OH group are substituted. The 3rd or 5th position of the phenolic compound serving as the skeleton may be unsubstituted or may have a substituent. In addition, the naphthol compound as a skeleton may be unsubstituted or may have a substituent other than the ortho position of the OH group.

The methylol group-containing compound according to (c) is a compound in which the ortho-position or para-position (2-position or 4-position) of the phenolic OH group is a hydrogen atom, and this is used as sodium hydroxide, potassium hydroxide, It can be obtained by reacting with formalin in the presence of a basic catalyst such as ammonia or tetraalkylammonium hydroxide.
The alkoxymethyl group-containing compound according to (c) can be obtained by heating the methylol group-containing compound according to (c) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like.
The acyloxymethyl group-containing compound according to (c) can be obtained by reacting the methylol group-containing compound according to (c) with an acyl chloride in the presence of a basic catalyst.

  Examples of the skeletal compound in the crosslinking agent (c) include a phenol compound, a naphthol compound, a hydroxyanthracene compound, etc., in which the ortho-position or para-position of the phenolic OH group is unsubstituted. For example, phenol, cresol isomers, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenols such as bisphenol A, 4,4′-bishydroxybiphenyl, TrisP-PA (Honshu Chemical) Kogyo Co., Ltd.), naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene, and the like are used.

  Specific examples of the crosslinking agent (c) include trimethylolphenol, tri (methoxymethyl) phenol, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, trimethylol-3-cresol, tri ( Methoxymethyl) -3-cresol, a compound obtained by methoxymethylating one or two methylol groups of trimethylol-3-cresol, dimethylolcresol such as 2,6-dimethylol-4-cresol, tetramethylolbisphenol A, tetra Methoxymethyl bisphenol A, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol bisphenol A, tetramethylol-4,4′-bishydroxybiphenyl, tetramethoxymethyl-4,4′-bishydroxybiphenyl, Tr Hexamethylol of sP-PA, hexamethoxymethyl of Tris P-PA, compounds in which 1 to 5 methylol groups have been methoxymethylated hexamethylol of Tris P-PA, Bis-hydroxymethyl naphthalene diol.

Examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene.
Examples of the acyloxymethyl group-containing compound include compounds obtained by partially or fully acyloxymethylating the methylol group of the methylol group-containing compound.

Among these compounds, trimethylolphenol, bishydroxymethyl-p-cresol, tetramethylolbisphenol A, trisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) or a methylol group thereof is preferable. Examples thereof include an alkoxymethyl group and a phenol compound substituted with both a methylol group and an alkoxymethyl group.
These compounds according to (c) may be used alone or in combination.

When the coloring curable composition of this invention contains a crosslinking agent, 1-70 mass% is preferable with respect to the total solid (mass) of this composition, and 5-50 mass% is preferable. More preferably, 7-30 mass% is especially preferable.
When the content is within the above range, it is possible to maintain a sufficient degree of cure and elution of the uncured part, and prevent the degree of cure of the cured part from being insufficient or the elution of the uncured part from being significantly reduced. be able to.

(Surfactant)
Various surfactants may be added to the colored curable composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

In particular, the colored curable composition of the present invention contains a fluorosurfactant, so that the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, so that the coating thickness uniformity And the liquid-saving property can be further improved.
That is, when a film is formed using a coating liquid to which a colored curable composition containing a fluorosurfactant is applied, by reducing the interfacial tension between the coated surface and the coating liquid, The wettability is improved, and the coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

  The fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. A fluorine-based surfactant having a fluorine content in this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in a colored curable composition.

  Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (above, manufactured by Asahi Glass Co., Ltd.).

  Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Sol Perth 20000 (Lubrizol Japan Co., Ltd.), and the like.

  Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.

  Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.

  Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Tore Silicone SH21PA”, “Toray Silicone SH28PA” manufactured by Toray Silicone Co., Ltd. ”,“ Tore Silicone SH29PA ”,“ Tore Silicone SH30PA ”,“ Tore Silicone SH8400 ”,“ TSF-4440 ”,“ TSF-4300 ”,“ TSF-4445 ”,“ TSF-4460 ”manufactured by Momentive Performance Materials, Inc. ”,“ TSF-4442 ”,“ KP341 ”,“ KF6001 ”,“ KF6002 ”manufactured by Shin-Etsu Silicone Co., Ltd.,“ BYK307 ”,“ BYK323 ”,“ BYK330 ”manufactured by BYK Chemie It is.

Only one type of surfactant may be used, or two or more types may be combined.
The addition amount of the surfactant is preferably 0.001% by mass to 2.0% by mass, more preferably 0.005% by mass to 1.0% by mass with respect to the total solid content of the colored curable composition. is there.

(Polymerization inhibitor)
In the colored curable composition of the present invention, it is desirable to add a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the colored curable composition. .
Examples of the 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-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.
The addition amount of the polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the whole composition.

<Various additives>
The colored curable composition of the present invention may further contain various additives such as fillers, polymer compounds other than those mentioned above, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents and the like as necessary. I can do it. Examples of these include additives described in paragraph numbers [0274] to [0276] of JP-A-2008-292970.

<Preparation method of colored curable composition>
In preparing the colored curable composition of the present invention, the above-described components of the composition may be blended together, or may be blended sequentially after each component is dissolved in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. A colored curable composition may be prepared by dissolving all components in a solvent at the same time, and if necessary, each component is appropriately made into two or more solutions, and these solutions are used at the time of use (at the time of application). May be mixed to prepare a colored curable composition.
The colored curable composition prepared as described above preferably uses a filter made of polyethylene, polypropylene, nylon having a pore diameter of about 0.01 to 3.0 μm, more preferably about 0.05 to 0.5 μm. After filtration, it can be used.

  The colored curable composition of the present invention can be suitably used for forming colored pixels of color filters used in solid-state imaging devices (for example, CCD, CMOS, etc.), liquid crystal display devices, organic EL display devices, and the like. In particular, it can be suitably used for forming color filters for solid-state imaging devices such as CCDs and CMOSs.

When the colored curable composition of the present invention is used, for example, in the production of a color filter by a photolithographic method, the colored pattern is formed in a thin film with a very small size, and a solid rectangular imaging profile requiring a good rectangular cross-sectional profile is required. It is particularly suitable for forming a color filter.
Specifically, when the pixel pattern size (side length of the pixel pattern viewed from the substrate normal direction) constituting the color filter is 2 μm or less (for example, 0.5 to 2.0 μm), the area is very small. For this reason, in particular, the sensitivity of soaking into other colors, color transfer, and residues is significantly reduced due to a decrease in color separation ability. This becomes more remarkable especially when the pixel pattern size is 0.5 to 1.7 μm (further 0.5 to 1.2 μm).
On the other hand, if the colored curable composition of the present invention is used, a color filter having excellent pattern formability and suppressing color mixing such as soaking, color transfer and residue even with a pixel pattern size of 2 μm or less as described above is produced. Can do.

  In general, in a colored curable composition using a dye, the dye is likely to permeate into a previously formed pattern (or layer) of another color at the time of application (color permeation at the time of application of the next color). Furthermore, a colored curable composition using a dye requires the addition of a large amount of dye, and as a result, the relative content of components that contribute to photolithographic properties is reduced. For this reason, the pattern is likely to be peeled off in a low exposure area due to a decrease in sensitivity, or a desired shape and color density cannot be obtained due to elution of dye during alkali development, etc. Dye elution). Furthermore, in a colored curable composition using a dye, when heat treatment is performed after film formation, color transfer is likely to occur between adjacent pixels or between layers in a stacked state (thermal diffusion by heat treatment).

  However, if the colored curable composition of the present invention containing a phthalocyanine pigment and a specific dye multimer is used, the above-mentioned dye-specific dye soaking at the time of application of the next color and alkali development are maintained while maintaining the same transparency as the dye. It is possible to produce a colored film (color filter) in which elution of the dye at the time and thermal diffusion (color transfer) due to heat treatment can be significantly suppressed.

≪Color filter and manufacturing method≫
The color filter of the present invention is formed using the colored curable composition of the present invention. For this reason, the color filter of the present invention suppresses elution of the dye during alkali development.

Next, a method for forming a color filter by the photolithography method using the colored curable composition of the present invention will be described.
Examples of a method for forming a pattern by the photolithography method using the colored curable composition of the present invention include the methods described in paragraph numbers [0277] to [0284] of JP-A-2008-292970.

  Specifically, a step of forming the colored layer by applying the colored curable composition on a support (hereinafter also referred to as “colored layer forming step”), and a pattern-like pattern with respect to the formed colored layer An exposure process (hereinafter also referred to as “exposure process”) that forms a latent image by exposure, and a development process (hereinafter referred to as “development process”) that develops the colored layer on which the latent image is formed to form a pattern. And a method for producing a color filter (hereinafter also referred to as “a method for producing a color filter of the present invention”).

<Colored layer forming step>
In the method for producing a color filter of the present invention, first, the above-described colored curable composition of the present invention is applied onto a support by a coating method such as spin coating, cast coating, roll coating, ink jet method, spray coating or the like. Then, a coating layer is formed, and then pre-curing (pre-baking) is performed as necessary, and the application layer is dried to form a colored layer (colored layer forming step).

  Examples of the support used in the method for producing a color filter of the present invention include alkali-free glass, soda glass, borosilicate glass (pyrex (registered trademark) glass), quartz used in liquid crystal display devices, organic EL display devices, and the like. Examples thereof include glass, and those obtained by attaching a transparent conductive film thereto, a photoelectric conversion element substrate used for a solid-state imaging device such as a CCD or CMOS, a silicon substrate, and the like. These substrates may have black stripes that separate pixels. Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the surface.

  In addition, when spin-coating the colored curable composition on the support, in order to reduce the amount of dripping of the liquid, before dropping the colored curable composition, by dropping and rotating an appropriate organic solvent, The familiarity of the colored curable composition with the support can be improved.

Examples of the prebaking condition include a condition of heating at 70 ° C. to 130 ° C. for about 0.5 minutes to 15 minutes using a hot plate or an oven.
The thickness of the colored layer formed from the colored curable composition is appropriately selected according to the purpose, but is generally preferably 0.2 μm to 5.0 μm, preferably 0.3 μm to 2 μm. More preferably, it is 0.5 μm, most preferably 0.3 μm to 1.5 μm. In addition, the thickness of the colored layer here is a film thickness after pre-baking.

<Exposure process>
Subsequently, in the method for producing a color filter of the present invention, the colored layer formed on the support is subjected to pattern-like exposure to form a latent image (exposure process). The pattern-like exposure may be performed through a mask.
As light or radiation applicable to this exposure, g-line, h-line, i-line, KrF light and ArF light are preferable, and i-line is particularly preferable. When using the i-line to the irradiation light is ^preferably irradiated at an exposure dose of ^{100mJ / cm 2 ~10000mJ / cm 2} .

  Other exposure rays include ultra high pressure, high pressure, medium pressure and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various visible and ultraviolet laser light sources, fluorescent lamps, tungsten lamps, solar Light or the like can also be used.

(Exposure process using laser light source)
In the exposure method using the laser light source, an ultraviolet laser can be used as the light source. Laser is an acronym for Light Amplification by Stimulated Emission of Radiation in English. Oscillators and amplifiers that produce monochromatic light with stronger coherence and directivity by amplification and oscillation of light waves, utilizing the phenomenon of stimulated emission that occurs in materials with inversion distribution, crystals, glass, liquids, dyes as excitation media, There are gases and the like, and lasers having an oscillation wavelength for known ultraviolet light such as solid laser, liquid laser, gas laser, and semiconductor laser can be used from these media. Among these, a solid laser and a gas laser are preferable from the viewpoint of laser output and oscillation wavelength.

  As a laser that can be used in the exposure method using the laser light source, an ultraviolet laser having a wavelength in the range of 300 nm to 380 nm is preferable, and an ultraviolet laser having a wavelength in the range of 300 nm to 360 nm is more preferable. It is preferable in that it matches the photosensitive wavelength of the resist (colored curable composition).

Specifically, the Nd: YAG laser third harmonic (355 nm), which is a relatively inexpensive solid output, and the excimer laser XeCl (308 nm), XeF (353 nm) can be suitably used. .
The exposure amount for the object to be exposed (colored ^layer), in the range of ^{1mJ / cm 2 ~100mJ / cm 2} , the range of 1mJ / cm ² ~50mJ / cm 2 is more preferable. An exposure amount within this range is preferable from the viewpoint of pattern formation productivity.

  An exposure apparatus that can be used for the exposure method using the laser light source is not particularly limited, but commercially available devices include Calisto (buoy technology), EGIS (buoy technology), and DF2200G ( Dainippon Screen Co., Ltd. can be used, and devices other than those described above are also preferably used.

  Further, a light emitting diode (LED) and a laser diode (LD) can be used as the active radiation source. In particular, when an ultraviolet light source is required, an ultraviolet LED and an ultraviolet LD can be used. For example, Nichia Corporation has introduced a purple LED whose main emission spectrum has a wavelength between 365 nm and 420 nm. When even shorter wavelengths are required, US Pat. No. 6,084,250 discloses an LED that can emit actinic radiation centered between 300 nm and 370 nm. Other ultraviolet LEDs are also available and can emit radiation in different ultraviolet bands. The actinic radiation source particularly preferred in the present invention is a UV-LED, particularly preferably a UV-LED having a peak wavelength at 340 to 370 m.

  Since the parallelism of the ultraviolet laser is good, pattern exposure can be performed without using a mask at the time of exposure. However, it is more preferable to expose the pattern using a mask because the linearity of the pattern is further increased.

The exposed colored layer can be heated at 70 ° C. to 180 ° C. for about 0.5 to 15 minutes using a hot plate or oven before the next development processing.
The exposure can be performed while flowing a nitrogen gas in the chamber in order to suppress oxidation fading of the colorant in the colored layer.

<Development process>
Subsequently, the colored layer after exposure is developed with a developer (development process). Thereby, a negative colored pattern (resist pattern) can be formed.
As long as the developing solution dissolves the uncured portion of the colored layer and does not dissolve the cured portion, a combination of various organic solvents or an alkaline aqueous solution can be used.
Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, Examples include aqueous solutions of alkaline compounds such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo- [5,4,0] -7-undecene.

When the developer is an alkaline aqueous solution, the alkali concentration is preferably adjusted to pH 11 to 13, more preferably pH 11.5 to 12.5. In particular, an alkaline aqueous solution prepared by adjusting tetramethylammonium hydroxide so that the concentration is 0.001% by mass to 10% by mass, preferably 0.01% by mass to 5% by mass can be used as the developer.
The development time is preferably 30 seconds to 300 seconds, more preferably 30 seconds to 120 seconds. The development temperature is preferably 20 ° C to 40 ° C, more preferably 23 ° C.
Development can be performed by a paddle method, a shower method, a spray method, or the like.

  Moreover, after developing using alkaline aqueous solution, it is preferable to wash | clean with water. The cleaning method is also appropriately selected according to the purpose. While rotating a support such as a silicon wafer substrate at a rotational speed of 10 rpm to 500 rpm, pure water is supplied from the ejection nozzle in a shower shape from above the rotation center. A rinsing process can be performed.

  Thereafter, if necessary, post-heating and / or post-exposure may be performed on the formed colored pattern to promote curing of the colored pattern (post-curing step).

<Post-curing process>
In this invention, it is preferable to implement the post-curing process which further hardens the obtained pattern further after the process of forming a pattern by above-described image development.
The post-curing step is performed by heating (post-heating) and / or exposure (post-exposure such as ultraviolet irradiation), and the step of further curing the obtained pattern to form a colored layer for forming the next color pattern, etc. Thus, it is possible to prevent dissolution of the pattern and improve the solvent resistance of the pixel of the obtained color filter.
The post-curing step is preferably an ultraviolet irradiation step by ultraviolet irradiation.

-UV irradiation process-
In the ultraviolet irradiation process, the pattern is cured by post-exposure.
More specifically, the pattern after performing a developing process in the patterning step, for example, the exposure amount in the exposure process before development [mJ / cm ^2] of 10 times or more of the irradiation light amount [mJ / cm ^2] Irradiate with ultraviolet light (UV light). By irradiating the developed pattern with UV light for a predetermined time between the development processing in the pattern forming step and the heat treatment described later, it is possible to effectively prevent color migration when heated later. If the irradiation light quantity in this step is less than 10 times, color transfer between colored pixels or between upper and lower layers may not be prevented.
Especially, the irradiation light quantity of UV light is preferably 12 times or more and 200 times or less, more preferably 15 times or more and 100 times or less the exposure amount at the time of exposure in the pattern forming step.

  The post-exposure can be performed with g-line, h-line, i-line, KrF, ArF, UV light, electron beam, X-ray, etc., but g-line, h-line, i-line, UV light is preferable, and UV is particularly preferable. Light is preferred. When performing irradiation with UV light (UV cure), it is preferable to carry out at a low temperature of 20 ° C. or more and 50 ° C. or less (preferably 25 ° C. or more and 40 ° C. or less). The wavelength of the UV light preferably includes a wavelength in the range of 200 to 300 nm. As the light source, for example, a high pressure mercury lamp, a low pressure mercury lamp, or the like can be used. The irradiation time is 10 to 180 seconds, preferably 20 to 120 seconds, and more preferably 30 to 60 seconds.

  As a light source for irradiating UV light, for example, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a DEEP UV lamp, or the like can be used. Among them, the ultraviolet light to be irradiated contains light having a wavelength of 275 nm or less, and the irradiation illuminance [mW / cm 2] of the light having a wavelength of 275 nm or less is 5% or more with respect to the integrated irradiation illuminance of all wavelengths of light in the ultraviolet light. What can irradiate a certain light is preferable. By setting the irradiation illuminance of light having a wavelength of 275 nm or less in ultraviolet light to 5% or more, the effect of suppressing color transfer between colored pixels and the upper and lower layers and the effect of improving light resistance can be more effectively enhanced. From this point, it is preferable to use a light source different from a light source such as an i-line or the like used for exposure in the pattern forming step, specifically, a high pressure mercury lamp, a low pressure mercury lamp, or the like. Among these, for the same reason as described above, 7% or more is preferable with respect to the integrated irradiation illuminance of all wavelength light in ultraviolet light. Moreover, the upper limit of the irradiation illuminance of light having a wavelength of 275 nm or less is preferably 25% or less.

The integrated irradiation illuminance is a curve with the illuminance for each spectral wavelength (radiant energy passing through a unit area per unit time; [mW / m ² ]) as the vertical axis and the wavelength [nm] of light as the horizontal axis. When drawn, it means the sum (area) of the illuminance of each wavelength light included in the irradiation light.

The integrated irradiation illuminance in the ultraviolet light irradiated in the post-exposure in the ultraviolet irradiation step is preferably 200 mW / cm ² or more. When the integrated irradiation illuminance is 200 mW / cm ² or more, the effect of suppressing color transfer between colored pixels and the upper and lower layers and the effect of improving light resistance can be more effectively enhanced. Among them, preferred is ^{250~2000mW / cm 2, 300~1000mW / cm} 2 is more preferable.

  Moreover, it is preferable to implement post-heating at 100 to 300 degreeC using a hotplate or oven, More preferably, it is 150 to 250 degreeC. The post-heating time is preferably 30 seconds to 30000 seconds, and more preferably 60 seconds to 1000 seconds.

  In the post-curing step, post-exposure and post-heating may be used together. In this case, either may be performed first, but it is preferable to perform post-exposure prior to post-heating. This is because curing is promoted by post-exposure, thereby suppressing deformation of the shape due to heat sagging and soaking of the pattern seen in the post-heating process.

The colored pattern thus obtained constitutes a colored pixel in the color filter.
In the production of a color filter having colored pixels of a plurality of hues, the colored layer forming step, the exposing step, and the developing step (and the post-curing step as necessary) are repeated according to the desired number of colors. Thus, a color filter configured to have a desired number of hues can be manufactured.

  Even when the colored curable composition of the present invention adheres to, for example, a nozzle of a coating apparatus discharge section, a piping section of a coating apparatus, the inside of a coating apparatus, etc., it can be easily washed and removed using a known cleaning liquid. In this case, in order to perform more efficient cleaning and removal, it is preferable to use the solvent described above as the cleaning liquid as the solvent contained in the colored curable composition of the present invention.

JP-A-7-128867, JP-A-7-146562, JP-A-8-278737, JP-A-2000-273370, JP-A-2006-85140, JP-A-2006-291191, The cleaning liquids described in JP 2007-2101 A, JP 2007-2102 A, JP 2007-281523 A, and the like can also be suitably used as cleaning liquids for cleaning and removing the colored curable composition of the present invention. it can.
As the cleaning liquid, it is preferable to use alkylene glycol monoalkyl ether carboxylate or alkylene glycol monoalkyl ether.
These solvents that can be used as the cleaning liquid may be used alone or in combination of two or more.
When mixing 2 or more types of solvent, the mixed solvent formed by mixing the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group is preferable. The mass ratio of the solvent having a hydroxyl group and the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 80/20. The mixed solvent is a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), and the ratio is particularly preferably 60/40.
In addition, in order to improve the permeability of the cleaning liquid to the colored curable composition, the surfactant described above as a surfactant that may be contained in the colored curable composition may be added to the cleaning liquid.

Furthermore, as a method for producing a color filter using the colored curable composition of the present invention, in addition to the above method, it can be used for an ink jet method.
The method for producing the color filter by the ink jet method is not particularly limited, and the colored curable composition of the present invention (specifically, the step of preparing a substrate having recesses partitioned by partition walls and the recesses by the ink jet method) Includes a step of forming a color pixel of a color filter by applying a droplet of an inkjet ink of the present invention described later. For example, the methods described in paragraph numbers [0114] to [0128] of JP-A-2008-250188 can be used.

  The color filter of the present invention may further have an indium tin oxide (ITO) layer as a transparent conductive film. Examples of the ITO layer forming method include in-line low-temperature sputtering method, in-line high-temperature sputtering method, batch-type low-temperature sputtering method, batch-type high-temperature sputtering method, vacuum deposition method, and plasma CVD method. In order to reduce damage, a low-temperature sputtering method is preferably used.

<< Use of the color filter of the present invention >>
The color filter of the present invention is, for example, a liquid crystal display device such as a TV or a personal computer, an organic EL display device, a liquid crystal projector, a portable terminal such as a game machine or a mobile phone, a display device such as a digital camera or a car navigation system, particularly a color display device. The present invention can be suitably applied without particular limitation.
Further, it can be suitably used as a color filter for a solid-state imaging device such as a CCD image sensor or a CMOS image sensor used in a digital camera, a digital video camera, an endoscope, a mobile phone, or the like. Particularly, it is suitable for a high-resolution CCD element or CMOS element exceeding 1 million pixels.

<Solid-state imaging device>
The solid-state imaging device of the present invention includes the color filter of the present invention.
Specifically, a CCD image sensor or a CMOS image sensor used for a digital camera, a digital video camera, an endoscope, a mobile phone, or the like is preferable as the solid-state imaging device of the present invention. Particularly, a high-resolution CCD image sensor or CMOS image sensor exceeding 1 million pixels is suitable.
The configuration of the solid-state imaging device is not particularly limited as long as it includes the color filter of the present invention and functions as a solid-state imaging device. For example, the following configuration can be given.
That is, it has a structure in which a transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area is provided on a support, the color filter of the present invention is provided thereon, and then a microlens is laminated. .

  Moreover, the camera system including the color filter of the present invention includes a cover glass, a microlens, and the like in which the camera lens and the IR cut film are dichroically coated from the viewpoint of the light fading property of the colorant. It is desirable that the characteristics absorb part or all of UV light of 400 nm or less. Further, the structure of the camera system is preferably such that the oxygen permeability to the color filter is reduced in order to suppress oxidation fading of the colorant. For example, a part or the whole of the camera system Is preferably sealed with nitrogen gas.

<Display devices such as liquid crystal display devices and organic EL display devices>
A display device such as a liquid crystal display device or an organic EL display device of the present invention includes the color filter of the present invention.
Specifically, as a display device of the present invention, a liquid crystal display (liquid crystal display device; LCD), an organic EL display (organic EL display device), a liquid crystal projector, a display device for a game machine, a display device for a portable terminal such as a mobile phone. Display devices such as digital camera display devices and car navigation display devices, particularly color display devices are suitable.

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

  The color filter of the present invention is particularly effective 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.

The color filter of the present invention can also be used for a bright and high-definition COA (Color-filter On Array) system. In the COA type liquid crystal display device, as the required characteristics for the color filter layer, in addition to the normal required characteristics, the required characteristics for the interlayer insulating film, that is, low dielectric constant and stripping solution resistance are required. In the color filter of the present invention, it is considered that the transparency of the ultraviolet light that is the exposure light can be increased by using an exposure method using an ultraviolet light laser, or by selecting the hue and film thickness of the colored pixels. . As a result, the curability of the colored pixels is improved, so that the colorant layer provided directly or indirectly on the TFT substrate is particularly improved in the resistance to peeling liquid, and is useful for a COA type liquid crystal display device. 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 15 μm in order to connect the ITO electrode arranged on the colored layer and the terminal of the driving substrate below the colored layer. It is necessary to form a conduction path such as a through-hole or a U-shaped depression, and the dimension of the conduction path (that is, the length of one side) is particularly preferably 5 μm or less. It is also possible to form a conduction path of 5 μm or less.
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)".

In addition to the color filter of the present invention, the liquid crystal display device includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film. 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, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi), etc. Have been described.

When the color filter of the present invention is used in a liquid crystal display device, a high contrast can be realized when combined with a 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.
In addition, when used in an organic EL display device, it is possible to provide an organic EL display device that achieves high contrast, high luminance, and high color purity and good color reproducibility.

  As described above, the colored curable composition, the color filter and the manufacturing method thereof, the solid-state imaging device, and the display device of the present invention have been described in detail with reference to various embodiments, but the present invention is not limited to the above embodiments. Of course, various improvements and modifications may be made without departing from the scope of the present invention.

  The present invention will be described more specifically with reference to the following examples. The materials, reagents, ratios, equipment, operations, and the like shown in the following examples can be appropriately changed without departing from the scope of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In the following examples, “%” and “parts” represent “% by mass” and “parts by mass” unless otherwise specified.

<Pigment Blue-15: 6 pigment dispersion>
C. I. Pigment Blue 15: 6 is 11.5 parts (average secondary particle diameter 55 nm), pigment dispersant BYK-161 (manufactured by BYK) is 3.5 parts, and propylene glycol monomethyl ether acetate (hereinafter “PGMEA”). ) 85 parts of the mixed solution was mixed and dispersed for 3 hours by a bead mill (zirconia beads 0.3 mm diameter). Thereafter, the dispersion treatment was further performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high-pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a pigment dispersion. With respect to the pigment dispersion, the average primary particle size of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)) and found to be 25 nm.

[Example 1]
<Preparation of colored curable composition 1>
The following components were mixed and dissolved to obtain a colored curable composition.
Pigment Blue-15: 6 pigment dispersion (the above pigment dispersion, solid content concentration 15%, pigment concentration 11.54%) 55.47 parts Exemplified compound 101 3.20 parts Polymerizable compound Dipentaerythritol hexaacrylate (Nippon Kayaku, KAYARAD DPHA) 4.15 parts Polymerizable compound Glycidyl methacrylate (manufactured by Wako Pure Chemicals, M-100) 0.80 parts Polymerization initiator OXE-02 (the following structure, manufactured by BASF; oxime series) Initiator) 0.96 parts, alkali-soluble resin benzyl methacrylate / methacrylic acid copolymer 30% PGMEA solution (resin A) (molar ratio = 70: 30, weight average molecular weight 30000) 0.53 parts surfactant (Solsperse 20000 (Nippon Lubrizol Co., Ltd.) 1% cyclohexanone solution 0.10 parts / solvent PGM A 34.79 parts

[Examples 2-8, Comparative Examples 1-2]
<Preparation of colored curable compositions 2 to 10>
Each component in the preparation of the colored curable composition 1 was changed as shown in Table 2, and other than that, the colored curable compositions 2 to 10 were prepared in the same manner as in the preparation of the colored curable composition 1.
The structures of the compounds used in Table 2 are shown below.
In Table 2, two or more compounds described in the same column indicate that two types were mixed and used, the numerator in the column of the amount represents the amount of the compound described above, and the denominator is Represents the amount of the described compound.

M-101: 2-methacryloyloxyethyl isocyanate (produced by Showa Denko KK, Karenz MOI)
M-102: 1,1-bis- (acryloyloxymethyl) ethyl isocyanate (produced by Showa Denko KK, Karenz BOI)

  In the preparation of the colored curable composition 5, in the preparation of the Pigment Blue-15: 6 pigment dispersion, 20% by mass of Pigment Blue-15: 6 was replaced with Pigment Violet-23, and the others were Pigment Blue. A pigment dispersion obtained in the same manner as in the preparation of the -15: 6 pigment dispersion was used.

Using the obtained colored curable compositions 1 to 10, development omission was evaluated by the following evaluation method.
1) Production of glass wafer with undercoat layer A 6-inch glass wafer was heat-treated in an oven at 200 ° C. for 30 minutes. Next, CT-4000 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) is applied on the glass wafer so as to have a dry film thickness of 1 μm, and further heated and dried on a hot plate at 200 ° C. for 5 minutes to form an undercoat layer. Then, a glass wafer with an undercoat layer was obtained.

2) Color application, exposure, development, and measurement of absorbance of the curable composition The color curable compositions 1 to 10 were applied on the undercoat layer of the glass wafer with the undercoat layer obtained in 1) above, and dried. A coating film of the colored curable composition was formed so that the film thickness was 0.6 μm. And after heat-processing (prebaking) for 120 second using a 100 degreeC hotplate, the light absorbency was measured using the microspectrophotometer (Lambda Vision LV microV) (measurement 1). Then, i-ray stepper exposure apparatus FPA-3000i5 + (Canon (Ltd.)) 100 mJ / cm ² exposure amount in the range of 100~2500mJ / cm ² pattern at a wavelength of 365nm through island pattern mask 5μm square using Irradiation was carried out by changing each step. Then, the glass wafer on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type; manufactured by Chemitronics), and an alkali developer CD-2000 ( Paddle development was performed at 23 ° C. for 300 seconds using FUJIFILM Electronics Materials Corporation. Next, while rotating the glass wafer at a rotation speed of 50 rpm, pure water was supplied from the upper part of the rotation center in a shower-like manner to perform a rinsing treatment, followed by spray drying to obtain a colored pattern. Then, the light absorbency of the colored pattern irradiated with the exposure amount in which the pattern of 5 micrometers was formed was measured using the microspectrophotometer (LV microV by Lambda Vision company) (measurement 2).

3) Evaluation The transmission absorption spectra obtained by the above-mentioned measurement 1 and measurement 2 were evaluated for the elution degree of whether or not the dye was eluted in the alkaline developer by the following formula.
(Elution degree)
= ((Absorbance at wavelength 550 nm of measurement 2) / (absorbance at wavelength 650 nm of measurement 2)-(absorbance at wavelength 550 nm of measurement 1) / (absorbance at wavelength 650 nm of measurement 1)) x 100 [%]

4) Evaluation criteria ○: Dissolution rate <20%
Δ: 20% ≦ elution degree <50%
×: Elution degree ≧ 50%

  As shown in Table 3, the colored curable composition of the present invention had a small dye elution when developed using an alkaline developer, and a colored pixel having a desired hue could be obtained.

Claims (9)

  (A) a phthalocyanine pigment, (B) a dye multimer containing a dipyrromethene structure, (C) a polymerization initiator, (D) a polymerizable compound, and (E) a solvent, wherein the (D) polymerizable compound is an epoxy group And a colored curable composition which is an ethylenically unsaturated polymerizable compound containing at least one of isocyanate groups.   2. The colored curable product according to claim 1, wherein the ethylenically unsaturated polymerizable compound containing at least one of the epoxy group and the isocyanate group is glycidyl (meth) acrylate or 2- (meth) acryloylethyloxyethyl isocyanate. Composition. The dye portion in the dye multimer containing the dipyrromethene structure is a structure derived from a dipyrromethene metal complex compound obtained from a dipyrromethene compound represented by the following general formula (M) and a metal or a metal compound, or a tautomer thereof. The colored curable composition of Claim 1 or Claim 2.

[In General Formula (M), R ^{4 to} R ¹⁰ each independently represents a hydrogen atom or a monovalent substituent. However, R ⁴ and R ⁹ are not bonded to each other to form a ring. ]   A colored curable composition, wherein the colored curable composition according to any one of claims 1 to 3 is used for forming a colored pixel by a photolithography method.   The color filter which uses the colored curable composition of any one of Claims 1-4.   A colored layer forming step of forming a colored layer by applying the colored curable composition according to any one of claims 1 to 4 on a support, and pattern-like exposure to the colored layer. And a developing process for forming a pattern by developing the colored layer on which the latent image is formed, and an exposure process for forming a latent image.   A solid-state imaging device comprising the color filter according to claim 5.   A liquid crystal display device comprising the color filter according to claim 5.   An organic EL display device comprising the color filter according to claim 5.