JP5986671B2 - COLORING COMPOSITION, INKJET INK, COLOR FILTER AND ITS MANUFACTURING METHOD, SOLID-STATE IMAGING DEVICE, AND DISPLAY DEVICE - Google Patents

Description

  The present invention relates to a coloring composition, an inkjet ink, a color filter and a method for producing the same, a solid-state imaging device, and a display device.

In recent years, with the development of personal computers, particularly large-screen liquid crystal televisions, the demand for liquid crystal displays (LCD), especially color liquid crystal displays, has been increasing. The spread of organic EL displays 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 displays and optical elements, 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 a display device or an image sensor, light passing therethrough is divided into three primary colors. It plays a role to draw.

  The colorant used in the color filter is commonly required to have the following characteristics. In other words, it has optical characteristics that are favorable for color reproducibility, optical scattering such as light scattering that causes a decrease in contrast of a liquid crystal display, and unevenness in optical density that causes color unevenness and roughness of a solid-state imaging device. There is a need for a high degree of fastness, such as heat resistance, light resistance, moisture resistance, and the like, a large molar extinction coefficient, and a thin film.

  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 radiation-sensitive 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, color filters manufactured by the photolithographic method using the pigment dispersion method are excellent in light resistance and heat resistance in liquid crystal displays, but have problems such as a decrease in contrast due to light scattering by pigment particles and an increase in haze. Have.

  In addition to the photolithography method, a method for forming a colored layer (color pixel) by spraying colored ink by an inkjet method has been proposed as a method for producing a color filter (see, for example, Patent Documents 1 and 2). .)

  The ink jet method is a recording method in which characters and images are obtained by ejecting and adhering ink droplets directly from a very fine nozzle to a recording member. The ink jet method has an advantage that a color filter having a large area can be manufactured with high productivity by sequentially moving the ink jet head, and the operability is low with low noise. Ink jet ink using a pigment dispersion method is used for manufacturing a color filter by such an ink jet method. As an inkjet ink using the pigment dispersion method, for example, an inkjet ink for a color filter containing a binder component, a pigment, and a solvent having a boiling point of 180 ° C. to 260 ° C. and a vapor pressure at room temperature of 0.5 mmHg or less. It has been proposed (see, for example, Patent Document 3).

  When ink jet ink using such a pigment dispersion method is used in the production of a color filter, nozzle clogging due to pigment aggregation of the ink frequently occurs, and therefore, improvement in discharge stability is desired. Furthermore, because of the aggregated pigment, the recovery function of the ink discharge state by the discharge recovery operation such as wiping and purging tends to be lowered. Further, during wiping, the nozzle surface may be rubbed by the aggregated pigment, and the ink may be ejected in a bent direction.

  When dyes are used instead of the pigment dispersion method, the color filters for solid-state image sensors can solve the problem of color unevenness and roughness, and high resolution can be achieved, while the color filters for liquid crystal displays and organic EL displays can be used for contrast and haze. Improvements in optical properties are expected. Ink jet methods using dyes generally have high ejection stability, and it is expected that the ink ejection state can be easily recovered by wiping or purging even when nozzle clogging occurs due to an increase in ink viscosity.

  Under the above background, the use of a dye as a colorant has been studied (for example, see Patent Document 4). 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 that optical characteristics change due to a high temperature during 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 The 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 a 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 5).
In addition, a method for producing a color filter is disclosed in which polymerization is performed with the exposure temperature raised by irradiating the colored pattern with light while heating the substrate after forming the colored pattern, thereby increasing the polymerization rate of the system. (For example, refer to Patent Document 6).
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 7).

Further, focusing on spectral characteristics suitable for color filters, colored curable compositions and pigment compounds using dipyrromethene dyes have been studied (for example, see Patent Document 8).
Moreover, regarding the improvement of the sublimation defect in color filter production, a color filter containing a polymer having a triphenylmethane dye in the molecule as a colorant has been proposed (for example, see Patent Document 9).

JP 59-75205 A JP 2004-339332 A JP 2002-201387 A JP-A-6-75375 Japanese Patent Laying-Open No. 2005-316012 Japanese Patent No. 3309514 JP 2006-258916 A JP 2008-292970 A Japanese Patent No. 3736221

In the coloring composition for a color filter containing a dye, there are essential problems peculiar to the following dyes (6) to (8) in addition to the above problems.
(6) Dye permeation at the time of next color application When forming a color pattern using a coloring composition using a dye, the dye is likely to permeate at the time of application to the other color pattern (or layer) previously formed, resulting in color mixing. Cheap.
(7) Dye elution during alkali development In a coloring 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 coloring 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.
In Patent Document 9, although there is a disclosure regarding sublimation suppression derived from the characteristics of a polymer having a triphenylmethane dye, elution of the colorant during alkali development, soaking of the colorant, and thermal diffusion of the colorant by heat treatment ( No mention is made of color transfer) and development residues.

This invention is made | formed in view of the said background, and makes it a subject to achieve the following objectives.
That is, the present invention provides a colored composition capable of forming a colored film in which elution of the colorant during alkali development, infiltration of the colorant, thermal diffusion (color transfer) of the colorant by heat treatment, and development residue is suppressed. The purpose is to do.
Another object of the present invention is to provide an inkjet ink that can form colored pixels with excellent heat resistance and has excellent ejection stability.
In addition, the present invention provides a color filter excellent in heat resistance in which colorant soaking, thermal diffusion (color transfer) of the colorant due to heat treatment, and color mixing due to development residue are suppressed, and a method for producing the same, and the color An object of the present invention is to provide a solid-state imaging device and a display device including a filter.

As a result of repeated investigations with dipyrromethene dye compounds, the present inventors have increased the amount of dyes to a specific molecular weight or more, so that the dye soaks in the next color coating, the elution of the dye during alkali development, and the thermal diffusion by heat treatment. (Color transfer), the knowledge that there is a tendency for development residue after development to be small. As a result of extensive studies, in addition to adjusting the molecular weight, the dye is adjusted so that it has a specific molecular weight distribution (dispersion degree), so that the dye soaks in the next color application, the elution of the dye during alkali development, and heat treatment As a result, it was found that all of the development residue after heat diffusion and development can be surprisingly improved.
Furthermore, when this knowledge was verified by increasing the amount of other dye compounds, it was found that the same remarkable effect could be obtained in the same molecular weight and dispersion range.

Although the above-mentioned Patent Document 9 also discloses a dye multimer (a polymer having a triphenylmethane dye in the molecule), these issues are not mentioned, and the physical properties are adjusted to this specific range. Thus, it was impossible to assume that these problems could be solved.
The present inventors have completed the present invention based on the above findings.
That is, specific means for solving the above problems are as follows.

<1> The colorant has a weight average molecular weight (Mw) of 5,000 or more and 20,000 or less, and a dispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 1.00 or more and 2.50. A dye multimer having at least one alkali-soluble group selected from a carboxyl group, a phosphono group, and a sulfo group,
Furthermore, it contains a polymerizable compound, a polymerization initiator, and a solvent,
The dye multimer is a dye multimer having at least one of structural units represented by the following general formula (A) in a range of 57% by mass or more and 100% by mass or less and having the alkali-soluble group.
The coloring composition in which the said polymerization initiator contains an oxime type compound.

[In General Formula (A), X ^A1 and X ^A2 each independently represent any one of the following (X-1) to (X-15) linking groups formed by polymerization. .
L ^A1 and L ^A2 are each independently a single bond, or a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, Substituted or unsubstituted heterocyclic linking group, —CH ₂ ═CH ₂ —, —O—, —S—, —NR—, —C (═O) —, —SO—, —SO ₂ —, (2), a linking group represented by the following general formula (3), a linking group represented by the following general formula (4), or a combination of two or more of these. Represents a divalent linking group. R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
Dye represents a dye residue obtained by removing 1 to 1 + m arbitrary hydrogen atoms from a dye compound. The dye compound is one selected from the group consisting of a cyanine dye, a triphenylmethane dye, a xanthene dye, and a dipyrromethene dye.
m represents an integer of 0 to 3.
Dye and LA ² may be linked by any of a covalent bond, an ionic bond, and a coordination bond. ]

[In (X-1) to (X-15), * represents a site linked to L ^A1 or L ^A2 . ]

[In General Formula (2) to General Formula (4), 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; Represents an integer of 0 to 4;
In general formula (2) to general formula (4), * represents a position bonded to X ^A1 or X ^A2 in general formula (A).
** represents a position bonded to Dye in the general formula (A). ]

<2> The colored composition according to <1>, wherein an acid value of the dye multimer is 0.5 mmol / g or more and 3.0 mmol / g or less.

<3> 1 to 1 + m of arbitrary hydrogen atoms are removed from a dye compound in which Dye in the general formula (A) is one selected from the group consisting of a triphenylmethane dye and a xanthene dye. The coloring composition according to <1> or <2>, which represents a dye residue.
<4> In any one of <1> to <3>, Dye in the general formula (A) represents a dye residue obtained by removing 1 to 1 + m of arbitrary hydrogen atoms from a triphenylmethane dye. The coloring composition as described.

<5> The colored composition according to any one of <1> to <4>, wherein the dye multimer has a weight average molecular weight (Mw) of 5,000 to 16,000.

<6> The colored composition according to any one of <1> to <5>, wherein the dye multimer has a maximum absorption wavelength in a range of 400 nm to 780 nm.

<7> The colored composition according to any one of <1> to <6>, wherein the content of the dye multimer in the total solid content is 0.1% by mass or more and 70% by mass or less.
<8> The colored composition according to any one of <1> to <6>, wherein the content of the dye multimer in the total solid content is 5% by mass or more and 60% by mass.

<9> The <1> to <8>, wherein the dye multimer has at least one of the structural units represented by the general formula (A) in a range of 65% by mass to 88% by mass. The coloring composition as described in.

<10> A color filter formed using the colored composition according to any one of <1> to <9>.

<11> An inkjet ink comprising the colored composition according to any one of <1> to <9>.

<12> a step of applying the colored composition according to any one of <1> to <9> on a support to form a colored layer;
Exposing the formed colored layer through a mask;
Developing the exposed colored layer to form a colored pattern;
The manufacturing method of the color filter which has this.

<13> a step of preparing a substrate having a recess partitioned by a partition;
Forming the colored pixels of the color filter by applying droplets of the inkjet ink according to <11> to the recesses by an inkjet method;
The manufacturing method of the color filter which has this.
<14> A solid-state imaging device including the color filter according to <10>.
<15> A display device comprising the color filter according to <10>.

According to the present invention, there is provided a coloring composition capable of forming a colored film in which elution of the colorant during alkali development, infiltration of the colorant, thermal diffusion (color transfer) of the colorant by heat treatment, and development residue is suppressed. can do.
In addition, according to the present invention, it is possible to provide a color pixel excellent in heat resistance and to provide an inkjet ink excellent in ejection stability.
Further, according to the present invention, the color filter soaked in the colorant, the thermal diffusion (color transfer) of the colorant due to the heat treatment, and the color mixture due to the development residue is suppressed, the color filter excellent in heat resistance, and the production method thereof, and A solid-state imaging device and a display device including the color filter can be provided.

Hereinafter, the coloring composition, ink-jet ink, color filter and production method thereof, solid-state imaging device, and 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.

≪Coloring composition≫
The coloring composition of the present invention has a weight average molecular weight (Mw) of 5,000 or more and 20,000 or less and a dispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 1 as a colorant. It contains a dye multimer having an alkali-soluble group that is 0.000 or more and 2.50 or less (hereinafter also referred to as “specific dye multimer”).
Hereinafter, the degree of dispersion (weight average molecular weight (Mw) / number average molecular weight (Mn)) is also simply referred to as “dispersion degree (Mw / Mn)”.
By forming the colored composition into the constitution of the present invention, when forming a colored film, elution of the colorant at the time of alkali development, soaking of the colorant, thermal diffusion (color transfer) of the colorant by heat treatment, and Development residue is suppressed.
Furthermore, the colored composition of the present invention can form a colored film excellent in fastness (heat resistance and light resistance), and is excellent in storage stability.
For this reason, the coloring composition of this invention is suitable for the use which produces the color filter by the photolitho method or the inkjet method.

As a specific form of the colored composition of the present invention, from the viewpoint of more effectively achieving the effects of the present invention described above, a negative or positive type containing a specific dye multimer and a radiation-sensitive compound. The form of the colored photosensitive composition is preferred.
Among these, from the viewpoint of achieving the effect of the present invention particularly effectively, a negative colored photosensitive composition comprising a specific dye multimer, a polymerization initiator that is a radiation-sensitive compound, a polymerizable monomer, and a solvent. It is preferable that it is a form of a thing (coloring curable composition).
Moreover, as another form of the coloring composition of this invention, the form of the ink for inkjets containing a specific pigment | dye multimer and at least one of a solvent and a polymeric compound is mentioned.
According to the form of the inkjet ink, colored pixels having excellent heat resistance can be formed, and the ejection stability is improved.
Hereinafter, the specific dye multimer will be described first.

<Specific dye multimer>
The specific dye multimer in the present invention has an alkali-soluble group having a weight average molecular weight (Mw) of 5,000 or more and 20,000 or less and a dispersity (Mw / Mn) of 1.00 or more and 2.50 or less. It is a multimer.
By satisfying this relationship, in the colored film formed from the colored composition of the present invention, elution of the colorant at the time of alkali development, penetration of the colorant, thermal diffusion (color transfer) of the colorant by heat treatment And development residue is greatly improved.

When the weight average molecular weight (Mw) is less than 5,000, when a colored film is formed, thermal diffusion (color transfer) of the colorant due to heat treatment, soaking of the colorant, alkali elution resistance, and solvent resistance are deteriorated. Tend to.
When the weight average molecular weight exceeds 20,000, the development residue tends to deteriorate.
The weight average molecular weight needs to be 5,000 or more and 20,000 or less, preferably 5,000 or more and 16,000 or less, and more preferably 6,000 or more and 12,000 or less.

Further, when the dispersity (Mw / Mn) exceeds 2.50, when a colored film is formed, thermal diffusion (color transfer) of the colorant by heat treatment, penetration of the colorant, alkali elution resistance, solvent resistance Tend to get worse.
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. It is.

  The weight average molecular weight and the molecular weight distribution are values measured by gel permeation chromatography (GPC) using HLC-8220 GPC (developing solvent NMP, detection RI, converted value by polystyrene) manufactured by Tosoh Corporation. .

In the present invention, as means for adjusting the weight average molecular weight (Mw) of the dye multimer to a range of 5,000 or more and 20,000 or less, for example, at the time of synthesis of the dye multimer, the amount of polymerization initiator or the chain transfer agent Means for adjusting the amount and means for adjusting the reaction temperature can be mentioned.
Specifically, the amount of the polymerization initiator is preferably 2 to 30 mol% and more preferably 2 to 20 mol% with respect to the total of the polymerizable dye monomer and the other polymerizable monomer.
Moreover, 1-20 mol% is preferable with respect to the sum total of a polymeric pigment | dye monomer and another polymerizable monomer, and, as for the amount of chain transfer agents, 2-15 mol% is more preferable.
The reaction temperature varies depending on the type of polymerization initiator used, but it is preferable to adjust the reaction initiator so that the half-life of the polymerization initiator is 15 minutes to 120 minutes. For example, in the case of V601 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.), 60 to 90 ° C is preferable, and 70 to 85 ° C is more preferable.

In the present invention, the means for adjusting the dispersity (Mw / Mn) of the dye multimer in the range of 1.00 or more and 2.50 or less is, for example, a means for adjusting by changing the kind and amount of the reprecipitation solvent. Is mentioned.
Specifically, it is preferable to select a solvent having high solubility of the polymerizable dye monomer to be used as the reprecipitation solvent, and it is more preferable to select a solvent having low solubility of the dye multimer in addition to this. By selecting such a solvent, the residual ratio of the polymerizable dye monomer can be lowered as much as possible, and at the same time, the low molecular weight side in the molecular weight distribution of the dye multimer can be selectively removed. Therefore, selecting the above-mentioned solvent is particularly effective for reducing the degree of dispersion of the dye multimer. Although different depending on the polymerizable dye monomer to be used, it is preferable to use lower alcohols (for example, methanol, ethanol, isopropanol and the like), acetonitrile and the like. It is also preferable to combine two or more solvents.
Moreover, the amount of the reprecipitation solvent with respect to the polymerization reaction solution of the dye multimer (the solution of the dye multimer when reprecipitation is repeated) is preferably 1 to 100 times by mass, and more preferably 2 to 50 times by mass.
Further, it is more preferable to dilute the polymerization reaction solution of the dye multimer (in the case of repeating reprecipitation, the dye multimer solution) with a reprecipitation solvent of 0.1 to 1 times by mass. This effectively removes the polymerizable dye monomer and is effective in reducing the degree of dispersion.
Moreover, repeating reprecipitation is also preferable as a means for adjusting the degree of dispersion. In this case, the same precipitation conditions may be repeated for the most precipitation conditions, or different conditions may be combined.

The “pigment multimer” herein is a multimer having a dye skeleton present in the range of the maximum absorption wavelength in the range of 400 nm to 780 nm, and is not particularly limited as long as it is a multimer having the maximum absorption wavelength in the above range. .
The dye skeleton is monomethine, dimethine, trimethine, cyanine, merocyanine, dicyanostyryl, diphenylmethane, triphenylmethane, xanthene, squarylium, quinophthalone, monoazo, bisazo, disazo, Trisazo, anthraquinone, anthrapyridone, perylene, diketopyrrolopyrrole, isoindoline, phthalocyanine, azomethine, dioxazine, and dipyrromethene dye skeletons and metal complexes thereof.
The maximum absorption wavelength was obtained by measuring an absorption spectrum in an ethyl acetate solution (concentration: 1 × 10 ⁻⁶ mol / L, optical path length: 10 mm) using an ultraviolet-visible spectrophotometer (UV3100 manufactured by Shimadzu Corporation). is there.

The dye multimer in the present invention 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.
The specific dye multimer in the present invention can be synthesized, for example, by the following (Method 1) to (Method 4), but may be synthesized by methods other than these, and is not limited by this description.

(Method 1) A method of synthesizing a polymerizable dye monomer by homopolymerization reaction.
This (Method 1) may be a method of synthesizing by a homopolymerization reaction of a polymerizable dye monomer having an alkali-soluble group, or may be a polymerizable dye monomer (not having an alkali-soluble group). Alternatively, a method of synthesizing a dye multimer synthesized by a homopolymerization reaction by introducing an alkali-soluble group by a polymer reaction may be used.

(Method 2) A method of synthesizing by a copolymerization reaction of at least one polymerizable dye monomer and at least one other polymerizable monomer (comonomer).
This (Method 2) may be a method using a monomer having an alkali-soluble group as at least one of a polymerizable dye monomer and another polymerizable monomer, or at least one of the polymerizable dye monomer and other A method of synthesizing a dye multimer synthesized by copolymerization with at least one polymerizable monomer (comonomer) by introducing an alkali-soluble group by a polymer reaction may be used.

(Method 3) A method of synthesis by introducing a dye structure (dye residue) into a polymer compound by a polymer reaction.
This (Method 3) may be a method of introducing a dye structure (dye residue) to a polymer compound having an alkali-soluble group by a polymer reaction, or may be a polymer compound (having an alkali-soluble group). Or a method of introducing a dye structure (dye residue) and an alkali-soluble group by a polymer reaction.

(Method 4) A method of linking two or more dye structures (dye residues) via a linking chain.
This (Method 4) may be a method of linking two or more dye structures (dye residues) via a linking chain having an alkali-soluble group, or two or more dye structures via a linking chain. It may be a method of linking (dye residue) and a structural unit having an alkali-soluble group, or a compound obtained by linking two or more dye structures (dye residue) via a linking chain. On the other hand, a method of introducing an alkali-soluble group may be used.

  The specific dye multimer in the present invention is preferably an oligomer or a polymer, and more preferably an oligomer or a polymer obtained by the above (Method 1) or the above (Method 2).

When the dye multimer used in the present invention is synthesized by a copolymerization reaction (in the case of (Method 2) above), the other polymerizable monomer (comonomer) is particularly limited as long as it can be polymerized with the polymerizable dye monomer. There is no.
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 “dye multimer having an alkali-soluble group” 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), and is an alkali. A dye multimer having a soluble group, or a dye multimer represented by the general formula (D) and having an alkali-soluble group.

(Structural unit represented by formula (A))

In the 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 removes 1 to 1 + m arbitrary hydrogen atoms from the dye compound. Represents a pigment residue. X ^A2 represents a linking group formed by polymerization, L ^A2 represents a single bond or a divalent linking group, and m represents an integer of 0 to 3. 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. Specifically, it is a linking group shown below.
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. 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 arbitrary hydrogen atoms of the dye compound.
Dye is a monomethine dye, dimethine dye, trimethine dye, cyanine dye, merocyanine dye, dicyanostyryl dye, diphenylmethane dye, triphenylmethane dye, xanthene dye, squarylium dye, quinophthalone dye, Monoazo dyes, bisazo dyes, disazo dyes, trisazo dyes, anthraquinone dyes, anthrapyridone dyes, perylene dyes, diketopyrrolopyrrole dyes, isoindoline dyes, phthalocyanine dyes, azomethine dyes, dioxazines This is a dye residue obtained by removing 1 to 1 + m hydrogen atoms from one dye compound selected from the group consisting of a dye and a dipyrromethene dye.

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 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, and m represents an integer of 0 to 3. 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 or a dye residue obtained by removing 1 to m arbitrary hydrogen atoms from the dye compound. Examples of the dye compound include the dye compounds mentioned in the description of Dye in the general formula (A).

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 dye residue obtained by removing two arbitrary hydrogen atoms from a dye compound.

In the general formula (C), Dye represents a divalent dye residue.
Dye is a monomethine dye, dimethine dye, trimethine dye, cyanine dye, merocyanine dye, dicyanostyryl dye, diphenylmethane dye, triphenylmethane dye, xanthene dye, squarylium dye, quinophthalone dye, Monoazo dyes, bisazo dyes, disazo dyes, trisazo dyes, anthraquinone dyes, anthrapyridone dyes, perylene dyes, diketopyrrolopyrrole dyes, isoindoline dyes, phthalocyanine dyes, azomethine dyes, dioxazines It is a dye residue obtained by removing two hydrogen atoms from one dye compound selected from the group consisting of a dye and a dipyrromethene dye.

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.

(Copolymerization component)
The dye multimer of the present invention may be composed only of structural units represented by the general formula (A), the general formula (B), and the general formula (C) (in this case, the general formula (A), the general formula (B), and the structural unit represented by the general formula (C) itself contains an alkali-soluble group), the general formula (A), the general formula (B), and the general formula ( C) may be configured to include at least one of the structural units represented by (C) and another structural unit (in this case, the general formula (A), the general formula (B), and the general formula ( At least one of the structural units represented by C) and at least one of the other structural units includes 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.

(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 Dye represents a dye residue obtained by removing one arbitrary hydrogen atom from a dye compound.

  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 in general formula (D) is synonymous with Dye in general formula (A) except that it is limited to monovalent.

(Dye monomer represented by general formula (1))
The specific dye monomer in the present invention is preferably a dye monomer obtained by polymerizing a dye monomer represented by the following general formula (1) and having an alkali-soluble group.

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 pigment residue. R ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
Dye in general formula (1) is synonymous with Dye in general formula (A), and its preferable range is also the same.

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. 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 represented by the general formula (1) is a dye ^{_{compound, - (L 2) n -}} (L 1) m -C (R 1) = polymerizable group represented by CH ₂ Is a compound introduced.
When both m and n are 0, a —C (R ¹ ) ═CH ₂ group is directly introduced into the dye compound.

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). 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 the preferred embodiment is 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, and k represents an integer of 0 to 4. * 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.

(Dye residue)
In the general formula (A), the general formula (B), the general formula (C), the general formula (D), and the general formula (1), Dye is a monomethine dye or a dimethine dye as described above. , Trimethine dyes, cyanine dyes, merocyanine dyes, dicyanostyryl dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, squarylium dyes, quinophthalone dyes, monoazo dyes, bisazo dyes, disazo dyes Group consisting of dye, trisazo dye, anthraquinone dye, anthrapyridone dye, perylene dye, diketopyrrolopyrrole dye, isoindoline dye, phthalocyanine dye, azomethine dye, dioxazine dye, and dipyrromethene dye From one dye compound selected from the group consisting of 1 to m hydrogen atoms Is a dye residue off with a single range.

Specific examples of the dipyrromethene dye include dipyrromethene metal complex compounds represented by the following general formula (5) or the following general formula (6).
However, the present invention is not limited to these.

-Dipyrromethene metal complex compound represented by 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. 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-based metal complex compound represented by the general formula (5) in order to form a dye residue, but in terms of synthesis compatibility, R Any one or two portions of ^{4 to} R ⁹ are preferred, any one or two portions of R ⁴ , R ⁶ , R ⁷ and R ⁹ are more preferred, and any one of R ⁴ and R ⁹ Or two sites are more preferred.

As a method of 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 of the dipyrromethene metal complex compound represented by the general formula (5) is used. Any one or two or more substituents of ^{4 to} R ¹⁰ , X ¹ and X ² can have an alkali-soluble group. Among these substituents, any ^one 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, for example, 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 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.

There is no particular limitation on the site where one or two hydrogen atoms are removed from the dipyrromethene-based metal complex compound represented by the general formula (6) in order to form a dye residue, but R ^{11 to} R ¹⁷ , X ¹ 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 of the dipyrromethene metal complex compound represented by the general formula (6) is used. Any one or two or more substituents of ^{11 to} R ¹⁷ , X ¹ and Y ^{1 to} Y ² may 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-based metal complex compound represented by the general formula (5) and the general formula (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-based 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. No. 2002-1555052, Japanese Patent No. 3614586, 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.

(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-%” represents “mass%” and “mol-%” represents “mol%”.

(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.

-Exemplary compound 4-3
The following dye monomer 4 (6.5 g), methacrylic acid (3.5 g) and 420 mg of n-dodecanethiol as a chain transfer agent were dissolved in 40 ml of methyl cellosolve and stirred at 85 ° C. under nitrogen. 478 mg of 2′-azobis (2-methylpropionate) was added. Thereafter, 478 mg of dimethyl 2,2′-azobis (2-methylpropionate) was additionally added 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 solvent was distilled off, the resulting residue was suspended in methanol, and the resulting crystals were filtered to give Exemplified Compound 4-3 (8.0 g).
The following dye monomer 4 can be synthesized by a synthesis method described in Japanese Patent No. 3736221, for example. 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 coloring 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 coloring composition of this invention, you may use together a specific coloring agent and another coloring agent. Examples of other colorants will be described later.
0.1-70 mass% is preferable, and, as for content (specific content in the case of 2 or more types) of the specific colorant in the total solid of the coloring composition of this invention, 1-65 mass% is more preferable. 5 to 60% by mass is particularly preferable.
1-70 mass% is preferable, and, as for the total colorant content in the total solid of the colored curable composition which used the specific coloring agent of this invention, and the other coloring agent of the following description together, 20-65 mass% is more preferable. 40 to 60% by mass is particularly preferable. The specific colorant of the present invention is particularly useful for increasing the amount of colorant in the total solid content of the colored curable composition from the viewpoint of thinning.

  The colored 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 pigments 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, Pigment Blue 15, 15: 6, 16, 22, 29, 60, 64, Pigment Green 7, 36, 58, Pigment Yellow 20, 24, 86, 81, 83, 93, 108, 109, 110, 117, 125, 137, 138, 139, 147, 148, 153, 154, 166, 168, 185, Pigment Orange 36, Pigment Violet 23, etc. However, it is not limited to these.

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, these dyes and pigments may be used in combination of two or more in order to obtain the desired hue.

<Polymerizable compound>
The coloring composition of the present invention preferably contains a polymerizable compound.
The polymerizable compound is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more.
Such compounds are widely known in the industrial field, and can be used without any particular limitation in the present invention.

  These have chemical forms such as monomers, prepolymers (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. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group, or a mercapto group and a monofunctional or polyfunctional isocyanate or epoxy, and a hydroxy 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. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group and a monofunctional or polyfunctional alcohol, amine, or thiol is also suitable. 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, for example, (meth) acrylic acid, pentaerythritol triacrylate succinic acid monoester, dipentaerythritol pentaacrylate succinic acid monoester, pentaerythritol triacrylate maleic acid monoester, dipenta Erythritol pentaacrylate maleic acid monoester, pentaerythritol triacrylate phthalic acid monoester, dipentaerythritol pentaacrylate phthalic acid monoester, pentaerythritol triacrylate tetrahydrophthalic acid monoester, dipentaerythritol pentaacrylate tetrahydrophthalic acid monoester It is done. 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.

  Further, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane compound containing two or more polymerizable vinyl groups 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. Etc.

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.

About these polymeric compounds, the details of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the performance design of a coloring composition. For example, it is selected from the following viewpoint.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. 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 compatibility and dispersibility with other components in the coloring composition (for example, resin, photopolymerization initiator, pigment), the selection and use method of the polymerizable compound is an important factor. In some cases, the compatibility can be improved by using a low-purity compound or by 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 in the solid content of the colored composition of the present invention is preferably 1% by mass to 90% by mass, more preferably 5% by mass to 80% by mass, and more preferably 10% by mass to More preferably, it is 70 mass%.

<Polymerization initiator>
The coloring composition of the present invention can contain 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 include metallocene compounds, hexaarylbiimidazole compounds, organic borate compounds, disulfonic acid compounds, oxime compounds, onium salt compounds, acylphosphine (oxide) compounds, and alkylamino compounds.
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. Bal et al, Polymer, 21, 423 (1980), diazonium salts described in U.S. Pat. No. 4,069,055, ammonium salts described in JP-A-4-365049, U.S. Pat. No. 4,069, Phosphonium salts described in the specifications of Nos. 055 and 4,069,056, iodonium salts described in European Patent Nos. 104 and 143, JP-A-2-150848, JP-A-2-296514, etc. Is mentioned.

  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. et al. 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, Darocur TPO and the like manufactured by Ciba Specialty Chemicals.

  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, from triazine compounds, oxime compounds, hexaarylbiimidazole compounds, and alkylamino compounds More preferred are at least one compound selected from the group consisting of oxime compounds.

  In particular, when the colored composition of the present invention is used for forming colored pixels in a color filter of a solid-state imaging device, the pigment concentration in the composition is high due to the formulation, so the amount of photopolymerization initiator added is reduced and the sensitivity is increased. May fall. 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. Considering these, as the photopolymerization initiator that satisfies the sensitivity and various performances, an oxime compound is preferable, and an oxime compound having absorption at 365 nm is most preferable.

  In the present invention, among the oxime compounds, a compound represented by the following general formula (d) is preferable from the viewpoints of sensitivity, stability over time, and coloring during post-heating. Moreover, Irgacure OXE-01, OXE-02, etc. manufactured by Ciba Specialty Chemicals 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.

  Specific examples of oxime compounds suitable for the colored composition of the present invention are shown below, but the present invention is not limited thereto.

  The content of the photopolymerization initiator in the total solid content of the colored 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, particularly Preferably they are 1 mass%-20 mass%. Within this range, good sensitivity and pattern formability can be obtained.

<Naphthoquinonediazide compound>
When the colored composition of the present invention is constituted into a positive colored photosensitive composition, the colored composition of the present invention preferably contains a naphthoquinonediazide compound as a radiation-sensitive compound.
The naphthoquinonediazide compound is a compound having at least one o-quinonediazide group. For example, o-naphthoquinonediazide-5-sulfonic acid ester, o-naphthoquinonediazide-5-sulfonic acid amide, o-naphthoquinonediazide-4- Examples thereof include sulfonic acid esters and o-naphthoquinonediazide-4-sulfonic acid amide. These esters and amide compounds can be produced by a known method using, for example, the phenol compound described in the general formula (I) in JP-A-2-84650 and JP-A-3-49437. .

  When the colored composition of the present invention is a positive colored photosensitive composition, the content of the naphthoquinonediazide compound in the colored composition is preferably 2% by mass to 50% by mass, and preferably 2% by mass to More preferably, it is 30 mass%.

<Alkali-soluble resin>
The colored 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.). Of these, more preferred are those which are soluble in an organic 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,
Examples thereof include vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, and polymethyl methacrylate macromonomer.

  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.

When the coloring composition of the present invention contains the polymer (a), the heat resistance and transparency of a cured coating film formed using the composition are further improved.
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 coloring 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 an 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 resin containing a carboxyl group; Urethane-modified polymerizable double bond-containing acrylic resin obtained by the above reaction, unsaturated group-containing acrylic obtained by reaction of an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule Resin, acid pendant type epoxy acrylate resin, OH group-containing acrylic resin and polymerizable double bond-containing acrylic resin obtained by reacting a polymerizable double bond, OH group-containing acrylic resin and isocyanate Resin obtained by reacting a compound having a polymerizable group, Japanese Patent Application Laid-Open No. 2002-229207 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 coloring 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, it is 3 -10 mass%.

(Alkali-soluble phenol resin)
When the colored composition of the present invention is a positive colored photosensitive composition, an alkali-soluble phenol resin can also be used as the binder. The alkali-soluble phenol resin can be suitably used when the colored photosensitive composition of the present invention is a positive composition. Examples of the alkali-soluble phenol resin include novolak resins and vinyl polymers.
Examples of the novolac resin include those obtained by condensing phenols and aldehydes in the presence of an acid catalyst. Examples of the phenols include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, and bisphenol A.
Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, and benzaldehyde.
The said phenols and aldehydes can be used individually or in combination of 2 or more types.

  Specific examples of the novolak resin include, for example, a condensation product of metacresol, paracresol or a mixture thereof and formalin.

  The novolak resin may be adjusted in molecular weight distribution by means of fractionation or the like. Moreover, you may mix the low molecular weight component which has phenolic hydroxyl groups, such as bisphenol C and bisphenol A, with the said novolak resin.

<Crosslinking agent>
The coloring 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 Tetravalent glycidyl group-containing low molecular weight compounds typified by tetra-A-glycidyl ether, polyvalent glycidyl group-containing low molecular weight compounds such as dipentaerythritol pentaglycidyl ether and dipentaerythritol hexaglycidyl ether, polyglycidyl ( And glycidyl group-containing polymer compounds represented by 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol and the like. .

  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 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 more preferable. 7 to 30% by mass is particularly 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.

<Solvent>
The coloring composition of the present invention may contain a solvent.
Although the use of the coloring composition of the present invention is not particularly limited, specifically, for example, as described later, it is used for production of a color filter by a photolithographic method, production of a color filter by an inkjet method, and the like.
And a solvent and another additive are used suitably as needed in consideration of applications and the like.
First, the case where the coloring composition of this invention is used for manufacture of the color filter by the photolithography method is demonstrated.
The colored composition of the present invention (colored composition in the form of a colored photosensitive composition) used for the photolithography method preferably has 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 composition, applicability, and the like. Basically, the material is not particularly limited as long as these desired physical properties are satisfied. However, 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 (PGMEA) 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 the ultraviolet absorber and the alkali-soluble resin, 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 solvent in the coloring 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 coloring composition for manufacture of the color filter by an inkjet method, as mentioned later, from the viewpoint of curability, it is preferable that the content of the (D) solvent is small, and (D) an embodiment in which no solvent is used. It is possible.

<Surfactant>
Various surfactants may be added to the colored 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 coloring composition of the present invention contains a fluorosurfactant, so that liquid properties (particularly fluidity) when prepared as a coating solution are further improved. Liquidity can be further improved.
That is, in the case of forming a film using a coating liquid to which a coloring composition containing a fluorosurfactant is applied, wetting the coated surface by reducing the interfacial tension between the coated surface and the coating liquid. The coating property 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 within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in a colored composition.

  Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F479, F482, 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, K393, KH-40 (manufactured by Asahi Glass Co., Ltd.), CW-1 (manufactured by GENECA), etc. It is done.

  Specific examples of nonionic surfactants include glycerol propoxylate, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate. , Polyethylene glycol distearate, sorbitan fatty acid ester (pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, manufactured by BASF, Tetronic 304, 701, 704, 901, 904, 150R1, etc.).

  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 Yushi 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-based surfactant include “Tore Silicone DC3PA”, “Tore Silicone SH7PA”, “Tore Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, and “Tore Silicone SH29PA” manufactured by Torre Silicone Co., Ltd. , “Tole Silicone SH30PA”, “Tole Silicone SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-444 (4) (5)” manufactured by Momentive Performance Materials 6) (7) 6 ”,“ TSF-4460 ”,“ TSF-4442 ”,“ KP341 ”manufactured by Shin-Etsu Silicone Co., Ltd.,“ BYK323 ”,“ BYK330 ”manufactured by Big Chemie.
Only one type of surfactant may be used, or two or more types may be combined.

<Polymerization inhibitor>
In the colored 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 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>
In the coloring composition of the present invention, various additives such as fillers, polymer compounds other than the above, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents and the like can be blended as necessary. . Examples of these include additives described in paragraph numbers [0274] to [0276] of JP-A-2008-292970.

<Method for preparing colored composition>
In preparing the colored composition of the present invention, the above-described components of the composition may be combined at once, or may be combined 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 composition may be prepared by dissolving all the components in a solvent at the same time. If necessary, each component is appropriately made into two or more solutions, and these solutions are mixed at the time of use (at the time of application). And may be prepared as a composition.
The composition prepared as described above is preferably filtered after using a filter having a pore size of 0.01 to 3.0 μm, more preferably a pore size of about 0.05 to 0.5 μm, and then used. You can also.

  The colored composition of the present invention can be suitably used for forming a colored pixel such as a color filter used in a liquid crystal display (LCD) or a solid-state imaging device (for example, CCD, CMOS, etc.). In particular, it can be suitably used for forming color filters for solid-state imaging devices such as CCDs and CMOSs.

When the colored composition of the present invention is used, for example, in the production of a color filter by a photolithography method, a color filter for a solid-state imaging device in which a colored pattern is formed in a thin film with a very small size and a good rectangular cross-sectional profile is required. It is particularly suitable for the formation of
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 composition of the present invention is used, it is possible to produce a color filter that is excellent in pattern formability and suppresses color mixing such as infiltration, color transfer, and residue even with a pixel pattern size of 2 μm or less as described above. .

  In general, in a coloring 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, and color mixing tends to occur (infiltration of the dye at the time of application of the next color). Furthermore, in a coloring 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, 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 coloring 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 coloring composition of the present invention containing a specific pigment multimer is used, while maintaining the transparency of the dye, the above-mentioned dye-specific dye soaking in the next color coating, elution of the dye during alkali development A colored film (color filter) in which thermal diffusion (color transfer) due to heat treatment can be significantly suppressed can be produced.

≪Color filter and manufacturing method≫
The color filter of the present invention is formed by using the colored composition of the present invention. For this reason, the color filter of the present invention suppresses color mixing caused by soaking, color transfer, and development residue. Moreover, it is excellent also in heat resistance.

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

  Specifically, a step of forming a colored layer by applying the colored composition on a support (hereinafter also referred to as “colored layer forming step”), and a step of exposing the formed colored layer through a mask (Hereinafter also referred to as “exposure step”) and a step of developing the exposed colored layer to form a colored pattern (hereinafter also referred to as “development step”). Also referred to as “color filter production method 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 composition of the present invention is coated on a support by a coating method such as spin coating, cast coating, roll coating or the like to form a coating layer. Thereafter, if necessary, preliminary curing (pre-baking) is performed, and the coating 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 soda glass, borosilicate glass (pyrex (registered trademark) glass), quartz glass, and quartz glass used for liquid crystal display elements and the like, and a transparent conductive film thereon. Examples include a deposited substrate and a photoelectric conversion element substrate used for an imaging element, such as a silicon substrate and a complementary metal oxide semiconductor (CMOS) substrate. 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 composition on the support, in order to reduce the dripping amount of the liquid, prior to the dropping of the colored composition, an appropriate organic solvent is dropped and rotated, so that Familiarity 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 composition is appropriately selected according to the purpose, but is generally preferably 0.2 μm to 5.0 μm, preferably 0.3 μm to 2.5 μm. Is more preferable, and 0.3 μm to 1.5 μm is most preferable. In addition, the thickness of the colored layer here is a film thickness after pre-baking.

<Exposure process>
Then, in the manufacturing method of the color filter of this invention, exposure through a mask is performed to the colored layer formed on the support body (exposure process).
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 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 (coloring ^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 or positive 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. 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 tetraethylammonium hydroxide so that its 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 to suppress deformation of the shape due to thermal 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 coloring composition of the present invention adheres to, for example, a nozzle of a coating apparatus discharge section, a piping section of a coating apparatus, or the inside of a coating apparatus, 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 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 composition of the present invention.
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 with respect to the coloring composition, the surfactant described above as a surfactant that may be contained in the coloring composition may be added to the cleaning liquid.

Furthermore, as a method for producing a color filter, in addition to the above method, a method using an ink jet method may be used.
The method for producing a color filter by the inkjet method is not particularly limited, and the step of preparing a substrate having a recess partitioned by a partition, and the recess according to the colored composition of the present invention (specifically, the inkjet method) And a step of forming colored pixels of the color filter by applying droplets of the 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.

≪Inkjet ink≫
The ink-jet ink of the present invention contains the colored composition of the present invention.
The ink-jet ink of the present invention can form colored pixels with excellent fastness (heat resistance and light resistance), is excellent in storage stability, and is excellent in ejection stability.

The inkjet ink of the present invention preferably includes the specific dye multimer and at least one of a solvent and a polymerizable compound.
That is, the ink-jet ink of the present invention may or may not contain a solvent. Examples of the form in which the inkjet ink does not include a solvent include a form in which a polymerizable compound serves as a solvent.

<Solvent>
The solvent is not particularly limited as long as it satisfies the solubility of each component and the boiling point of the solvent described later, but is preferably selected in consideration of the solubility, applicability, and safety of the binder described later. . Specific examples of the solvent include the solvents described in paragraph numbers [0030] to [0040] of JP-A-2009-13206.
Moreover, as a solvent, the solvent demonstrated as a solvent in the coloring composition of this invention as stated above can also be used.

  The content of the solvent is preferably 30 to 90% by mass, and more preferably 50 to 90% by mass with respect to the total amount of the ink jet ink. When the amount is 30% by mass or more, the amount of ink ejected in one pixel is maintained, and the wetting and spreading of the ink in the pixel is good. Further, when it is 90% by mass or less, the amount of components other than the solvent for forming a functional film (for example, a pixel or the like) in the ink can be kept at a predetermined amount or more. As a result, when forming a color filter, the required amount of ink per pixel does not increase too much. For example, when ink is applied to the concave portion partitioned by the partition wall by the ink jet method, the ink overflows from the concave portion. And the occurrence of color mixing with adjacent pixels can be suppressed.

  The ink-jet ink of the present invention preferably contains a solvent having a high boiling point among the above-mentioned solvents from the viewpoints of ink discharge performance with respect to the nozzle and wettability with respect to the substrate.

The boiling point of the solvent is preferably 130 to 280 ° C.
If the boiling point of the solvent is 130 ° C. or higher, the uniformity of the in-plane pixel shape is further improved.
If the boiling point of the said solvent is 280 degrees C or less, the solvent removability by prebaking will improve more.
The boiling point of the solvent means a boiling point under a pressure of 1 atm, and can be known from a physical property table such as a compound dictionary (Chapman & Hall). These may be used alone or in combination of two or more.

The above-mentioned binder may be added to the ink-jet ink of the present invention as necessary for the purpose of adjusting the viscosity or adjusting the ink hardness. As the binder, a binder resin that is simply dried and solidified such that it is composed only of a resin that is not polymerized by itself may be used. However, in order to impart sufficient strength, durability, and adhesion to the coating film, a binder that can cure the pixel by a polymerization reaction after forming a pixel pattern on the substrate by an inkjet method is used. For example, a binder that can be polymerized and cured, such as a photocurable binder that can be polymerized and cured by visible light, ultraviolet light, electron beam, or the like, or a thermosetting binder that can be polymerized and cured by heating. Can be used.
Moreover, what was demonstrated as a binder in the coloring composition of this invention can also be used as binder resin in the inkjet ink of this invention.

<Crosslinking agent>
Moreover, the inkjet ink of the present invention may contain a crosslinking agent.
As the cross-linking agent, the curing agent and the accelerator described in Chapter 3 of “Review Epoxy Basic Fundamentals I” issued on November 19, 2003, published by the Epoxy Resin Technology Association, can be suitably used. Carboxylic anhydride or polyvalent carboxylic acid can be used.

Moreover, the inkjet ink of the present invention may further contain a surfactant.
As examples of the surfactant, the surfactants disclosed in JP-A-7-216276, paragraph [0021], JP-A-2003-337424, and JP-A-11-133600 are preferable. As mentioned. As for content of surfactant, 5 mass% or less is preferable with respect to coloring composition whole quantity.
Moreover, what was demonstrated as surfactant in the coloring composition of this invention can also be used as surfactant in the inkjet ink of this invention.

  Examples of other additives included in the inkjet ink of the present invention as needed include other additives described in paragraph numbers [0058] to [0071] of JP-A No. 2000-310706.

For the production of the coloring composition of the present invention used in the ink jet method, a known ink jet ink production method can be applied.
(B) When preparing a solution of the polymerizable compound, if the solubility of the material used in the solvent is low, heating, ultrasonic treatment, etc. within the range in which the polymerizable compound does not cause a polymerization reaction It is possible to appropriately perform the process.

The physical property value of the colored composition of the present invention used in the ink jet method is not particularly limited as long as it is within a range that can be ejected by an ink jet head, but the viscosity at the time of ejection is 2 to 30 mPa · s from the viewpoint of stable ejection. Preferably, 2 to 20 mPa · s is more preferable. Moreover, when ejecting with an apparatus, it is preferable to maintain the temperature of the inkjet ink at a substantially constant temperature in the range of 20 to 80 ° C. If the temperature of the device is set to a high temperature, the viscosity of the ink decreases and it becomes possible to eject higher viscosity ink. However, due to the increase in temperature, the ink is denatured by heat and the thermal polymerization reaction occurs in the head. The temperature of the apparatus is preferably in the range of 20 to 80 ° C. because the solvent evaporates on the surface of the nozzle that ejects ink or nozzle clogging easily occurs.
The viscosity is measured by using a commonly used E-type viscometer (for example, an E-type viscometer (RE-80L) manufactured by Toki Sangyo Co., Ltd.) with the inkjet ink held at 25 ° C. Value.

  Further, the surface tension (static surface tension) at 25 ° C. of the colored composition of the present invention used in the ink jet method is 20 to 40 mN / m in terms of improving wettability with respect to a non-permeable substrate and discharging stability. Is preferable, and 20-35 mN / m is more preferable. Moreover, when discharging with an apparatus, it is preferable to maintain the temperature of the ink for inkjet in the range of 20-80 degreeC, and it is preferable to make the surface tension at that time into 20-40 mN / m. In order to keep the temperature of the inkjet ink constant with a predetermined accuracy, the ink temperature detecting means, the ink heating or cooling means, and the control means for controlling the heating or cooling according to the detected ink temperature are provided. It is preferable to use an apparatus. Alternatively, it is also preferable to have a means for reducing the influence on the ink physical property change by controlling the energy applied to the means for ejecting ink according to the ink temperature.

  The above surface tension is measured by a Wilhelmy method at a liquid temperature of 25 ° C. and 60% using a generally used surface tension meter (for example, surface tension meter FACE SURFACE TENSIOMETER CBVB-A3 manufactured by Kyowa Interface Science Co., Ltd.). It is a value measured by RH.

  Moreover, in order to maintain the shape in which the colored composition of the present invention wets and spreads after landing on the substrate properly, it is preferable to maintain the liquid properties of the colored composition after landing on the substrate. For this purpose, it is preferable to keep the substrate and / or the vicinity of the substrate within a predetermined temperature range. Alternatively, it is also effective to reduce the influence of temperature change by increasing the heat capacity of the table that supports the substrate.

  When the colored composition of the present invention is used for production of a color filter by an ink jet method, it has excellent ink storage stability and suppresses aggregation and decomposition of the ink. Also, during continuous and intermittent discharge, it is difficult for discharge disturbance such as flying bend and non-discharge, excellent discharge stability, recovery after a certain period of rest, non-discharge etc. Excellent recoverability.

  A method for producing a color filter by the ink jet method using the colored composition of the present invention is not particularly limited. For example, a method described in paragraph numbers [0114] to [0128] of JP-A-2008-250188 is used. be able to.

<Use of the color filter of the present invention>
The color filter of the present invention is suitable for use in a display device such as a liquid crystal display, an organic EL display, a liquid crystal projector, a game machine, and a mobile terminal such as a mobile phone, a digital camera, and a car navigation system, in particular, a color display device. Applicable.
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. .

  In addition, the camera system including the color filter of the present invention includes a cover lens, a microlens, and the like in which a camera lens and an IR cut film are dichroically coated, from the viewpoint of light fading of a color material. 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 color material. For example, a part or the whole of the camera system Is preferably sealed with nitrogen gas.

≪Display device≫
The 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 pixel is improved, and a pixel free from chipping, peeling, or twisting can be formed. Therefore, the resistance to the peeling liquid of the colored layer provided directly or indirectly on the TFT substrate is improved. Useful for liquid crystal display devices. In order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.
Further, the colored layer formed by the COA method has a rectangular shape with a side length of about 1 to 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.

  As described above, the colored composition, the ink-jet ink, 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. 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. However, Examples 26 and 28 to 33 are reference examples. In the following examples, “%” and “parts” represent “% by mass” and “parts by mass” unless otherwise specified.

[Example 1]
(1) Preparation of resist solution A (negative type)
The following components were mixed and dissolved to prepare a resist solution A.
Propylene glycol monomethyl ether acetate: 5.20 parts Cyclohexanone: 52.60 parts Binder: 30.50 parts (benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate copolymer, molar ratio = 60: 20 : 20, average molecular weight 30200 (polystyrene conversion), 41% cyclohexanone solution)
Dipentaerythritol hexaacrylate ... 10.20 parts Polymerization inhibitor (p-methoxyphenol) 0.006 parts Fluorosurfactant (F-475 manufactured by DIC Corporation) 0.80 parts Photopolymerization Initiator: 4-Benzoxolane-2,6-bis (trichloromethyl) -s-triazine (manufactured by Midori Chemical Co., Ltd. TAZ-107) 0.58 parts

(2) Production of glass substrate with undercoat layer A glass substrate (Corning 1737) was ultrasonically washed with 0.5% NaOH water, and then washed with water and dehydrated (200 ° C./20 minutes). Next, the resist solution A obtained in the above (1) was applied on a glass substrate washed with a spin coater so that the film thickness after drying was 2 μm, and was dried by heating at 220 ° C. for 1 hour to form an undercoat layer An attached glass substrate was prepared.

(3) Preparation of colored composition The following components were mixed and dispersed and dissolved to obtain a colored composition.

Cyclohexanone: 1.133 parts Benzyl methacrylate / methacrylic acid copolymer (20% CyH solution) (molar ratio = 70:30, weight average molecular weight 30000) ... 1.009 parts Polymerizable monomer (KAYARAD DPHA ( Nippon Kayaku))) 3.84 parts Fluorosurfactant (1% CyH solution) (Zeneca Solsperse 20000)
... 0.125 parts · Oxime-based photopolymerization initiator (compound with the following structure) · · 0.087 parts · Dye multimer (Exemplary compound 1-4 / weight average molecular weight (Mw) 5200 / dispersion degree (Mw / Mn) 1 .66) ... 0.183 parts Pigment Blue 15: 6 dispersion ... 2.418 parts (solid content concentration 17.70%, pigment concentration 11.80%)
Nonionic surfactant: glycerol propoxylate (1% CyH solution)
… 0.048 parts

-C. I. Preparation of Pigment Blue 15: 6 Dispersion-
C. above. I. Pigment Blue 15: 6 dispersion was prepared as follows.
That is, C.I. I. Pigment Blue 15: 6 (11.8 parts by mass (average particle diameter 55 nm)), pigment dispersant BY-161 (manufactured by BYK) 5.9 parts by mass, and PGMEA 82.3 parts by mass were mixed with a bead mill (zirconia). A pigment dispersion was prepared by mixing and dispersing for 3 hours using beads having a diameter of 0.3 mm. 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 (CI Pigment Blue 15: 6 dispersion). With respect to the obtained pigment dispersion, the average primary particle diameter of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)) and found to be 24 nm.

(4) Exposure and development of colored composition (colored pattern formation)
Apply the colored composition obtained in (3) above onto the undercoat layer of the glass substrate with undercoat obtained in (2) above using a spin coater so that the film thickness after drying is 0.6 μm. And prebaking at 100 ° C. for 120 seconds.
Next, using an exposure apparatus UX3100-SR (manufactured by USHIO INC.), The coating film was irradiated at a wavelength of 365 nm through a mask having a line width of 2 μm with an exposure amount of 200 mJ / cm ² . After the exposure, development was performed using a developer CD-2000 (manufactured by Fuji Film Electronics Materials Co., Ltd.) at 25 ° C. for 40 seconds. Then, after rinsing with running water for 30 seconds, spray drying was performed to obtain a colored pattern.

Then, it heated at 200 degreeC for 300 seconds (post-baking), and the coloring pattern was hardened.
Thus, a glass substrate with a colored pattern (blue monochromatic color filter) was obtained.

(5) Evaluation The coloring pattern formed on the glass substrate using the coloring composition, alkali elution resistance, solvent resistance, color transfer due to thermal diffusion, development residue on the substrate, development residue on other colors and Dye penetration was evaluated as follows. The evaluation results are shown in Tables 1 to 5 below.

(Alkali elution resistance)
The spectrum (spectrum A) of the coating film after the pre-baking in (4) above and the spectrum (spectrum B) after development at the exposed portion of the coating film are measured. %) Was calculated and used as an index for evaluating resistance to alkali elution. This value indicates that the closer to 100%, the better the alkali elution resistance.

[Solvent resistance]
The spectrum of the colored pattern after post-baking obtained in (4) above was measured (spectrum A). After applying the resist solution A obtained in (1) above to the colored pattern forming surface so as to have a film thickness of 1 μm and pre-baking the substrate with the colored pattern (color filter), CD-2000 (Fuji Film Electronics Co., Ltd.) Development was carried out under the conditions of 23 ° C. and 120 seconds using a developer (manufactured by Materials Co., Ltd.), and the spectrum was measured again (spectrum B). The dye residual ratio (%) was calculated from the difference between the spectrum A and the spectrum B, and this was used as an index for evaluating the solvent resistance. This value indicates that the closer to 100%, the better the solvent resistance.

[Color transfer by thermal diffusion]
A CT-2000L solution (base clearing agent, manufactured by FUJIFILM Electronics Materials Co., Ltd.) is applied to the colored pattern forming surface of the substrate with a color filter produced as described in (4) above so that the dry film thickness becomes 1 μm. After coating and drying to form a transparent film, heat treatment was performed at 200 ° C. for 5 minutes. After the heating, the absorbance of the transparent film adjacent to the colored pattern was measured with a microspectrophotometer (LCF-1500M manufactured by Otsuka Electronics Co., Ltd.). The ratio [%] of the absorbance value of the obtained transparent film to the absorbance of the colored pattern similarly measured before heating was calculated and used as an index for evaluating the color transfer.
-Criteria-
Color transfer to adjacent pixels (%)
A: Color transfer to adjacent pixels <1%
○: 1% <color transfer to adjacent pixels ≦ 10%
Δ: 10% ≦ color transfer to adjacent pixel ≦ 30%
×: Color transfer to adjacent pixels> 30%

[Development residue on the substrate]
The developed pattern obtained in (4) above can be developed cleanly with no residue by observing the unexposed area with a scanning electron microscope (Hitachi ultra-high resolution field emission scanning electron microscope S-4800, magnification 20000 times). A three-step sensory evaluation was performed by assigning “◯” to “A”, “A” indicating that there was some residue but being developed, and “B” indicating that development was not possible.

[Development residue / dye soaking into other colors]
The following colored composition (G) was applied on the undercoat layer of the glass substrate with the undercoat layer obtained in (2) above using a spin coater so that the film thickness after drying was 0.6 μm, and 100 ° C. For 120 seconds, and then using an exposure apparatus UX3100-SR (manufactured by USHIO INC.), The coating film was irradiated on the entire surface with a wavelength of 365 nm with an exposure dose of 200 mJ / cm ² without using a mask. After the exposure, development was performed using a developer CD-2000 (manufactured by Fuji Film Electronics Materials Co., Ltd.) at 25 ° C. for 40 seconds. Then, after rinsing with running water for 30 seconds, spray drying was performed. Thereafter, post-baking was performed at 200 ° C. for 15 minutes, and the spectrum of this coating film was measured (spectrum A). Further thereon, the coloring composition of (3) above was applied using a spin coater so that the film thickness after drying was 0.6 μm, prebaked at 100 ° C. for 120 seconds, and the developer CD without exposure. Development was performed under the condition of 25 ° C. for 40 seconds using −2000 (manufactured by Fuji Film Electronics Materials Co., Ltd.). Then, after rinsing with running water for 30 seconds, spray drying was performed and the spectrum was measured (spectrum B). From the difference between the spectra A and B, the residue on the other color + soaking was calculated as an absolute value of transmittance reduction (T% reduction), and used as an index for evaluating the soaking of the development residue / dye on the other color.

-Criteria-
Development residue / dye soaking into other colors (T% reduction)
○: T% decrease <1%
Δ: 1% ≦ T% decrease ≦ 5%
×: T% decrease> 5%

-Coloring composition G-
C. I. Pigment Green 36 and C.I. I. Mixing of 40 parts of 30/70 [mass ratio] mixture with Pigment Yellow 219, 50 parts of Disperbyk-161 (manufactured by BYK), 30% solution) as a dispersant, and 110 parts of propylene glycol monomethyl ether as a solvent The liquid was mixed and dispersed by a bead mill for 15 hours to prepare a pigment dispersion (P1).
A colored composition G was prepared by stirring and mixing the pigment dispersion (P1) subjected to the dispersion treatment so as to have the following composition ratio.
<Composition>
Colorant (pigment dispersion (P1)) 350 parts Polymerization initiator (oxime photopolymerization initiator) (CGI-124, manufactured by Ciba Specialty Chemicals) 30 parts TO-1382 25 parts ( Polymerizable compound Toa Gosei Chemical Co., Ltd. Carboxyl group-containing pentafunctional acrylate)
Dipentaerythritol hexaacrylate 30 parts Solvent (PGMEA) 200 parts Substrate adhesion agent (3-methacryloxypropyltrimethoxysilane) 1 part

[Examples 2-33 and Comparative Examples 1-27]
Examples 2-33 and Comparative Examples 1-27 were evaluated in the same manner except that the dye multimer of Example 1 was changed to the dye multimer described in Tables 1 to 5.

In the exemplary compounds of each example and the exemplary compounds of each comparative example, the weight average molecular weight (Mw) was adjusted by increasing / decreasing the amount of chain transfer agent and increasing / decreasing the amount of initiator. In the present invention, the weight average molecular weight is adjusted by a polymerization reaction using a chain transfer agent that can be adjusted relatively easily. Specifically, in a nitrogen atmosphere, it is fixed to a polymerization initiator / chain transfer agent (2/1, molar ratio), and polymerization starts with respect to the total molar amount of the polymerizable dye monomer (and copolymerization component monomer). Preliminary polymerization reaction is carried out at 3 points of 3 mol%, 6 mol% and 9 mol% on the basis of the agent, GPC of the reaction solution is measured, and each target weight average molecular weight (Mw) is measured. By creating a calibration curve with these three points and calculating the amount of polymerization initiator and chain transfer agent necessary to obtain the desired weight average molecular weight (Mw), a large amount of dye having the desired weight average molecular weight (Mw) The body can be synthesized. When the desired weight average molecular weight (Mw) cannot be obtained within this calibration curve range, the reaction temperature is increased or decreased, the solvent type is changed, the polymerization initiator type is changed, the chain transfer agent type is a known molecular weight adjustment method. The weight average molecular weight (Mw) can be adjusted by changing the reaction concentration.
Specifically, in Examples 1 to 33, the polymerization initiator amount and the chain transfer agent amount were determined such that the weight average molecular weight (Mw) was 5000 or more and 20000 or less from the calibration curve as described above, and the polymerization reaction was performed. The weight average molecular weight (Mw) was adjusted to be in the range of 5000 or more and 20000 or less (the same applies to Examples 2-1, 3-1, and 3-2 described later).
In Comparative Examples 1 to 27, as described above, the weight average molecular weight (Mw) was determined from the calibration curve so that the polymerization initiator amount and the chain transfer agent amount were less than 5000, and the polymerization reaction was carried out to obtain the weight average. The molecular weight (Mw) is adjusted to be less than 5000, or the polymerization initiator amount and the chain transfer agent amount such that the weight average molecular weight (Mw) exceeds 20000 are determined from the calibration curve as described above, By performing a polymerization reaction, the weight average molecular weight (Mw) was adjusted to exceed 20000.

In each example and each comparative example, the degree of dispersion (Mw / Mn) was adjusted by changing the presence / absence of reprecipitation, the type / amount of reprecipitation solvent, and the number of times.
Specifically, in Examples 1 to 33, the solution was diluted with PGMEA / methanol (1/1, volume ratio) to a volume ratio of 3 times with respect to the polymerization reaction solution, and then this solution was about 20 to 100 times volume ratio. The desired degree of dispersion was adjusted by reprecipitation using acetonitrile (or acetonitrile / methanol mixed solvent, 7/3, volume ratio). If the desired degree of dispersion is not achieved, the dye multimer obtained by reprecipitation is dissolved in THF (or cyclohexanone, PGMEA) in a weight ratio of 3 to 5 times that of the dye multimer. By repeating reprecipitation using acetonitrile (or acetonitrile / methanol mixed solvent, 7/3, volume ratio) having a volume ratio of about 20 to 100 times, the dispersity (Mw / Mn) is 1.00 or more and 2.50 or less. (Examples 2-1, 3-1, and 3-2 described later are the same).
In Comparative Examples 1 to 27, the degree of dispersion (Mw / Mn) was adjusted to exceed 2.50 by not performing reprecipitation or concentrating the reaction solution.

  Illustrative compound A in Table 5 is polymer A (copolymer of the following dye monomer and 2-acrylamido-2-methylpropanesulfonic acid, 2-hydroxyethyl methacrylate, and methacrylic acid) described in Japanese Patent No. 3736221.

As shown in Tables 1 to 5 above, Examples 1 to 33 using dye multimers controlled to have specific physical properties of the present invention were more resistant to alkali elution than Comparative Examples 1 to 27. It can be seen that it has excellent properties and solvent resistance. In addition, it was excellent in color transfer due to thermal diffusion, residue on the substrate and other colors, and dye penetration, and showed a remarkable color mixing improvement effect.
In addition, the coating liquid (coloring composition) using the dye multimer controlled to have specific physical properties of the present invention has unexpectedly very good coating properties and is free from slits and uneven color on the coating surface. It was found to have sex.
Although the example which forms a blue coloring pattern (blue color filter) on a glass substrate was demonstrated as Examples 1-33 above, the solid-state image sensor substrate (Silicon wafer substrate in which image sensors, such as CCD and CMOS, were formed) In the same manner as in Examples 1 to 33 above, the blue color filter is formed on the image pickup element forming surface side by a known method using a green color resist, and the green color filter is formed by a known method using a red color resist. By producing the red color filters, three color filters can be produced on the solid-state imaging device substrate. The solid-state imaging device having these three color filters is excellent in color reproducibility and sensitivity because colorant soaking, colorant thermal diffusion (color transfer) due to heat treatment, and color mixing due to development residue are suppressed. .

[Example 2-1]
(1) Preparation of Colored Composition [Positive Type] Ethyl Lactate (EL) 30 parts / Resin P-1 3.0 Part / Naphthoquinone Diazide Compound N-1 1.8 Part Crosslinking Agent: Hexa Methoxymethylolated melamine: 0.6 parts, photoacid generator: TAZ-107 (manufactured by Midori Chemical Co., Ltd.): 1.2 parts, fluorosurfactant (F-475, manufactured by DIC Corporation): 0.0005 Part / colorant: Exemplified compound 1-4 (average molecular weight 5200, dispersity 1.66) 0.3 part or more was mixed and dissolved to obtain a colored composition [positive type].

  The resin P-1 and the naphthoquinone diazide compound (N-1) were synthesized as follows.

(2) Synthesis of Resin P-1 70.0 g of benzyl methacrylate, 13.0 g of methacrylic acid, 17.0 g of methacrylic acid-2-hydroxyethyl and 600 g of 2-methoxypropanol were charged into a three-necked flask, and a stirrer, reflux condenser A thermometer was attached, and a polymerization amount of a polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) was added at 65 ° C. under a nitrogen stream, followed by stirring for 10 hours. The obtained resin solution was added dropwise to 20 L of ion exchange water with vigorous stirring to obtain a white powder. This white powder was vacuum-dried at 40 ° C. for 24 hours to obtain 145 g of resin P-1. When the molecular weight was measured by GPC, the weight average molecular weight Mw = 28,000 and the number average molecular weight Mn = 11,000.

(3) Synthesis of naphthoquinone diazide compound (N-1) Trispamine PA (Honshu Chemical) 42.45 g, o-naphthoquinone diazide-5-sulfonyl chloride 61.80 g, and acetone 300 ml were charged into a three-necked flask and triethylamine 24 at room temperature. .44 g was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was further stirred for 2 hours, and then the reaction solution was poured into a large amount of water while stirring. The precipitated naphthoquinone diazide sulfonic acid ester was collected by suction filtration and vacuum dried at 40 ° C. for 24 hours to obtain photosensitive compound N-1.

  As a result of evaluating the colored composition [positive type] obtained above by the method according to Example 1, the alkali elution resistance was improved, the solvent resistance was improved, the color transfer was suppressed by thermal diffusion, the residue on the substrate and other colors It showed excellent effects in terms of suppression and suppression of dye penetration.

[Examples 3-1 and 3-2]
(Preparation of dark color composition for barrier rib formation)
The dark-color composition K1 first measures K pigment dispersion 1 and propylene glycol monomethyl ether acetate in the amounts shown in Table 6, mixes at a temperature of 24 ° C. (± 2 ° C.), and stirs at 150 rpm for 10 minutes. While stirring, the amounts of methyl ethyl ketone (2-butanone), binder 2, hydroquinone monomethyl ether, DPHA solution, 2,4-bis (trichloromethyl) -6- [4 ′-(N, N-bis) shown in Table 6 Ethoxycarbonylmethyl) amino-3′-bromophenyl] -s-triazine and surfactant 1 are weighed out and added in this order at a temperature of 25 ° C. (± 2 ° C.) and 150 rpm at a temperature of 40 ° C. (± 2 ° C.). For 30 minutes. In addition, the quantity of Table 6 is a mass part, and has the following composition in detail.

<K pigment dispersion 1>
・ Carbon black (Nippex 35 manufactured by Degussa) ... 13.1%
・ Dispersant (Compound B1 described below) 0.65%
-Polymer (Random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio, molecular weight 37,000) ... 6.72%
・ Propylene glycol monomethyl ether acetate: 79.53%

<Binder 2>
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio random copolymer, molecular weight 38,000) 27%
・ Propylene glycol monomethyl ether acetate 73%

<DPHA solution>
Dipentaerythritol hexaacrylate (containing 500 ppm of polymerization inhibitor MEHQ, manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) ... 76%
・ Propylene glycol monomethyl ether acetate: 24%

<Surfactant 1>
・ The following structure 1… 30%
・ Methyl ethyl ketone 70%

(Formation of partition walls)
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.
After cooling the substrate and adjusting the temperature to 23 ° C., a dark color composition prepared as described above with a glass substrate coater (manufactured by FS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle Material K1 was applied. Subsequently, a part of the solvent was dried with a VCD (vacuum drying apparatus, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, and then pre-baked at 120 ° C. for 3 minutes to increase the thickness to 2.3 μm. A color composition layer K1 was obtained.
With a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) that has an ultra-high pressure mercury lamp, the exposure mask surface and the dark color photosensitive film with the substrate and mask (quartz exposure mask with image pattern) standing vertically The distance between the layers K1 was set to 200 μm, and pattern exposure was performed under a nitrogen atmosphere with an exposure amount of 300 mJ / cm ² to a partition wall width of 20 μm and a space width of 100 μm.

Next, pure water is sprayed with a shower nozzle to uniformly wet the surface of the dark color composition layer K1, and then a KOH developer (containing a nonionic surfactant, trade names: CDK-1, Fuji Film). Electronics Materials Co., Ltd. 100-fold diluted) was subjected to shower development at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, ultrapure water is sprayed at a pressure of 9.8 MPa with an ultrahigh pressure cleaning nozzle to remove the residue, and a dark color composition layer K1 of the substrate is formed at an exposure amount of 2500 mJ / cm ^{2 in} the atmosphere. The film was post-exposed from the surface side and heated in an oven at 240 ° C. for 50 minutes to obtain a stripe-shaped partition wall having an opening having a thickness of 2.0 μm, an optical density of 4.0, and a width of 100 μm.

(Ink-repellent plasma treatment)
The substrate on which the barrier ribs were formed was subjected to ink repellent plasma treatment under the following conditions using a cathode coupling parallel plate type plasma treatment apparatus.

Gas used: CF ₄
Gas flow rate: 80sccm
Pressure: 40Pa
RF power: 50W
Processing time: 30 sec

(Method for preparing purple (V) ink)
The components shown in Table 7 below were mixed and stirred for 1 hour. Thereafter, the ink was filtered under reduced pressure through a microfilter having an average pore diameter of 0.25 μm to prepare purple (V) ink liquids (ink V-1 and ink V-2).

Details of the components used are shown below.
Coloring agent: exemplary compound 2-3 (average molecular weight 8820, dispersity 1.77, acid value 2.65 mmol / g)
DPCA-60 (manufactured by Nippon Kayaku Co., Ltd. (KAYARAD DPCA-60)): caprolactone-modified dipentaerythritol hexaacrylate KF-353 (manufactured by Shin-Etsu Chemical Co., Ltd.): polyether-modified silicone oil

(Measurement of viscosity and surface tension)
While adjusting the temperature of the obtained ink to 25 ° C., the viscosity was measured under the following conditions using an E-type viscometer (RE-80L) manufactured by Toki Sangyo Co., Ltd.
-Measurement conditions-
-Rotor used: 1 ° 34 'x R24
・ Measurement time: 2 minutes ・ Measurement temperature: 25 ° C

The surface tension meter (FACE) manufactured by Kyowa Interface Science Co., Ltd.
Surface tension was measured using SURFACE TENSIOMETER CBVB-A3).

(Contrast measurement method)
When using a cold cathode tube light source with a diffusion plate as a backlight unit, a monochromatic substrate is installed between two polarizing plates (Lukeo's POLAX-15N), and the polarizing plates are installed in parallel Nicols. The contrast was determined by dividing the Y value of the chromaticity of the light passing therethrough by the Y value of the chromaticity of the light passing through when installed in crossed Nicols. A color luminance meter (BM-5A manufactured by Topcon Co., Ltd.) was used for the measurement of chromaticity. The monochromatic substrate was produced by the following method.
Using V ink (ink V-1 and ink V-2) constituting a color filter, a solid film is formed on a glass substrate by an ink jet method or a spin coat method, and prebaked (preliminary) in the same manner as the color filter formation. Heating (temperature 100 ° C., 2 minutes) and post-baking (post-heating) (temperature 220 ° C., 30 minutes) were performed to form a film thickness of 2 μm.

The measurement angle of the color luminance meter was set to 1 °, and the measurement was performed with a visual field of 5 mm on the sample. The amount of light of the backlight was set so that the luminance when the two polarizing plates were installed in parallel Nicol was 400 cd / m ² with no sample installed.

  When the contrast of the monochromatic substrates (two types) obtained above was measured, a value of 50000 or more was obtained with any monochromatic substrate.

(ITO layer production)
Next, using a sputtering apparatus on the monochromatic substrate obtained above, ITO (indium tin oxide) is sputtered at a film surface temperature of 200 ° C. for 15 minutes to form an ITO film having a thickness of 1500 mm. A color filter substrate was produced.

(Change in spectral characteristics before and after ITO sputtering)
Before and after ITO sputtering, a spectral transmittance curve in a wavelength range of 400 nm to 700 nm was obtained using an ultraviolet-visible absorption spectrometer (V-570 manufactured by JASCO Corporation). When the amount of change in spectral transmittance at the maximum peak before and after sputtering is small, it means excellent heat resistance. It was found that the produced substrate had almost no change in spectral shape before and after ITO sputtering and had high heat resistance.

[Comparative Example 3-1]
(Preparation of pigment dispersion)
17.5 parts by mass of C.I. Pigment Violet 23 (manufactured by Dainichi Seika Co., Ltd.), 2.5 parts by mass of pigment dispersant (compound B1) and solvent ((1,3-butanediol diacetate) 80 parts by mass of 1,3-BGDA) and MMPGAC (ethylene glycol monomethyl ether acetate), premixing, and then motor mill M-50 (manufactured by Eiger Japan), zirconia beads with a diameter of 0.65 mm Was dispersed at a peripheral speed of 9 m / s for 25 hours to prepare a pigment dispersion for V.

(Preparation of comparative ink)
As a comparative example, a pigment ink prepared in the amount shown in Table 8 below was prepared using the above pigment dispersion. The materials used are as follows.
DPS100 (Nippon Kayaku Co., Ltd.): KAYARAD DPS100
・ TMPTA (Nippon Kayaku Co., Ltd.): KAYARAD TMPTA
Surfactant: the aforementioned surfactant 1
V-40 (manufactured by Wako Pure Chemical Industries): Azobis (cyclohexane-1-carbonitrile)

(Method for producing color filter for evaluation)
Using the ink prepared above, the ink jet printer DMP-2831 manufactured by Fuji Film Dimatix was used to discharge the ink in the region (the concave portion surrounded by the convex portion) divided by the partition on the substrate obtained above. And then heated in an oven at 100 ° C. for 2 minutes. Next, the monochromatic color filter was produced by leaving still for 30 minutes in 220 degreeC oven.

(Ink storage stability evaluation)
Each color ink prepared above is stored in a thermostatic chamber at 50 ° C., and the viscosity after 30 days is measured, and the difference (%) from the value immediately after the ink preparation [(viscosity after 30 days−viscosity immediately after preparation) / preparation. Evaluation was performed according to [Viscosity immediately after]. Evaluation criteria were classified as follows.
A: Difference from viscosity immediately after ink preparation is less than 10% B: Difference from viscosity immediately after ink preparation is 10% or more and less than 20% Δ: Difference from viscosity immediately after ink preparation is 20% or more and less than 30% X: The difference from the viscosity immediately after ink preparation is 30% or more

(Continuous discharge stability evaluation)
Using the ink prepared above, the ejection stability was evaluated. The evaluation method was performed using an inkjet printer DMP-2831, manufactured by Fujifilm Dimatix, a head cartridge with a droplet ejection amount of 10 pL, and a droplet ejection frequency of 10 kHz, and the state when continuously ejected for 30 minutes was observed. Evaluation criteria were classified as follows.
-Evaluation criteria-
◎: Continuous discharge is possible without problems ○: Slight non-ejection, ejection disturbance, etc. are observed during ejection, but it returns during ejection, and there is almost no problem Δ: Non-ejection, ejection disturbance occurs during ejection, State that does not return during discharge but returns to normal state due to maintenance x: State where non-discharge or discharge disturbance occurs during discharge, normal discharge cannot be performed, and discharge does not return even after maintenance DMP-2831 Purging (pressurizing ink in the head and forcibly ejecting ink from the nozzle) and blotting (sucking ink on the nozzle surface by slightly bringing the head nozzle surface into contact with the cleaning pad).

(Evaluation of ejection stability after pause)
Using the ink prepared above, the ejection stability was evaluated. The evaluation method is the same as the continuous discharge stability evaluation, using an inkjet printer DMP-2831, manufactured by Fujifilm Dimatix, and a head cartridge with a droplet ejection amount of 10 pL, and ejecting once for 5 minutes at a droplet ejection frequency of 10 kHz. The state when the discharge was started again under the same conditions was observed. Evaluation criteria were classified as follows.
-Evaluation criteria-
◎: Discharge can be performed without any problems at the same time as the droplet ejection instruction ○: Immediately after the droplet ejection instruction, a slight non-ejection, ejection disturbance, etc. are observed, but it returns during ejection and there is almost no problem Δ: Non-ejection, ejection disturbance Occurs, but does not return during discharge, but returns to normal state by maintenance ×: non-discharge, discharge disturbance occurs, normal discharge cannot be performed, and discharge does not return to normal level even by maintenance. Purging with DMP-2831 (pressurizing ink in the head and forcibly ejecting ink from the nozzle) and blotting (with the head nozzle surface slightly in contact with the cleaning pad and sucking ink from the nozzle surface) were performed.

(Heat resistance evaluation)
The color filters of each color prepared above were placed in an oven heated to 230 ° C. and left for 1 hour, and then the hue was measured. For the measurement of hue, UV-560 (manufactured by JASCO Corporation) was used, and ΔEab before and after the evaluation was evaluated as ○ when less than 5. ΔEab is 5 or more and less than 15, and ΔEab is 15 or more.

(Chemical resistance evaluation)
The color filter of each color produced above was immersed in the chemical | medical agent (N-methylpyrrolidone, 2-propanol, 5% sulfuric acid aqueous solution, 5% sodium hydroxide aqueous solution) to evaluate for 20 minutes, and the hue before and behind that was measured. For the measurement of hue, UV-560 (manufactured by JASCO Corporation) was used, and ΔEab was less than 5 as ◯. ΔEab is 5 or more and less than 15, and ΔEab is 15 or more. The evaluation method for ΔEab is the same as described above.

  Table 9 below collectively shows the evaluation results of the inkjet ink and the color filter.

As shown in Table 9, the ink-jet ink described in the present invention was excellent in storage stability and discharge stability. Moreover, the color filter manufactured using the ink-jet ink described in the present invention had excellent chemical resistance and heat resistance comparable to those obtained when pigment ink was used.
On the other hand, in the comparative example using the pigment ink, the ejection stability was poor and lacked practicality.

Claims (15)

As a colorant, the weight average molecular weight (Mw) is 5,000 or more and 20,000 or less, and the dispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) is 1.00 or more and 2.50 or less. A dye multimer having at least one alkali-soluble group selected from a carboxyl group, a phosphono group, and a sulfo group,
Furthermore, it contains a polymerizable compound, a polymerization initiator, and a solvent,
The dye multimer is a dye multimer having at least one of structural units represented by the following general formula (A) in a range of 57% by mass or more and 100% by mass or less,
The coloring composition in which the said polymerization initiator contains an oxime type compound.

[In General Formula (A), X ^A1 and X ^A2 each independently represent any one of the following (X-1) to (X-15) linking groups formed by polymerization. .
L ^A1 and L ^A2 are each independently a single bond, or a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, Substituted or unsubstituted heterocyclic linking group, —CH ₂ ═CH ₂ —, —O—, —S—, —NR—, —C (═O) —, —SO—, —SO ₂ —, (2), a linking group represented by the following general formula (3), a linking group represented by the following general formula (4), or a combination of two or more of these. Represents a divalent linking group. R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
Dye represents a dye residue obtained by removing 1 to 1 + m arbitrary hydrogen atoms from a dye compound. The dye compound is one selected from the group consisting of a cyanine dye, a triphenylmethane dye, a xanthene dye, and a dipyrromethene dye.
m represents an integer of 0 to 3.
Dye and LA ² may be linked by any of a covalent bond, an ionic bond, and a coordination bond. ]

[In (X-1) to (X-15), * represents a site linked to L ^A1 or L ^A2 . ]

[In General Formula (2) to General Formula (4), 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; Represents an integer of 0 to 4;
In general formula (2) to general formula (4), * represents a position bonded to X ^A1 or X ^A2 in general formula (A).
** represents a position bonded to Dye in the general formula (A). ]   The colored composition according to claim 1, wherein an acid value of the dye multimer is 0.5 mmol / g or more and 3.0 mmol / g or less.   Dye residue obtained by removing any 1 to 1 + m hydrogen atoms from a dye compound in which Dye in the general formula (A) is one selected from the group consisting of triphenylmethane dyes and xanthene dyes The coloring composition of Claim 1 or Claim 2 showing.   The coloring according to any one of claims 1 to 3, wherein Dye in the general formula (A) represents a dye residue obtained by removing any 1 to 1 + m hydrogen atoms from a triphenylmethane dye. Composition.   The colored composition according to any one of claims 1 to 4, wherein the dye multimer has a weight average molecular weight (Mw) of 5,000 or more and 16,000 or less.   The coloring composition according to any one of claims 1 to 5, wherein the dye multimer has a maximum absorption wavelength in a range of 400 nm to 780 nm.   7. The colored composition according to claim 1, wherein the content of the dye multimer in the total solid content is 0.1% by mass or more and 70% by mass or less.   The coloring composition according to any one of claims 1 to 6, wherein the content of the dye multimer in the total solid content is 5% by mass or more and 60% by mass or less.   The said pigment | dye multimer has at least one of the structural unit represented by the said general formula (A) in 65 to 88 mass% of range of any one of Claims 1-8. Coloring composition.   The color filter formed using the coloring composition of any one of Claims 1-9.   An ink-jet ink comprising the colored composition according to any one of claims 1 to 9. Applying the colored composition according to any one of claims 1 to 9 on a support to form a colored layer;
Exposing the formed colored layer through a mask;
Developing the exposed colored layer to form a colored pattern;
The manufacturing method of the color filter which has this. Preparing a substrate having a recess partitioned by a partition;
Applying the ink-jet ink droplets according to claim 11 to the recesses by an ink-jet method to form colored pixels of a color filter;
The manufacturing method of the color filter which has this.   A solid-state imaging device comprising the color filter according to claim 10.   A display device comprising the color filter according to claim 10.