JP5623934B2 - Colored composition, colored radiation-sensitive composition, method for producing dye multimer, ink jet ink, color filter and method for producing the same, solid-state imaging device, and display device - Google Patents

Description

  The present invention relates to a colored composition, a colored radiation-sensitive composition, a method for producing a dye multimer, 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.
For this reason, it is common to use a pigment as a colorant.

In recent years, there has been a demand for higher definition of color filters for solid-state imaging devices.
However, it is difficult to further improve the resolution with the conventional means using a pigment as a colorant from the standpoint of color unevenness due to coarse particles of the pigment. Also, in the liquid crystal display, when a pigment is used as a colorant, although it has excellent light resistance and heat resistance, there are problems such as a decrease in contrast and an increase in haze due to light scattering by the pigment particles.

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

  For this reason, the use of dyes as colorants instead of pigments is being investigated. When dyes are used, the color filters for solid-state image sensors eliminate the problem of uneven color and roughness and achieve high resolution. However, liquid crystal displays and color filters for organic EL displays are expected to improve optical characteristics such as contrast and haze. 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 (see, for example, Patent Document 3). However, dye-containing curable compositions generally have poor light resistance and heat resistance compared to pigments, and tend to suppress radical polymerization reactions, solubilities in alkaline aqueous solutions or organic solvents (hereinafter also simply referred to as solvents). Therefore, it is difficult to obtain a curable composition having a desired spectrum. In many cases, it exhibits an interaction with other components, and it is difficult to adjust the solubility (developability) of the non-cured portion. Thus, it has been difficult to form a colored pattern of a color filter that has high definition, a thin film, and excellent fastness by using a dye.

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 4).
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 5).
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 6).

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

  In a coloring composition for a color filter containing a dye, in order to prevent the elution and coloring of the dye, it has been studied to multimerize the dye. Although the elution and color transfer are suppressed by the multimerization of the dye, the present inventors have found that a new problem of color unevenness that has not been observed in a coloring composition using a dye has occurred. This color unevenness is “color unevenness caused by the generation of fine, dot-like high density regions”, and gives the appearance that the entire colored pattern is rough. Sometimes called “Zara”.

  Zara (color unevenness) refers to pixel density unevenness. When a dye multimer is used as a colorant, the cause of zara generation is examined. Among the components of the dye multimer, the dye composition ratio is high. It became clear that it is easy to generate Zara.

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 is a coloration in which elution of the colorant at the time of alkali development, infiltration of the colorant, thermal diffusion (color transfer) of the colorant by heat treatment, and development residue are suppressed, and the roughness (color unevenness) is good. It aims at providing the coloring composition which can form a film | membrane, and the coloring radiation sensitive composition using the same.
A further object of the present invention is to provide an inkjet ink that can form colored pixels with excellent heat resistance and is excellent in ejection stability.
In addition, the present invention suppresses colorant soaking, thermal diffusion (color transfer) of the colorant due to heat treatment, and color mixing caused by the development residue, and has good roughness (color unevenness) and excellent heat resistance. It is an object of the present invention to provide a color filter, a manufacturing method thereof, and a solid-state imaging device and a display device including the color filter.
Furthermore, the present invention is less likely to cause roughness (color unevenness) even when applied to a colored composition. It aims at providing the manufacturing method of the pigment | dye multimer in which the elution and the bleeding of the coloring agent were suppressed.

As a result of diligent studies, the present inventors have found that a dye homopolymer has a zara structure with respect to a dye multimer copolymerized with a monomer other than a large amount of dose (hereinafter referred to as a dye monomer) containing a dye as a partial structure. The composition ratio of pigment monomer and monomer other than dye is improved by increasing the composition ratio of monomer other than pigment (including dye structure) monomer. The present invention has been completed by finding that Zara is improved by suppressing aggregation of structural units derived from a dye monomer even in a dye multimer.
That is, specific means for solving the above problems are as follows.
<1> Synthesized using a dye monomer capable of forming a structural unit represented by the following general formula (A1) and a monomer capable of forming a structural unit represented by the following general formula (A2). dye monomer necessary for the synthesis of the body is a dye monomer capable of forming a structural unit represented by the following general formula (A1), the total dye monomers sac Chi 1 used for the synthesis of the dye polymer 5% by mass or more and 70% by mass or less of a dye monomer capable of forming a structural unit represented by the following general formula (A1), a monomer capable of forming a structural unit represented by the following general formula (A2), And a monomer that can form the remaining structural unit represented by the following general formula (A1) and the following general formula (A2). a monomer capable of forming a structural unit, a dropping polymerization for dropping a liquid containing a monomer containing Manufactured by Ukoto, the content of the structural unit represented by the following general formula constituting the dye multimer (A2) a (mol%) and (a2), the content of the structural unit represented by the following general formula (A1) A coloring composition containing a dye multimer having a relation between the two satisfying the following formula (1) and having an alkali-soluble group in the molecule when (mol%) is (a1).
Formula (1) (a2) / (a1) ≧ 0.3

[In General Formula (A1), X ^A1 represents a linking group formed by polymerization, L ^A1 represents a single bond or a divalent linking group, and Dye represents a dye obtained by removing one arbitrary hydrogen atom from a dye compound. Represents a residue. In general formula (A2), X ^A2 represents a linking group formed by polymerization, L ^A2 represents a single bond or a divalent linking group, and R represents a hydrogen atom, an alkyl group, or an ethylenic group shown below. Represents a monovalent substituent containing a partial structure having an unsaturated double bond. A plurality of X ^A1 , L ^A1 and Dye present in the molecule of the dye multimer may be the same as or different from each other, and a plurality of X ^A2 , L ^A2 and R may be the same or different from each other. It may be. ]

<2> The dye multimer has a degree of dispersion [Mw (weight average molecular weight) / Mn (number average molecular weight)] in the range of 1.0 <Mw / Mn <2.0 and is measured by GPC method. The colored composition according to <1>, which is a dye multimer having a weight average molecular weight (Mw) of 5,000 or more and 20,000 or less.
<3> Dye in the general formula (A) and the general formula (A1) is a dye residue in which one arbitrary hydrogen atom is removed from the dipyrromethene-based metal complex compound represented by the following general formula (5), or In the dipyrromethene-based metal complex compound represented by the general formula (6), a dye residue in which one hydrogen atom of any ^one of R ^{11 to} R ¹⁷ , X ¹ , and Y ^{1 to} Y ² is removed < The coloring composition as described in 1> or <2>.

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

[In General Formula (6), R ¹¹ and R ¹⁶ each independently represents 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. ]
<4> All of the charging liquid including the dye monomer that can form the structural unit represented by the general formula (A1) and the monomer that can form the structural unit represented by the general formula (A2). The colored composition according to any one of <1> to <3>, wherein the monomer concentration is 15% by mass or more and 100% by mass or less.
<5> The colored composition according to any one of <1> to <4>, wherein the dye multimer is a dye multimer produced by radical polymerization.
<6> The colored composition according to any one of <1> to <5>, wherein the dye multimer is a dye multimer produced by living radical polymerization.

<7> A colored radiation-sensitive composition comprising the colored composition according to any one of <1> to <6>, a polymerizable compound, and a polymerization initiator.
<8> A color filter comprising a colored pattern formed using the colored radiation-sensitive composition according to <7>.

<9> The step of forming the colored radiation-sensitive composition layer by applying the colored radiation-sensitive composition according to <8> on a support, and the formed colored radiation-sensitive composition layer in a pattern form A method for producing a color filter, which comprises: a step of exposing to light; and a step of developing the exposed colored radiation-sensitive composition layer to form a colored pattern in this order.
<10> An ink-jet ink containing the coloring composition according to any one of <1> to <6> and a polymerizable compound.
<11> A color filter comprising a colored pattern formed using the ink-jet ink according to <10>.
<12> A step of preparing a substrate having a recess partitioned by a partition, and applying the inkjet ink droplet according to <12> to the recess by an inkjet method to form a colored pixel of a color filter And a process for producing a color filter.
<13> A solid-state imaging device comprising the color filter according to <8> or <11>.
<14> A display device comprising the color filter according to <8> or <11 > .

<15> A method for producing a dye multimer comprising a structural unit represented by the following general formula (A1) and a structural unit represented by the following general formula (A2):
Synthesis of a dye multimer synthesized using a dye monomer capable of forming a structural unit represented by the following general formula (A1) and a monomer capable of forming a structural unit represented by the following general formula (A2) The dye monomer necessary for the dye is a dye monomer that can form the structural unit represented by the following general formula (A1), and among all the dye monomers used for the synthesis of the dye multimer , 15% by mass or more A monomer comprising 70% by mass or less of a dye monomer capable of forming a structural unit represented by the following general formula (A1) and a monomer capable of forming a structural unit represented by the following general formula (A2) A preparation liquid in which the body is previously prepared is prepared, and the remaining dye monomer capable of forming the structural unit represented by the following general formula (A1) and the structural unit represented by the following general formula (A2) are prepared in the charging liquid. colors performing a monomer capable of forming, a dropping polymerization for dropping a liquid containing a monomer containing Method for producing a multimeric.

[In General Formula (A1), X ^A1 represents a linking group formed by polymerization, L ^A1 represents a single bond or a divalent linking group, and Dye represents a dye obtained by removing one arbitrary hydrogen atom from a dye compound. Represents a residue. In general formula (A2), X ^A2 represents a linking group formed by polymerization, L ^A2 represents a single bond or a divalent linking group, and R represents a hydrogen atom, an alkyl group, or an ethylenic group shown below. Represents a monovalent substituent containing a partial structure having an unsaturated double bond. A plurality of X ^A1 , L ^A1 and Dye present in the molecule of the dye multimer may be the same as or different from each other, and a plurality of X ^A2 , L ^A2 and R may be the same or different from each other. It may be. ]

<16> All of the charge liquid including the dye monomer that can form the structural unit represented by the general formula (A1) and the monomer that can form the structural unit represented by the general formula (A2). The method for producing a dye multimer according to <15>, wherein the monomer concentration is 15% by mass or more and 100% by mass or less.
<17> The method for producing a dye multimer according to <15> or <16>, wherein the dropping polymerization is radical polymerization.
<18> The method for producing a dye multimer according to <17>, wherein the dropping polymerization is living radical polymerization.

According to the study by the present inventors, the dye homopolymer is greatly deteriorated in the Zara with respect to the dye multimer copolymerized with a monomer other than the dye, and the composition ratio of the monomer other than the dye monomer. Zara is improved by increasing the composition, so that the composition ratio of the dye monomer and the monomer other than the dye is in a specific range, and also in the dye multimer, the structural unit derived from the dye monomer It has been found that Zara improves by suppressing the aggregation of.
Further, when the monomer reactivity ratio (r ₁ is the relative reactivity of M ₁ and M _{2 with} respect to the polymer growth terminal M ₁ ^* ) is calculated (copolymerization 1-reaction analysis- / The Society of Polymer Science / Baifukan, experiment of polymer synthesis) Law / Takayuki Otsu / Chemical Doujin). When the dye monomer is M1, if r ₁ is larger than _{1, the} dye is polymerized in a block manner, and if it is smaller than 1, the dye monomer and other monomers are easily polymerized alternately. . The value of r ₁ is greater dye monomer, Zara than the value smaller dye monomers r _1, it became clear that tends to generate.

From these studies, the dye multimer component with a high dye composition ratio has a low solvent solubility and a high cohesiveness. Also, the compatibility with other polymers deteriorates, the interaction with the pigment, and the dispersant pulling. It is thought that Zara is likely to be induced due to various factors such as destruction of the dispersion system due to peeling.
Based on these results, it is necessary to synthesize dye multimers in order to study how narrow the dispersion of dye multimers is and to achieve uniform composition ratio distribution and to suppress aggregation derived from dye monomers. It is effective to first add a specific amount of the dye monomer to the charging solution and then perform the dropping polymerization while gradually adding the remaining dye monomer without adding a single dye monomer at a time. I found out. In the dye multimer obtained by this production method, the composition ratio of the dye monomer containing the dye as a partial structure to the copolymer component other than the dye monomer (other than the dye monomer, that is, the dye as a partial structure). Copolymer component not included as a component / copolymer component included as a partial structure including a dye: pigment monomer) can be 0.3 or more, and the portion that is probabilistically rich in dye and in which the dye is unevenly distributed in the molecule It was clarified that this is an effective means that can suppress the production of multimers. In addition, it has been found that living radical polymerization, which can generally reduce the degree of dispersion, is also effective. It has been found that even in radical polymerization, the degree of dispersion can be narrowed and a uniform composition ratio distribution can be realized by adjusting the amount of monomer charged and the amount of dripping in the production, and by carrying out the polymerization under a uniform monomer concentration.

According to the present invention, the elution of the colorant at the time of alkali development, the soaking of the colorant, the thermal diffusion (color transfer) of the colorant due to the heat treatment, and the development residue are suppressed, and the colored film having good roughness (color unevenness) It is possible to provide a colored composition and a colored radiation-sensitive composition capable of forming a colorant.
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.
In addition, according to the present invention, colorant soaking, thermal diffusion (color transfer) of the colorant due to heat treatment, and color mixing due to the development residue are suppressed, and a good roughness (color unevenness) and excellent heat resistance. The color filter and the manufacturing method thereof, and the solid-state imaging device and the display device including the color filter can be provided.
Furthermore, according to the present invention, even when applied to a colored composition, rough (color unevenness) hardly occurs and. It is possible to provide a method for producing a dye multimer in which elution and bleeding of a colorant are suppressed.

Hereinafter, the colored composition, colored radiation-sensitive composition, dye multimer production method of the present invention, ink jet ink, color filter and production method thereof, solid-state imaging device, and display device 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 includes, as a colorant, a dye monomer that can form a structural unit represented by the following general formula (A1) and a monomer that can form a structural unit represented by the following general formula (A2). Among all the dye monomers necessary for the synthesis of the dye multimer, 15% by weight to 70% by weight of a dye unit capable of forming a structural unit represented by the following general formula (A1) Prepared in advance and a monomer containing a monomer capable of forming a structural unit represented by the following general formula (A2), and the remaining general formula (A1) Performing dropwise polymerization by dropping a liquid containing a monomer containing a dye monomer capable of forming the structural unit shown and a monomer capable of forming the structural unit represented by the following general formula (A2) A structural unit represented by the following general formula (A2) that is produced by the process and constitutes a dye multimer Content (mol%) and (a2), when the content of the structural unit represented by the following general formula (A1) (molar%) and (a1), both (a2) / (a1) ≧ 0. A dye monomer satisfying the relationship 3 and containing a dye multimer having an alkali-soluble group in the molecule (hereinafter also referred to as “specific dye multimer”).

[In General Formula (A1), X ^A1 represents a linking group formed by polymerization, L ^A1 represents a single bond or a divalent linking group, and Dye represents a dye obtained by removing one arbitrary hydrogen atom from a dye compound. Represents a residue. In general formula (A2), X ^A2 represents a linking group formed by polymerization, L ^A2 represents a single bond or a divalent linking group, and R represents a hydrogen atom, an alkyl group, or an ethylenic group shown below. Represents a monovalent substituent containing a partial structure having an unsaturated double bond. A plurality of X ^A1 , L ^A1 and Dye present in the molecule of the dye multimer may be the same as or different from each other, and a plurality of X ^A2 , L ^A2 and R may be the same or different from each other. It may be. ]

By passing through the above process, in the dye multimer, the structural unit derived from the dye monomer [the structural unit represented by the above general formula (A1)] may cause a fear of generating a rough structure, for example, (A1) The structural unit represented by general formula (A2) derived from an acrylic acid monomer, an acrylate monomer, etc. does not form a block formed by bonding 4 or more structural units represented by It is considered that a preferable embodiment can be adopted in which a so-called spacer is arranged between the structural units represented by the formula (A1).
As described above, the dye-derived partial structure-Dye tends to aggregate itself. When a dye multimer is synthesized by a general synthesis method, the structural units having the dye-derived partial structure-Dye block each other. Therefore, as described above, it is important that a uniform dye multimer with a low molecular weight copolymer component is formed by drop polymerization using a predetermined amount of a dye monomer.

In particular, when applied to the photolithographic method, it is necessary to have an alkali-soluble group in the molecule from the viewpoint of pattern formation.
Furthermore, as a preferred embodiment of the present invention, the specific dye multimer 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)). ) Is preferably 1.00 or more and 2.0 or less.
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)”. The weight average molecular weight in the present invention is a value measured by GPC method as described in detail below.
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 colored composition of the present invention is suitably used for the production of colored radiation-sensitive compositions and inkjet inks used in photolithography, and the obtained colored radiation-sensitive compositions and inkjet inks are colored. It is suitable for use in producing a filter.

The specific form of the colored composition of the present invention is selected from a specific dye multimer and a radiation sensitive compound (polymerizable compound and polymerization initiator) from the viewpoint of more effectively achieving the effects of the present invention described above. And a negative or positive colored photosensitive composition containing the compound).
Among these, from the viewpoint of achieving the effect of the present invention particularly effectively, a negative coloring radiation radiation containing a specific dye multimer, a polymerization initiator that is a radiation sensitive compound, a polymerizable compound, and a solvent. It is preferable that it is a form of an adhesive composition (colored 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 is a dye multimer having a partial structure represented by the general formula (A1) and the general formula (A2), and preferably has a weight average molecular weight (Mw) of 5,000 or more and 20 The dye multimer having an alkali-soluble group having a dispersity (Mw / Mn) of 1.0 or more and 2.0 or less.
By making the molecular weight and dispersity of the dye multimer satisfy the above 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, and heat treatment The colorant thermal diffusion (color transfer) and development residue are 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 is preferably 5,000 or more and 20,000 or less, more preferably 5,000 or more and 16,000 or less, and most preferably 6,000 or more and 12,000 or less.

Further, when the dispersity (Mw / Mn) exceeds 2.0, when a colored film is formed, thermal diffusion (color transfer) of the colorant by heat treatment, soaking of the colorant, alkali elution resistance, solvent resistance Tend to get worse.
The dispersity (Mw / Mn) is preferably 1.0 or more and 2.0 or less, more preferably 1.0 or more and 1.8 or less, and most preferably 1.0 or more and 1.6 or less. is there.

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

As a means for suppressing aggregation of the structural unit represented by the general formula (A1) and adjusting the weight average molecular weight (Mw) in the range of 5,000 or more and 20,000 or less, for example, at the time of synthesis of the dye multimer In the method, means for adjusting the polymerization initiator amount and chain transfer agent amount, and means for adjusting the reaction temperature can be mentioned.
Specifically, the amount of the polymerization initiator is preferably 2 to 30 mol%, preferably 2 to 20 mol%, based on the sum of the polymerizable dye monomer and the polymerizable monomer that is another copolymerization component. Is more preferable.
Moreover, 1-20 mol% is preferable with respect to the sum total of a polymerizable 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. .
That is, examples of the dye skeleton that can be the partial structure -Dye contained in the structural unit represented by the general formula (A1) include monomethine, dimethine, trimethine, cyanine, merocyanine, dicyanostyryl, and diphenylmethane. , Triphenylmethane, xanthene, squarylium, quinophthalone, monoazo, bisazo, disazo, trisazo, quinophthalone, anthraquinone, anthrapyridone, perylene, diketopyrrolopyrrole, isoindoline Phthalocyanine, azomethine, dioxazine, and dipyrromethene dye skeletons and their metal complexes are preferred.
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 contained in the colorant composition of 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.
The alkali-soluble group may be included as a substituent in the general formula (A1) which is a structural unit derived from the dye monomer described above, and is included in the partial structure represented by the following general formula (A2). You may introduce | transduce into a pigment | dye multimer as a copolymerization component. In addition, when the dye multimer contains different general formulas (A2), the case where the dye multimer contains a structure forming an anti-salt structure in the molecule or between molecules, an anhydride structure, or the like is also included.

  Examples of the specific dye multimer in the present invention include dimers, trimers, oligomers, and polymers. Here, the specific dye dimer refers to a compound containing two partial structures represented by the general formula (A1) in the molecule.

For example, when the dye multimer is a polymer, the production method includes the following methods.
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 may be a method using a monomer having an alkali-soluble group as at least one of the polymerizable dye monomer and the other polymerizable monomer, or at least one of the polymerizable dye monomer. This is a method of synthesizing a dye multimer synthesized by a copolymerization reaction of a seed and at least one other polymerizable monomer (comonomer) by introducing an alkali-soluble group by a polymer reaction. May be.

When the dye multimer used in the present invention is synthesized by a copolymerization reaction, the obtained dye multimer has a partial structure represented by the following general formula (A1) and a partial structure represented by the general formula (A2). As long as the other polymerizable monomer (comonomer) is polymerizable with the polymerizable dye monomer, there is no particular limitation. The other polymerizable monomer may be contained in at least one of the partial structure represented by the following general formula (A1) and the partial structure represented by the general formula (A2). ) And a partial structure (structural unit) represented by formula (A2) and a copolymer component outside the partial structure that is copolymerized with the partial structure (structural unit).
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 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.

  The copolymerization ratio of the polymerizable dye monomer and the comonomer varies depending on the type of the polymerizable dye monomer, but is usually preferably a ratio of 5 to 10,000 g of the comonomer with respect to 100 g of the polymerizable dye monomer. The ratio is more preferably 5 to 1000 g of comonomer, and particularly preferably 5 to 100 g of comonomer.

The “dye multimer having an alkali-soluble group” contained in the coloring composition of the present invention has an alkali-soluble group in the molecule and has a partial structure represented by the following general formula (A1) and the general formula (A2). (A) is a dye multimer synthesized using a monomer capable of forming the partial structure represented by (A), and more specifically, among all the dye monomers necessary for the synthesis of the dye multimer, 15 A monomer comprising a pigment monomer capable of forming a structural unit represented by the following general formula (A1) and a monomer capable of forming a structural unit represented by the following general formula (A2) in an amount of not less than 70% by mass and not more than 70% by mass. A charge liquid in which a monomer is charged in advance is prepared, and the remaining dye monomer capable of forming the structural unit represented by the following general formula (A1) and the structural unit represented by the following general formula (A2) are prepared in the charged liquid. performing dropping polymerization for dropping a liquid containing the monomer and a monomer capable of forming It is produced by the.

[In General Formula (A1), X ^A1 represents a linking group formed by polymerization, L ^A1 represents a single bond or a divalent linking group, and Dye represents a dye obtained by removing one arbitrary hydrogen atom from a dye compound. Represents a residue. In general formula (A2), X ^A2 represents a linking group formed by polymerization, L ^A2 represents a single bond or a divalent linking group, and R represents a hydrogen atom, an alkyl group, or an ethylenic group shown below. Represents a monovalent substituent containing a partial structure having an unsaturated double bond. A plurality of X ^A1 , L ^A1 and Dye present in the molecule of the dye multimer may be the same as or different from each other, and a plurality of X ^A2 , L ^A2 and R may be the same or different from each other. It may be. ]

The content of the structural unit represented by the general formula (A2) constituting the dye multimer according to the present invention is defined as (a2) (mol%), and the content of the structural unit represented by the general formula (A1). Is (a1) (mol%), it is important that the relationship between the two satisfies the following formula (1).
Formula (1) (a2) / (a1) ≧ 0.3

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

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 the general formula (A1) contained in the dye multimer according to the present invention, the partial structure derived from the dye skeleton represented by Dye may be only one type in a molecule or two or more types.

In the general formula (A1), Dye represents a dye residue obtained by removing one arbitrary hydrogen atom of the dye compound.
Dye includes monomethine dyes, dimethine dyes, trimethine dyes, cyanine dyes, merocyanine dyes, dicyanostyryl dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, squarylium dyes, quinophthalone dyes , Monoazo dyes, bisazo dyes, disazo dyes, trisazo dyes, quinophthalone dyes, anthraquinone dyes, anthrapyridone dyes, perylene dyes, diketopyrrolopyrrole dyes, isoindoline dyes, phthalocyanine dyes, It is preferably a dye residue obtained by removing one hydrogen atom from one dye compound selected from the group consisting of azomethine dyes, dioxazine dyes, and dipyrromethene dyes.

(Dye monomer represented by the 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 ¹¹ represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group. L ^A1 has the same meaning as L ^A1 in formula (A1), preferably a single bond, —N (R ² ) C (═O) —, —OC (═O) —, —C (═O ) N (R ² ) —, —C (═O) O—, a group represented by the following general formula (2), a group represented by the following general formula (3), or a group represented by the following general formula (4) Represents a group. L ^A1 may further have a structure composed of the above-described divalent group and another divalent linking group. Dye has the same meaning as Dye in formula (A). R ² in the following general formulas (2) to (4) 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, a -L A1 ^{-C (R} 11) = compound polymerizable group is introduced, represented by CH _2.
In addition, when L ^A1 represents a single bond, a —C (R ¹ ) ═CH ₂ group is directly introduced into the dye residue derived from the dye compound.

In the general formula (1), R ¹¹ represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group. When R ¹¹ is an alkyl group or an aryl group, it may be unsubstituted or substituted.

When R ¹¹ 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 ¹¹ 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 ¹¹ is a substituted alkyl group or a substituted aryl group, the substituent is a halogen atom (for example, fluorine, chlorine, bromine, iodine) or 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-imidazo Silyl, 1-pyrazolyl, benzotriazol-1-yl), a 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 2 carbon atoms) More preferably an aryloxy group having 6 to 12 carbon atoms, for example, phenoxy, 1-naphthoxy), a heterocyclic oxy group (preferably having 1 to 24 carbon atoms, more preferably a heterocyclic oxy group having 1 to 12 carbon atoms). And, 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, such as trimethylsilyloxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy), 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) An alkoxycarbonyloxy group (preferably having a carbon number) To an alkoxycarbonyloxy group having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, more preferably ethoxycarbonyloxy, t-butoxycarbonyloxy), cycloalkyloxycarbonyloxy (for example, cyclohexyloxy). Carbonyloxy)), aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 24 carbon atoms, more preferably 7 to 12 carbon atoms, such as phenoxycarbonyloxy), a carbamoyloxy group (preferably having a carbon number) A carbamoyloxy group having 1 to 24 carbon atoms, more preferably 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 having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and still more preferably 1 to 6 carbon atoms) Groups such as methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexylsulfonyloxy), arylsulfonyloxy groups (preferably C6-C24, more preferably C6-C12 arylsulfonyloxy groups such as phenyl Sulfonyloxy), acyl groups (preferably having 1 to 4, 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), an 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 ¹¹ 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 ¹¹ are further substitutable groups, they may be substituted with the substituents described above. When substituted with the above substituents, these substituents may be the same or different.

In the general formula (1), L ^A1 is preferably —N (R ² ) C (═O) —, —OC (═O) —, —C (═O) N (R ² ) —, — C (= O) 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 same as the alkyl group, aryl group, and hetero group described in the substituent of the substituted alkyl group and substituted aryl group of R ^11. A cyclic group is mentioned as an example, and a preferable aspect 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 ¹¹ (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 a position bonded to the —C (R ¹ ) ═CH ₂ group in the general formula (1), and ** represents L ^A1 or Dye (when 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 ¹¹ , 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 the L ^A1 , 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, in the general formula (1), L ^A1 may further have a linking group shown below.
That is, as a divalent linking group for linking —C (R ¹ ) ═CH ₂ group (when m = 0) and Dye, L ^A1 is constituted by linking with the above-mentioned preferable divalent linking group. May be.
Such a divalent linking group 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 the divalent linking group included as the partial structure of L ^A1 is an alkylene group, an aralkylene group, or an arylene group, it may be unsubstituted or substituted, and when it is substituted, the R ¹¹ may be substituted with the substituents described above, and when substituted with two or more substituents, these substituents may be the same or different.
When the divalent linking group included as the partial structure of L ^A1 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 6 to 6 carbon atoms 18 arylene groups are preferred, alkylene groups having 1 to 8 carbon atoms, aralkylene groups having 6 to 16 carbon atoms, and arylene groups having 6 to 12 carbon atoms are more preferred, alkylene groups having 1 to 6 carbon atoms, and 6 to 6 carbon atoms. Twelve aralkylene groups are more preferred.

Preferred combinations of the divalent linking group represented by L ^A1 include —N (R ² ) C (═O) —, —OC (═O) —, —C (═O) N (R ² ) —. And at least one selected from —C (═O) O—, 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, and 2 to 2 carbon atoms. An embodiment of a divalent linking group obtained by combining at least one selected from 18 alkyl thioethers, C 2-18 alkylcarbonamide groups, and C 2-18 alkylaminocarbonyl groups is preferred. More preferably, one selected from —OC (═O) —, —C (═O) N (R ² ) —, and —C (═O) O—, and an alkylene group having 1 to 8 carbon atoms, From 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 It is an embodiment formed by linking one selected, and more preferably —C (═O) N (R ² ) — or —C (═O) O— and alkylene having 1 to 6 carbon atoms. A group formed by bonding a group, an aralkylene group having 6 to 12 carbon atoms, an alkylthioether having 2 to 6 carbon atoms, an alkylcarbonamide group having 2 to 6 carbon atoms, or an alkylaminocarbonyl group having 2 to 6 carbon atoms. .

Below, examples of the polymerizable group represented in the general formula (1) in ^{-L A1 -C (R 1) =} CH 2. However, the present invention is not limited to these.

(Dye residue)
In the general formula (A1) and Dye in the general formula (1), as described above, monomethine dye, dimethine dye, trimethine dye, cyanine dye, merocyanine dye, dicyanostyryl dye, diphenylmethane Dyes, triphenylmethane dyes, xanthene dyes, squarylium dyes, quinophthalone dyes, monoazo dyes, bisazo dyes, disazo dyes, trisazo dyes, quinophthalone dyes, anthraquinone dyes, anthrapyridone dyes, 1 hydrogen atom from one dye compound selected from the group consisting of perylene dyes, diketopyrrolopyrrole dyes, isoindoline dyes, phthalocyanine dyes, azomethine dyes, dioxazine dyes, and dipyrromethene dyes Pigment residue deviated in the range of 1 to m + 1 It is preferable that.

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. However, R ⁴ and R ⁹ do not form a ring.

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 for introducing an alkali-soluble group into the specific dye multimer in the present invention, the dipyrromethene metal complex will be described as an example. When a dye monomer or a structural unit having an alkali-soluble group is used, Any one or two or more substituents of R ^{4 to} R ¹⁰ , X ¹ and X ² of the dipyrromethene-based metal complex compound represented by 5) 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 acyl group (preferably an acyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl, cyclohexanoyl), an alkoxycarbonyl group (preferably carbon An alkoxycarbonyl group having 2 to 48, more preferably 2 to 24 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl, 2,6-di-tert-butyl-4-methylcyclohexyloxy Carbonyl), an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 32 carbon atoms, more preferably an aryloxycarbonyl group having 7 to 24 carbon atoms, such as phenoxycarbonyl), a carbamoyl group (preferably having 1 to 48 carbon atoms, more preferably Is carbon 1 to 24 carbamoyl groups such as carbamoyl, N, N-diethylcarbamoyl, N-ethyl-N-octylcarbamoyl, N, N-dibutylcarbamoyl, N-propylcarbamoyl, N-phenylcarbamoyl, N-methyl, N -Phenylcarbamoyl, N, N-dicyclohexylcarbamoyl), an amino 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 anilino group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, such as anilino, N-methylanilino), heterocyclic amino Group (preferably having 1 to 32 carbon atoms, more preferably carbon A heterocyclic amino group having 1-18, for example, 4-pyridylamino), a carbonamido group (preferably a carbonamide group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, acetamide, benzamide, tetradecane Amide, pivaloylamide, cyclohexaneamide), 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), imide A group (preferably an imide group having 36 or less carbon atoms, more preferably 24 or less carbon atoms, such as N-succinimide or N-phthalimide), an alkoxycarbonylamino group (preferably having 2 to 48 carbon atoms, more preferably a carbon number). 2-24 alkoxycarbonylamino groups such as methoxy Bonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino, cyclohexyloxycarbonylamino), aryloxycarbonylamino group (preferably having 7 to 32 carbon atoms, more preferably having 7 to 24 carbon atoms) A group such as phenoxycarbonylamino), a sulfonamide group (preferably a sulfonamide group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methanesulfonamide, butanesulfonamide, benzenesulfonamide, Hexadecanesulfonamide, cyclohexanesulfonamide), a sulfamoylamino group (preferably a sulfamoylamino group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, N, N-dip Pils sulfamoyl amino, N- ethyl -N- dodecyl sulfamoylamino)

  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, for example, phenylthio), 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 an arylsulfinyl group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, such as phenylsulfinyl), an alkylsulfonyl group (preferably having 1 to 48 carbon atoms, more preferably having 1 to 24 carbon atoms) An alkylsulfonyl group such as methyls Phenyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecylsulfonyl, octylsulfonyl, cyclohexylsulfonyl), arylsulfonyl groups (preferably having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms). An arylsulfonyl group 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 group). Moyl, N-ethyl-N-dodecylsulfamoyl, N-ethyl-N-phenylsulfamoyl, N-cyclohexylsulfamoyl), sulfo group, phosphonyl group (preferably having 1 to 32 carbon atoms, Ri preferably include phosphonyl group having 1 to 24 carbon atoms.

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 More preferably a branched chain having 1 to 12 carbon atoms or a cyclic substituted or unsubstituted alkyl group, and more specifically, for example, an isopropyl group, a cyclopropyl group, an 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. There, more specifically, for example, isopropyl, cyclopropyl, i- butyl, t- butyl group, a cyclobutyl group, a 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, among exemplary compounds of the specific dye multimer in the present invention, examples of the compound having a polymer structure are structural units derived from the dye monomer represented by the general formula (A1) included in the dye multimer and other compounds. Although it shows by disclosing the structural unit derived from a monomer (The structural unit represented by general formula (A2) and the arbitrary copolymerization component contained as needed), its content, and a weight average molecular weight, this invention is shown. Is not limited to the following exemplified compounds.
In the following exemplary compounds, “Mw” represents “weight average molecular weight”, and “mol%” represents “mol%”.

<Method for producing dye multimer>
In the method for producing a specific dye multimer according to the present invention, a dye monomer capable of forming a structural unit represented by the following general formula (A1) is used as a total of 15 dye monomers necessary for the synthesis of the dye multimer. advance the charged charge liquid over mass% 70 mass% was prepared, then, involves dropping polymerization using the remaining dye monomer. The method for producing a dye multimer of the present invention is an embodiment of this production method.
Manufacturing process This, the dye monomer charged in advance, which is the ratio of the dye monomer is added by the remaining dropping, characterized by being adjusted so that each monomer is homogeneously consumed In addition, the reaction temperature, the molecular weight of the polymer, the yield, and the like can be optimized by controlling them within a range where there is no problem in production.

The general formula (A1) is as described above.
In this production method, the total monomer concentration in the charging solution is preferably 15% by mass or more and 100% by mass or less.
Moreover, it is preferable from a viewpoint of hardening that the said dropping polymerization is implemented as radical polymerization or living radical polymerization.

(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 Example 1: Synthesis Example of Exemplary Compound 1-3)
The following dye monomer 1: 6 g (total dye monomer), methacrylic acid: 0.56 g, dodecanethiol: 0.22 g, and propylene glycol monomethyl ether acetate (PGMEA): 15.3 g mixed solution 40 Stir for 5 minutes at a temperature of 7.31 g, which is 33.3% of the solution, in a 200 ml three-necked flask (containing 33.3% of all dye monomers) and stir at 85 ° C. under nitrogen. did. 0.51 g of radical initiator (dimethyl 2,2′-azobis (2-methylpropionate) · V-601) was added to the remaining 66.6% solution, and the dissolved solution was added to the flask. The solution was added dropwise over 1 hour. After completion of the dropping, the mixture was stirred at 85 ° C. for 1 hour under nitrogen, and then 0.051 g of a radical initiator (V-601) was added, and further stirred at 85 ° C. for 2 hours under nitrogen, followed by stirring and heating. Stopped.

A solution obtained by adding PGMEA: 68 ml and methanol: 90 ml to the reaction solution at room temperature was added dropwise to acetonitrile: 362 ml over 20 minutes at room temperature. The mixture was then stirred for 20 minutes, and the precipitated dye multimer was filtered off and dried at 40 ° C. under reduced pressure for 12 hours. Illustrative compound 1-3: 3.85 g was obtained. The yield was 58.7%.
(Synthesis Example 2: Synthesis of Exemplified Compound 4-3)
Illustrative compounds 1-3 and 3 g obtained above, 0.27 g of glycidyl methacrylate, 0.0033 g of p-methoxyphenol, and 18.5 g of propylene glycol monomethyl ether acetate (PGMEA) were placed in a 100 ml three-necked flask and stirred at 100 ° C. . Thereafter, 0.048 g of tetra n-butylammonium bromide was added into the flask, and the mixture was stirred at 100 ° C. for 7 hours, and then stirring and heating were stopped.
The reaction solution that had reached room temperature was added dropwise to 218 ml of acetonitrile over 20 minutes at room temperature. Thereafter, the mixture was stirred for 20 minutes, and the precipitated dye multimer was filtered off and dried at 40 ° C. for 12 hours under blowing. Exemplary compound 4-3: 2.5 g was obtained in a yield of 76.5%.

(Synthesis Example 3: Synthesis of Exemplary Compound 5-3)
Dye monomer 2:35 g (total dye monomer) having the following structure, methacrylic acid: 9.26 g, dodecanethiol: 3.12 g, and propylene glycol monomethyl ether acetate (PGMEA) 250.8 g Was stirred for 5 minutes at 40 ° C., and 198.8 g (containing 66.6% of the total dye monomer), which was 66.6% of the solution, was pre-charged into a 1 L three-necked flask. Was stirred at. To the remaining 66.6% solution, 7.11 g of radical initiator (dimethyl 2,2′-azobis (2-methylpropionate) · V-601) was added, and the dissolved solution was added to the flask. It was added dropwise over 30 minutes. After completion of dropping, the mixture was stirred at 85 ° C. for 1 hour under nitrogen, and then 2.13 g of a radical initiator (V-601) was added, and further stirred at 85 ° C. for 2 hours under nitrogen, followed by stirring and heating. Stopped.

  A solution obtained by adding 916 ml of PGMEA and 1221 ml of methanol to the reaction solution at room temperature was added dropwise to 4884 ml of acetonitrile over 20 minutes at room temperature. The mixture was then stirred for 20 minutes, and the precipitated dye multimer was filtered off and dried at 40 ° C. under reduced pressure for 12 hours. Exemplary compound 5-3: 26.5 g was obtained in a yield of 59.8%.

(Synthesis Example 4: Synthesis of Exemplary Compound 7-3)
A solution in which pigment monomers 3, 10 g (total pigment monomers) having the following structure, methacrylic acid, 1.85 g, dodecanethiol 0.36 g, and propylene glycol monomethyl ether acetate (PGMEA) 17.78 g were mixed at 40 ° C. The mixture was stirred for 5 minutes, and 15.8 g (containing 50% of the total dye monomer) as 50% of the solution was charged into a 100 ml three-necked flask and stirred at 85 ° C. under nitrogen. 1.65 g of a radical initiator (dimethyl 2,2′-azobis (2-methylpropionate) · V-601) was added to the remaining 50% solution, and the dissolved solution was added to the flask for 1 hour. It was dripped over. After completion of the dropwise addition, the mixture was stirred for 1 hour at 85 ° C. under nitrogen, and then 0.5 g of a radical initiator (V-601) was added, and further stirred for 2 hours at 85 ° C. under nitrogen, followed by stirring and heating. Stopped.

  A solution obtained by adding 95 ml of PGMEA and 127 ml of methanol to the reaction solution at room temperature was added dropwise to 506 ml of acetonitrile over 20 minutes at room temperature. The mixture was then stirred for 20 minutes, and the precipitated dye multimer was filtered off and dried at 40 ° C. under reduced pressure for 12 hours. Example compound 7-3: 5.22 g was obtained with a yield of 44.1%.

(Synthesis Example 5: Synthesis of Exemplary Compound 9-3)
Dye monomer 4:12 g (total dye monomer) having the following structure, methacrylic acid: 2.79 g, dodecanethiol: 1.64 g, and propylene glycol monomethyl ether acetate (PGMEA): 27.5 g were mixed. The solution was stirred at 40 ° C. for 5 minutes, and 70% of the solution, 30.8 g, was charged into a 200 ml three-necked flask and stirred at 85 ° C. under nitrogen. 2.49 g of radical initiator (dimethyl 2,2′-azobis (2-methylpropionate) · V-601) was added to the remaining 10% solution, and the dissolved solution was added to the flask for 30 minutes. It was dripped over. After completion of dropping, the mixture was stirred at 85 ° C. for 1 hour under nitrogen, and then 0.75 g of a radical initiator (V-601) was added, and further stirred at 85 ° C. for 2 hours under nitrogen, followed by stirring and heating. Stopped.

  A solution obtained by adding 139 ml of PGMEA and 186 ml of methanol to the reaction solution at room temperature was added dropwise to 742 ml of acetonitrile over 20 minutes at room temperature. The mixture was then stirred for 20 minutes, and the precipitated dye multimer was filtered off and dried at 40 ° C. under reduced pressure for 12 hours. Example compound 9-3: 5.81 g was obtained in a yield of 39.3%.

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.
When the pigment is contained, it is preferably contained in the form of a pigment dispersion containing a pigment, a dispersant, and a solvent.
The coloring composition of the present invention contains various colorants because the occurrence of uneven color unevenness due to the aggregation structure of the dyes is suppressed while the elution and bleeding by the dye multimers are suppressed. It is suitably used for applications.

<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.
When the colored composition of the present invention used for the photolithography method is used in the form of a colored radiation-sensitive composition described later, the colored composition 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 the below-mentioned, it is preferable that there is little content of a solvent from a sclerosing | hardenable viewpoint, and the form which does not use a solvent may also exist.

In addition to the specific dye monomer and other colorants, the colored composition of the present invention includes, in addition to the above-described solvents depending on the purpose, a dispersant for improving dispersion stability, a surfactant, and the like. Other components may be used in combination.
When the coloring composition is applied to a curable composition, it may be used as a radiation-sensitive composition that is cured by radiation by adding a polymerization initiator and a polymerizable compound, as described in detail below. .

<< Colored radiation-sensitive composition >>
<Polymerizable compound>
In a preferred embodiment, the colored composition of the present invention is a colored radiation-sensitive composition containing a polymerizable compound and a polymerization initiator. By taking such an aspect, a colored cured film or a colored pattern can be formed.
Specifically, the polymerizable compound is selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more. Such a compound group is widely known in the industrial field, and these can be used without particular limitation in the present invention. These may be in any chemical form such as, for example, monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and multimers thereof. The polymeric compound in this invention may be used individually by 1 type, and may use 2 or more types together.

More specifically, examples of monomers and prepolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, And multimers thereof, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and multimers thereof. is there. Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and further a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a compound group in which an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is used instead of the unsaturated carboxylic acid.
As these specific compounds, the compounds described in paragraphs [0095] to [0108] of JP-A-2009-288705 can also be suitably used in the present invention.

The polymerizable compound is also preferably a compound having at least one addition-polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as anurate, glycerin and trimethylolethane, JP-B-48-41708, JP-B-50-6034, JP-A-51- Urethane (meth) acrylates as described in JP-B-37193, polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates and the like, which are reaction products of epoxy resins and (meth) acrylic acid, and mixtures thereof.
A polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group can also be used.
Other preferred polymerizable compounds include compounds having a fluorene ring and having two or more functional ethylenically unsaturated groups described in JP-A 2010-160418, JP-A 2010-129825, and Japanese Patent 4364216, and cardo resins. Can also be used.

  Moreover, as a compound having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group, paragraph numbers [0254] to [0257] of JP-A-2008-292970 are disclosed. Also suitable are the compounds described in.

  In addition to the above, radically polymerizable monomers represented by the following general formulas (MO-1) to (MO-5) can also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

In the said general formula, n is 0-14 and m is 1-8. A plurality of R and T present in one molecule may be the same or different.
In each of the polymerizable compounds represented by the general formulas (MO-1) to (MO-5), at least one of a plurality of Rs is —OC (═O) CH═CH ₂ or —OC. (= O) represents a group represented by C (CH ₃ ) ═CH ₂ .
Specific examples of the polymerizable compounds represented by the general formulas (MO-1) to (MO-5) include the compounds described in paragraphs 0248 to 0251 of JP-A-2007-26979. It can be suitably used in the invention.

  Moreover, the compound which (meth) acrylate-ized after adding ethylene oxide and propylene oxide to the said polyfunctional alcohol described with the specific example as general formula (1) and (2) in Unexamined-Japanese-Patent No. 10-62986 is also, It can be used as a polymerizable compound.

  Among these, as the polymerizable compound, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; Nippon Kayaku Co., Ltd.) Dipentaerythritol penta (meth) acrylate (commercially available product: KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available product: KAYARAD DPHA; Nippon Kayaku Co., Ltd.) And a structure in which these (meth) acryloyl groups are interposed via ethylene glycol and propylene glycol residues. These oligomer types can also be used. Preferred embodiments of the polymerizable compound are shown below.

  As a polymeric compound, it is a polyfunctional monomer, Comprising: You may have acid groups, such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. If the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, this can be used as it is. Non-aromatic carboxylic acid anhydrides may be reacted to introduce acid groups. In this case, specific examples of the non-aromatic carboxylic acid anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.

  In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having an acid group is preferred, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

These monomers may be used alone, but since it is difficult to use a single compound in production, two or more kinds may be mixed and used. Moreover, you may use together the polyfunctional monomer which does not have an acid group as a monomer, and the polyfunctional monomer which has an acid group as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g. If the acid value of the polyfunctional monomer is too low, the developing dissolution properties are lowered, and if it is too high, the production and handling are difficult, the photopolymerization performance is lowered, and the curability such as the surface smoothness of the pixel is deteriorated. Accordingly, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer should be adjusted so as to fall within the above range. Is preferred.

Moreover, it is also a preferable aspect to contain a polyfunctional monomer having a caprolactone structure as the polymerizable monomer.
The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, penta Ε-caprolactone modified polyfunctionality obtained by esterifying polyhydric alcohol such as erythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone ( Mention may be made of (meth) acrylates. Especially, the polyfunctional monomer which has a caprolactone structure represented with the following general formula (Z-1) is preferable.

  In general formula (Z-1), all six R are groups represented by the following general formula (Z-2), or 1 to 5 of the six Rs are represented by the following general formula (Z -2), and the remainder is a group represented by the following general formula (Z-3).

In General Formula (Z-2), R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and “*” represents a bond.

In General Formula (Z-3), R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond. )

Such a polyfunctional monomer having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and DPCA-20 (m = 1 in the above formulas (1) to (3)). , Number of groups represented by formula (2) = 2, compound in which R ¹ is all hydrogen atoms, DPCA-30 (same formula, m = 1, number of groups represented by formula (2) = 3 , Compounds in which R ¹ is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (2) = 6, compounds in which R ¹ are all hydrogen atoms), DPCA- 120 (a compound in which m = 2 in the same formula, the number of groups represented by formula (2) = 6, and all R ¹ are hydrogen atoms).
In this invention, the polyfunctional monomer which has a caprolactone structure can be used individually or in mixture of 2 or more types.

  In addition, the specific monomer in the present invention is preferably at least one selected from the group of compounds represented by the following general formula (Z-4) or (Z-5).

In the general formulas (Z-4) and (Z-5), each E independently represents — ((CH ₂ ) yCH ₂ O) — or — ((CH ₂ ) yCH (CH ₃ ) O) —. Y represents each independently an integer of 0 to 10, and X each independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.
In the general formula (Z-4), the total of the acryloyl group and the methacryloyl group is 3 or 4, each m independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40. is there. However, when the total of each m is 0, any one of X is a carboxyl group.
In the general formula (ii), the total number of acryloyl groups and methacryloyl groups is 5 or 6, each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60. However, when the total of each n is 0, any one of X is a carboxyl group.

In the general formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Moreover, the integer of 2-40 is preferable, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable as the sum total of each m.
In the general formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Further, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
In general formula (Z-4) or general formula (Z-5) in the _{- ((CH 2) yCH 2} O) - or _{- ((CH 2) yCH (} CH 3) O) - , the oxygen atom side A form in which the terminal of X is bonded to X is preferred.

  The compound represented by the general formula (Z-4) or the general formula (Z-5) may be used alone or in combination of two or more. In particular, in the general formula (ii), a form in which all six Xs are acryloyl groups is preferable.

  Moreover, as a total content in the polymeric compound of the compound represented by general formula (Z-4) or general formula (Z-5), 20 mass% or more is preferable, and 50 mass% or more is more preferable.

  The compound represented by the general formula (Z-4) or the general formula (Z-5) is a conventionally known process, which is a ring opening of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol. It can be synthesized from a step of bonding a ring-opening skeleton by an addition reaction and a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with a terminal hydroxyl group of the ring-opening skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (i) or (ii).

Among the compounds represented by the general formula (Z-4) or the general formula (Z-5), a pentaerythritol derivative and / or a dipentaerythritol derivative are more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”), and among them, exemplary compounds (a) and ( b), (e) and (f) are preferred.

  Examples of commercially available polymerizable compounds represented by the general formulas (Z-4) and (Z-5) include SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, Nippon Kayaku Examples thereof include DPCA-60, which is a hexafunctional acrylate having 6 pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having 3 isobutyleneoxy chains.

Examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, Also suitable are urethane compounds having an ethylene oxide-based skeleton described in 58-49860, JP-B 56-17654, JP-B 62-39417, and JP-B 62-39418. Further, as polymerizable compounds, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are exemplified. By using it, it is possible to obtain a curable composition having an extremely excellent photosensitive speed.
Commercially available polymerizable compounds include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 "(manufactured by Shin-Nakamura Chemical 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) and the like.

About these polymerizable compounds, the details of usage such as the structure, single use or combination, addition amount and the like can be arbitrarily set in accordance with the final performance design of the colored curable composition. For example, from the viewpoint of sensitivity, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, from the viewpoint of increasing the strength of the colored cured film, those having 3 or more functional groups are preferred, those having 4 or more functional groups are preferable, and those having 5 or more functional groups are more preferable. Furthermore, a method of adjusting both sensitivity and strength by using different functional groups and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound) is also effective. Further, it is preferable to use a polymerizable compound having three or more functionalities and different ethylene oxide chain lengths in that the developability of the radiation-sensitive composition can be adjusted and excellent pattern forming ability can be obtained. .
In addition, the selection of the polymerizable compound is also possible with respect to the compatibility and dispersibility with other components (for example, photopolymerization initiator, colorant (pigment), binder polymer, etc.) contained in the radiation-sensitive composition. The method of use is an important factor. For example, compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected from the viewpoint of improving adhesion to a hard surface such as a support.

  As for content of the polymeric compound in the radiation sensitive composition of this invention, 0.1 mass%-90 mass% are preferable with respect to solid content in a radiation sensitive composition, and 1.0 mass%-80 mass. % Is more preferable, and 2.0% by mass to 70% by mass is particularly preferable.

<Polymerization initiator>
The colored radiation-sensitive composition of the present invention can contain a polymerization initiator.
The photopolymerization initiator in the present invention is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferable. Further, it may be an activator that generates some action with a photoexcited sensitizer and generates an active radical, or may be an initiator that initiates cationic polymerization according to the type of monomer.
The photopolymerization initiator preferably contains at least one compound having a molecular extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

  Examples of the photopolymerization initiator in the present invention include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, and hexaarylbiimidazoles. Oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, and the like. Of these, oxime compounds are preferred.

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Pat. No. 4,221,976 And the compounds described in the book.

  Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenonetetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenone (for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bisdicyclohexyl) Amino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylaminobenzene Zophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro -Thioxanthone, 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, benzo Down propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro acridone, N- methyl acridone, N- butyl acridone, N- butyl - such as chloro acrylic pyrrolidone.

As the polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by Ciba Japan) can be used. As the aminoacetophenone initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by Ciba Japan) can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long-wave light source such as 365 nm or 405 nm can also be used. Moreover, IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by Ciba Japan), which are commercially available products, can be used as the acylphosphine initiator.

  More preferred examples of the polymerization initiator include oxime compounds. Specific examples of the oxime initiator include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.

  Examples of oxime compounds such as oxime derivatives that are preferably used as a polymerization initiator in the present invention include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutan-2-one, and 3-propionyloxyimibutane. 2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4- Toluenesulfonyloxy) iminobutan-2-one and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.

Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 15
6-162, Journal of Photopolymer Science and Technology (1995), pp. 6-162. 202-232, compounds described in JP-A No. 2000-66385, compounds described in JP-A No. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
IRGACURE OX-01 (manufactured by BASF) and IRGACURE OXE-02 (manufactured by BASF) are also preferably used as commercial products.

  Further, as oxime ester compounds other than those described above, compounds described in JP-T 2009-519904, in which an oxime is linked to the N-position of carbazole, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, A compound described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced into the dye moiety, a ketoxime compound described in International Patent Publication No. 2009-131189, the triazine skeleton and the oxime skeleton are the same A compound described in US Pat. No. 7,556,910 contained in the molecule, a compound described in JP 2009-221114 A having an absorption maximum at 405 nm and good sensitivity to a g-ray light source may be used.

Preferably, it can also be suitably used for the cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744. Among the cyclic oxime compounds, the cyclic oxime compounds fused to the carbazole dyes described in JP2010-32985A and JP2010-185072A in particular have high light absorptivity from the viewpoint of high sensitivity. preferable.
Further, the compound described in JP-A-2009-242469 having an unsaturated bond at a specific site of the oxime compound can be preferably used because it can achieve high sensitivity by regenerating active radicals from polymerization inert radicals. it can.

Most preferably, the oxime compound which has a specific substituent shown by Unexamined-Japanese-Patent No. 2007-267979 and the oxime compound which has a thioaryl group shown by Unexamined-Japanese-Patent No. 2009-191061 are mentioned.
Specifically, the oxime polymerization initiator is preferably a compound represented by the following formula (OX-1). The N—O bond of the oxime may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .

(In formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.)
In the formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group. , Dodecyl group, octadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1- Naphthoylmethyl group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2- Methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, and , 3 Nitorofenashiru group can be exemplified.

  The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, specifically, a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, or a 9-anthryl group. 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-tolyl group, m-tolyl group, p -Tolyl group, xylyl group, o-cumenyl group, m-cumenyl group and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, full Oranthenyl, acenaphthylenyl, aceanthrylenyl, phenalenyl, fluorenyl, ant Ryl group, bianthracenyl group, teranthracenyl group, quarteranthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrycenyl group, naphthacenyl group, pleiadenyl group, picenyl group, perylenyl group, pentaphenyl group, Examples thereof include a pentacenyl group, a tetraphenylenyl group, a hexaphenyl group, a hexacenyl group, a ruvicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an ovalenyl group.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, specifically, an acetyl group, a propanoyl group, a butanoyl group, a trifluoroacetyl group, a pentanoyl group, a benzoyl group, 1-naphthoyl group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2 -Methoxybenzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, and And 4-methoxybenzoyl group.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, specifically, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, or a hexyloxy group. Examples thereof include a carbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.

  Specific examples of the aryloxycarbonyl group which may have a substituent include phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenylsulfanyl. Phenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxy Carbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl , 4-fluorophenyl oxycarbonyl group, 4-cyanophenyl oxycarbonyl group, and a 4-methoxy phenyloxy carbonyl group can be exemplified.

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

  Specific examples of the alkylthiocarbonyl group which may have a substituent include a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, an octylthiocarbonyl group, a decylthiocarbonyl group, and an octadecylthiocarbonyl group. Examples thereof include a group and a trifluoromethylthiocarbonyl group.

  Specific examples of the arylthiocarbonyl group which may have a substituent include a 1-naphthylthiocarbonyl group, a 2-naphthylthiocarbonyl group, a 4-methylsulfanylphenylthiocarbonyl group, and a 4-phenylsulfanylphenylthiocarbonyl group. 4-dimethylaminophenylthiocarbonyl group, 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3 -Chlorophenylthiocarbonyl group, 3-trifluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenyl Two thiocarbonyl group, and a and a 4-methoxyphenylthiocarbonyl group.

  In the formula (OX-1), the monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

Of these, the structures shown below are particularly preferred.
In the following structure, Y, X, and n have the same meanings as Y, X, and n in formula (OX-2) described later, and preferred examples are also the same.

In the formula (OX-1), examples of the divalent organic group represented by A include an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, and an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Among them, A in the formula (OX-1) is an unsubstituted alkylene group, an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, dodecyl) from the viewpoint of increasing sensitivity and suppressing coloring due to heating. Group) substituted alkylene group, alkenyl group (eg vinyl group, allyl group) alkylene group, aryl group (eg phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl) Group, a phenanthryl group, and a styryl group) are preferable.

In the formula (OX-1), the aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms, and may have a substituent. Examples of the substituent include the same substituents as those introduced into the substituted aryl group mentioned above as specific examples of the aryl group which may have a substituent.
Among these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

  In the formula (OX-1), it is preferable from the viewpoint of sensitivity that the structure of “SAr” formed by Ar in the formula (OX-1) and S adjacent thereto is a structure shown below. Me represents a methyl group, and Et represents an ethyl group.

  The oxime compound is preferably a compound represented by the following formula (OX-2).

(In Formula (OX-2), R and X each independently represent a monovalent substituent, A and Y each independently represent a divalent organic group, Ar represents an aryl group, and n represents 0 to 0. (It is an integer of 5.)
R, A and Ar in the formula (OX-2) have the same meanings as R, A and Ar in the formula (OX-1), and preferred examples are also the same.

  In the formula (OX-2), the monovalent substituent represented by X includes an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an amino group, and a heterocyclic ring. Group and halogen atom. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

Among these, as X in Formula (OX-2), an alkyl group is preferable from the viewpoints of solvent solubility and improvement in absorption efficiency in the long wavelength region.
Moreover, n in Formula (2) represents the integer of 0-5, and the integer of 0-2 is preferable.

  In the formula (OX-2), examples of the divalent organic group represented by Y include the structures shown below. In the groups shown below, “*” represents a bonding position between Y and an adjacent carbon atom in the formula (OX-2).

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

  Furthermore, the oxime compound is preferably a compound represented by the following formula (OX-3).

(In Formula (OX-3), R and X each independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and n is an integer of 0 to 5. .)
R, X, A, Ar, and n in Formula (OX-3) have the same meanings as R, X, A, Ar, and n in Formula (OX-2), respectively, and preferred examples are also the same. is there.

  Specific examples (C-4) to (C-14) of oxime compounds that can be suitably used are shown below, but the present invention is not limited thereto.

  The oxime compound has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably has high absorbance at 365 nm and 455 nm.

The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred.
For the molar extinction coefficient of the compound, a known method can be used. Specifically, for example, 0.01 g of an ultraviolet-visible spectrophotometer (Varian Inc., Carry-5 spectrphotometer) is used with an ethyl acetate solvent. It is preferable to measure at a concentration of / L.

The polymerization initiator used in the present invention may be used in combination of two or more as required.

  As a polymerization initiator used in the radiation-sensitive composition of the present invention, from the viewpoint of exposure sensitivity, a trihalomethyltriazine compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, phosphine Oxide compound, metallocene compound, oxime compound, triallylimidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound and derivative thereof, cyclopentadiene-benzene-iron complex and salt thereof, halomethyloxadiazole compound, 3- Compounds selected from the group consisting of aryl substituted coumarin compounds are preferred.

  More preferred are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, trihalomethyltriazine compounds, α-aminoketones. Most preferred is at least one compound selected from the group consisting of compounds, oxime compounds, triallylimidazole dimer, and benzophenone compounds.

  In particular, when the radiation-sensitive composition of the present invention is used for the production of a color filter of a solid-state imaging device, it is necessary to form a fine pattern with a sharp shape, so that a residue is left in the unexposed area together with curability. It is important that there is no development. From such a viewpoint, it is particularly preferable to use an oxime compound as the polymerization initiator. In particular, when a fine pattern is formed in a solid-state imaging device, stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and it is necessary to keep the addition amount of a polymerization initiator low. Considering these points, it is most preferable to use an oxime compound as a polymerization initiator for forming a fine pattern such as a solid-state imaging device.

  The content of the polymerization initiator contained in the radiation-sensitive composition of the present invention is preferably 0.1% by mass or more and 50% by mass or less, more preferably based on the total solid content of the radiation-sensitive composition. It is 0.5 mass% or more and 30 mass% or less, More preferably, it is 1 mass% or more and 20 mass% or less. Within this range, good sensitivity and pattern formability can be obtained.

<Naphthoquinonediazide compound>
Another embodiment of the colored radiation-sensitive composition of the present invention is a positive colored radiation-sensitive composition. When constituting a positive radiation sensitive 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 radiation-sensitive 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, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene monomer Romonoma, mention may be made of 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; Kill 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, a benzyl group, etc. 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, JP 2002-229207 A And a resin obtained by performing a basic treatment on a resin having an ester group having a leaving group such as a halogen atom or a sulfonate group at the α-position or β-position described in JP-A-2003-335814 Etc. are preferable.

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

  As content in the 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 colored radiation-sensitive composition of the present invention may contain a crosslinking agent.
The crosslinking agent is not particularly limited as long as it can cure the film 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 tetramethylol guanamine, tetramethoxymethyl guanamine, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol guanamine or a mixture thereof, tetramethoxyethyl guanamine, tetraacyloxymethyl guanamine, tetramethylol. Examples thereof include compounds obtained by acyloxymethylating 1 to 3 methylol groups of guanamine 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 in which 1 to 3 are acyloxymethylated 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 2-position and 4-position 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, a sufficient degree of curing and elution of the uncured part can be maintained, the degree of curing of the cured part is insufficient, or the elution of the uncured part is significantly reduced. Can be prevented.

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

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

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

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

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

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

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

Only one type of surfactant may be used, or two or more types may be combined.
The addition amount of the surfactant is preferably 0.001% by mass to 2.0% by mass, more preferably 0.005% by mass to 1.0% by mass with respect to the total mass of the radiation-sensitive composition of the present invention. %.

<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.

<Organic carboxylic acid, organic carboxylic anhydride>
The colored radiation-sensitive composition of the present invention may contain one or more compounds selected from organic carboxylic acids having a molecular weight of 1000 or less and organic carboxylic anhydrides.
Specific examples of the organic carboxylic acid compound include aliphatic carboxylic acids and aromatic carboxylic acids. Examples of aliphatic carboxylic acids include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, acrylic acid, methacrylic acid, oxalic acid, malonic acid, succinic acid, Examples thereof include dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid and fumaric acid, and tricarboxylic acids such as tricarbaryl acid and aconitic acid. Examples of the aromatic carboxylic acid include carboxylic acids in which a carboxyl group is directly bonded to a phenyl group such as benzoic acid and phthalic acid, and carboxylic acids in which a carboxyl group is bonded to the phenyl group through a carbon bond. Among these, those having a molecular weight of 600 or less, particularly a molecular weight of 50 to 500, specifically maleic acid, malonic acid, succinic acid, and itaconic acid are preferred.

Examples of organic carboxylic acid anhydrides include aliphatic carboxylic acid anhydrides and aromatic carboxylic acid anhydrides. Specific examples include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, and tetrahydrophthalic anhydride. Succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, etc. An aliphatic carboxylic acid anhydride is mentioned. Examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride. Among these, those having a molecular weight of 600 or less, particularly a molecular weight of 50 to 500, specifically, maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride are preferable.
The amount of the compound selected from these organic carboxylic acids and organic carboxylic anhydrides is usually 0.01 to 10% by weight, preferably 0.03 to 5% by weight, more preferably 0.05, based on the total solid content. It is in the range of ˜3% by weight.
When forming a pattern with a colored radiation-sensitive composition by adding an organic carboxylic acid or organic carboxylic acid anhydride having a molecular weight of 1000 or less, while maintaining the high pattern adhesion, It becomes possible to further reduce the residue of the dissolved matter.

<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.

<Preparation method>
In preparing the radiation-sensitive composition of the present invention, the above-described components of the composition may be blended together, or may be blended sequentially after each component is dissolved in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. A 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 is applied to a radiation-sensitive composition used for a liquid crystal display (LCD) or a solid-state imaging device (for example, CCD, CMOS, etc.), an inkjet ink, etc., and these colored compositions of the present invention. The composition having a curing property can be suitably used for forming a colored pixel such as a color filter. In particular, it can be suitably used for forming color filters for solid-state imaging devices such as CCDs and CMOSs.

The colored composition of the present invention is applied to a colored radiation-sensitive composition used for producing a color filter by, for example, a photolithography method. In that case, it is particularly suitable for forming 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.
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 colored radiation-sensitive composition using a dye, the dye is likely to permeate into the previously formed pattern (or layer) of another color at the time of application (a dye permeation at the time of application of the next color). Furthermore, in a colored radiation-sensitive 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 the 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 colored radiation-sensitive composition of the present invention containing a specific dye multimer is used, while maintaining the transparency as a dye, the above-mentioned dye-specific dye soaks at the time of application of the next color, at the time of alkali development A colored film (color filter) in which elution of dye and thermal diffusion (color transfer) due to heat treatment can be significantly suppressed can be produced.

≪Color filter and manufacturing method≫
First, the case where the colored radiation-sensitive composition of the present invention is used in the color filter of the present invention will be described. The color filter of the present invention provided with a colored pattern made of a colored radiation-sensitive composition has suppressed color mixing due to soaking, color transfer, and development residue. Moreover, it is excellent also in heat resistance.

  Examples of the method for forming a pattern by the photolithography method using the colored radiation-sensitive composition of the present invention include the methods described in paragraph numbers [0277] to [0284] of JP-A-2008-292970. .

  Specifically, a step of forming the colored layer by applying the colored radiation-sensitive composition on a support (hereinafter also referred to as “colored layer forming step”), and the formed colored layer through a mask A method for producing a color filter having a step of exposing (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”) ( Hereinafter, it is also referred to as “a method for producing a color filter of the present invention”).

<Colored layer forming step>
In the method for producing a color filter of the present invention, first, the colored radiation-sensitive composition of the present invention described above is coated on a support by a coating method such as spin coating, cast coating, roll coating, and the like. After that, 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 the colored radiation-sensitive composition is spin-coated on a support, an appropriate organic solvent is dropped and rotated prior to the dropping of the colored radiation-sensitive composition in order to reduce the amount of liquid dripping. Thus, the familiarity of the colored radiation-sensitive composition with the support can be improved.

Examples of the prebaking condition include a condition of heating at 70 ° C. to 130 ° C. for about 0.5 minutes to 15 minutes using a hot plate or an oven.
The thickness of the colored layer formed from the colored radiation-sensitive composition is appropriately selected according to the purpose, but is generally preferably 0.2 μm to 5.0 μm, preferably 0.3 μm to More preferably, it is 2.5 μm, most preferably 0.3 μm to 1.5 μm. In addition, the thickness of the colored layer here is a film thickness after pre-baking.

<Exposure process>
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 English Light Amplification by Stimulated Emission of Radiation. 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 radiation-sensitive composition).

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

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

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

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

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

<Development process>
Subsequently, the colored layer after exposure is developed with a developer (development process). Thereby, a negative 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 as to have a concentration of 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 irradiated ultraviolet light includes 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 the wavelength light in the ultraviolet light. The thing which can irradiate the light which is is preferable. By setting the irradiation illuminance of light having a wavelength of 275 nm or less in ultraviolet light to 5% or more, the effect of suppressing color transfer between colored pixels and the upper and lower layers and the effect of improving light resistance can be more effectively enhanced. From this point, it is preferable to use a light source different from a light source such as an i-line or the like used for exposure in the pattern forming step, specifically, a high pressure mercury lamp, a low pressure mercury lamp, or the like. Among these, for the same reason as described above, 7% or more is preferable with respect to the integrated irradiation illuminance of all wavelength light in ultraviolet light. Moreover, the upper limit of the irradiation illuminance of light having a wavelength of 275 nm or less is preferably 25% or less.

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

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

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

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

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

  The colored radiation-sensitive composition of the present invention can be easily cleaned and removed using a known cleaning liquid even when it 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. . 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 radiation-sensitive 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, etc. are also preferably used as cleaning liquids for cleaning and removing the colored radiation-sensitive composition of the present invention. Can do.
As the cleaning liquid, it is preferable to use alkylene glycol monoalkyl ether carboxylate or alkylene glycol monoalkyl ether.
These solvents that can be used as the cleaning liquid may be used alone or in combination of two or more.
When mixing 2 or more types of solvent, the mixed solvent formed by mixing the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group is preferable. The mass ratio of the solvent having a hydroxyl group and the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 80/20. The mixed solvent is a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), and the ratio is particularly preferably 60/40.
In addition, in order to improve the permeability of the cleaning liquid to the colored radiation-sensitive composition, the surfactant described above as a surfactant that may be contained in the colored radiation-sensitive 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 the color filter by the ink jet method is not particularly limited, and the step of preparing a substrate having a recess partitioned by a partition and the color composition of the present invention in the recess by the ink jet method will be described later. Forming an ink jet ink of the present invention, and applying droplets of the ink on a substrate to form colored pixels of a color filter. 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 and a polymerizable compound.
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: Solvent suitable for inkjet applications>
The solvent suitably included in the inkjet application is not particularly limited as long as the solubility of each component and the boiling point of the solvent described below are satisfied, but in particular, the solubility, coating property, and safety of the binder described below are taken into consideration. Is preferably selected. 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 the content is 90% by mass or less, the amount of components other than the solvent for forming a functional film (for example, a pixel) in the ink can be maintained 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 solvents described above, 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 property value 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.
When preparing a solution of the polymerizable compound, if the solubility of the material used in the solvent is low, treatment such as heating or ultrasonic treatment is performed within a range in which the polymerizable compound does not cause a polymerization reaction. It can be performed as appropriate.

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-mentioned surface tension is measured by a Wilhelmy method using a commonly used surface tension meter (for example, Kyowa Interface Science Co., Ltd., surface tension meter FACE SURFACE TENSIOMETER CBVB-A3), 60% liquid temperature. 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 to cause disturbance of discharge 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 fine COA (Color-filter On Array) system. In the COA type liquid crystal display device, as the required characteristics for the color filter layer, in addition to the normal required characteristics, the required characteristics for the interlayer insulating film, that is, low dielectric constant and stripping solution resistance are required. In the color filter of the present invention, it is considered that the transparency of the ultraviolet light that is the exposure light can be increased by using an exposure method using an ultraviolet light laser, or by selecting the hue and film thickness of the colored pixels. . As a result, the curability of the colored pixels is improved, and a pixel free from chipping, peeling, or twisting can be formed. Therefore, particularly 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. In the following examples, “%” and “parts” represent “% by mass” and “parts by mass” unless otherwise specified.

[Example 1-1]
(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 (DIC, F-475) 0.80 parts Photopolymerization Initiator: 4-Benzoxolane-2,6-bis (trichloromethyl) -s-triazine (Midori Chemical Co., 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 radiation-sensitive composition The following components were mixed and dispersed and dissolved to obtain a colored radiation-sensitive composition.

Cyclohexanone (solvent) (hereinafter abbreviated as CyH) 1.133 parts benzyl methacrylate / methacrylic acid copolymer (molar ratio = 70: 30,
Weight average molecular weight 30000) (20% CyH solution) (alkali-soluble resin)
... 1.009 parts, polymerizable compound (KAYARAD DPHA (manufactured by Nippon Kayaku)) ... 3.84 parts, fluorosurfactant (Megafac F475, DIC) (1% CyH solution)
(Surfactant) ... 0.12 part · Oxime-based photopolymerization initiator (compound with the following structure) · · · 0.087 part · Specific dye multimer (Exemplary compound 1-3 / weight average molecular weight (Mw) 5300 / dispersion degree (Mw / Mn) 1.85) ... 0.183 part · Pigment Blue 15: 6 dispersion ... 2.418 parts (solid content concentration 17.70%, pigment concentration 11.80%: other colorant)
Nonionic surfactant: glycerol propoxylate (1% CyH solution)
(Surfactant) ... 0.048 part

-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 size 55 nm)), pigment dispersant BYK-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 radiation-sensitive composition (colored pattern formation)
Using a spin coater, the colored radiation-sensitive composition obtained in (3) above is dried on the undercoat layer of the glass substrate with an undercoat layer obtained in (2) so that the film thickness after drying is 0.6 μm. And prebaked 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 colored radiation-sensitive composition, alkali elution resistance, solvent resistance, color transfer due to thermal diffusion, development residue on the substrate, and other colors The development residue and dye penetration were evaluated as follows. The evaluation results are shown in Tables 1 to 5 below.

[Evaluation of zara (color unevenness)]
The obtained monochromatic color filter (colored pattern) is placed between the observation lens and the light source of the optical microscope to irradiate the light toward the observation lens, and a digital camera with a magnification of 1000 times installs the transmitted light state. Was observed with an optical microscope. A digital camera installed in the optical microscope is equipped with a CCD with 1.28 million pixels, and the surface of the coating film in a transmitted light state was photographed. The photographed image was stored as digitally converted data (digital image) in an 8-bit bitmap format.

The film surface of the colored pattern was photographed on 20 arbitrarily selected areas. Also, the digitally converted data was stored by digitizing the captured image as a density distribution of 256 gradations from 0 to 255 for each of the R G B primary colors.
Next, the stored digital image was divided into a lattice shape so that one lattice size corresponds to 2 μm square on the actual substrate, and the luminance in one partition was averaged. In this example, since an image of 1000 times optical was captured with a 1.28 million pixel digital camera, 2 μm on the actual substrate was 2 mm on the captured image, and the image size on the display was 452 mm × 352 mm. The total number of sections in one area was 39976.

For all the sections in each region, an arbitrary luminance and the average luminance of all adjacent sections adjacent to it were measured. A partition having a difference of 5 or more from the average brightness of adjacent partitions is recognized as a significant difference partition, and the average total number of significant difference partitions in all regions and the average total number of significant difference partitions in all regions are the total number of partitions in each region (39976). The ratio of the total to the total) was calculated. The results are shown in Table 1 below.
The smaller this value is, the smaller the density difference from the adjacent section is, indicating that there is less roughness.

(Alkali elution resistance)
The spectrum (spectrum A) of the coating film after the pre-baking (4) 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 spectroscopy was again measured (spectral 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 radiation-sensitive composition (G) is applied on the undercoat layer of the glass substrate with the undercoat obtained in (2) above using a spin coater so that the film thickness after drying is 0.6 μm. , Pre-baked at 100 ° C. for 120 seconds, and then using an exposure apparatus UX3100-SR (manufactured by Ushio Electric Co., Ltd.), the entire surface of the coating film is exposed to a dose of 200 mJ / cm ² without a mask at a wavelength of 365 nm Irradiated. 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 on this, the colored radiation-sensitive composition of the present invention obtained in (3) above was applied using a spin coater so that the film thickness after drying was 0.6 μm, and prebaked at 100 ° C. for 120 seconds. The film was developed using a developer CD-2000 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) without exposure to light at 25 ° C. for 40 seconds. 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%

-Colored radiation-sensitive composition G for evaluating dye penetration-
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 radiation-sensitive composition G was prepared by stirring and mixing the pigment dispersion liquid (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 Polymerizable compound (KAYARAD DPHA ( Nippon Kayaku Co., Ltd.) ... 30 parts / solvent (PGMEA) ... 200 parts / substrate adhesive (3-methacryloxypropyltrimethoxysilane) ... 1 part

[Examples 1-2 to 1-14 and Comparative Examples 1-1 to 1-14]
Examples 1-2 to 1-14 and Comparative Examples 1-1 to 1-14 were evaluated in the same manner except that the dye multimer of Example 1 was changed to the dye multimer described in Table 1.

In each of Examples 1-2 to 1-14, the production method according to the present invention, that is, 15% to 70% of the total amount of the dye monomer is charged into the flask, and the remaining dye monomer is used. It is the evaluation result using the exemplary compound synthesized using the method of dropping polymerization.
As comparative examples respectively corresponding to these examples, evaluation was performed using exemplary compounds synthesized using a conventional production method (a method in which a monomer of 10% of the total amount of monomers was charged in advance and dropped over 2 hours). The results obtained are Comparative Examples 1-1 to 1-14.

As shown in Table 1 above, Examples 1 to 14 using the dye multimer obtained by the specific production method of the present invention are more resistant to alkali elution than Comparative Examples 1 to 14. Solvent resistance, color transfer due to thermal diffusion, residue on substrates and other colors, and suppression of dye penetration are equally excellent, especially the degree of roughness is greatly improved, and the occurrence of roughness is effectively suppressed I understand that.
In addition, the coating liquid (colored radiation-sensitive composition) using the dye multimer controlled to have specific physical properties of the present invention has unexpectedly very good coating properties, and there are no slits or uneven color on the coating surface. It was found to have excellent coating properties.
Although the example which forms a blue coloring pattern (blue color filter) on a glass substrate was demonstrated as Examples 1-14 above, the solid-state image sensor board | substrate (Silicon wafer board | substrate with 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. .

[Examples 1-15 to 1-16]
A commercially available oxime initiator IRGACURE OXE-01 (manufactured by BASF) and IRGACURE OXE-02 (manufactured by BASF)) were used in place of the oxime initiator having the structure used in Example 1-1. Were the same as in Example 1-1, and the colored radiation-sensitive compositions of Examples 1-15 and 1-15 were obtained and evaluated in the same manner as in Example 1-1. Compared to comparative examples, alkali elution resistance, solvent resistance, color transfer due to thermal diffusion, residue on substrates and other colors, and suppression of dye penetration are equally excellent, and the occurrence of roughening is effectively suppressed. I found out.

[Example 2-1]
(1) Preparation of colored radiation-sensitive composition [positive type]-Ethyl lactate (EL) ... 30 parts-The following resin P-1 ... 3.0 parts (alkali-soluble resin)
・ The following naphthoquinonediazide compound N-1: 1.8 parts ・ Crosslinking agent: hexamethoxymethylolated melamine: 0.6 parts ・ Photoacid generator: TAZ-107 (manufactured by Midori Chemical Co., Ltd.): 1.2 parts ・ Fluorine series Surfactant (F-475, manufactured by DIC Corporation) ... 0.0005 part (surfactant)
Specific dye multimer: (Exemplary compound 1-3 / weight average molecular weight (Mw) 5300 / dispersion degree (Mw / Mn) 1.85) ... 0.3 parts or more are mixed, dissolved, and a colored radiation-sensitive composition [Positive type] was obtained.

  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 radiation-sensitive composition [positive type] obtained above by the method according to Example 1, improvement in alkali elution resistance, improvement in solvent resistance, suppression of color transfer due to thermal diffusion, on substrate and others Excellent effects on color residue control and dye penetration control.

[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 2, 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 2 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 obtain a thick film having a thickness of 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 3 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.
Specific dye multimer: exemplary compound 4-3 (weight average molecular weight 6000, dispersity 1.98, acid value 1.25 mmol / g)
DPCA-60 (manufactured by Nippon Kayaku Co., Ltd. (KAYARAD DPCA-60)): caprolactone-modified dipentaerythritol hexaacrylate (polymerizable compound)
-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. was maintained with the temperature of the obtained ink adjusted to 25 ° C.
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 a pigment dispersant (compound B1) and a solvent [1,3-butanediol diacetate (hereinafter 1, 3-BGDA) and 1-methoxy-2-propylacetate (MMPGAC) mixed solvent with a mass ratio of 1.2: 1], 80 parts by mass, and after premixing, motor mill M-50 ( Manufactured by Eiger Japan Co., Ltd.), a zirconia bead having a diameter of 0.65 mm was used at a filling rate of 80% and dispersed at a peripheral speed of 9 m / s for 25 hours to prepare a pigment dispersion for V.

1.2: 1
(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.

[Evaluation of Zara]
Zara was evaluated in the same manner as in Example 1-1. The results are shown in Table 5 below.

(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 5 below summarizes the evaluation results of the inkjet ink and the color filter.

As shown in Table 5, 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 (18)

Synthesis of a dye multimer synthesized using a dye monomer capable of forming a structural unit represented by the following general formula (A1) and a monomer capable of forming a structural unit represented by the following general formula (A2) dye monomer represented by the following general formula required (A1) a dye monomer capable of forming a structural unit represented by, 1 total pigment monomers sac Chi used in the synthesis of the dye polymer 5 wt% A monomer containing a dye monomer capable of forming a structural unit represented by the following general formula (A1) of 70% by mass or less and a monomer capable of forming a structural unit represented by the following general formula (A2). A charge liquid prepared in advance with a monomer is prepared, and the remaining dye monomer capable of forming the structural unit represented by the following general formula (A1) in the charged liquid, and the structural unit represented by the following general formula (A2) A dropping polymerization in which a liquid containing a monomer containing Produced by the content of the structural unit represented by the following general formula constituting the dye multimer (A2) a (mol%) and (a2), the content of the structural unit represented by the following general formula (A1) (moles %) Is a coloring composition containing a dye multimer that satisfies the following formula (1) and has an alkali-soluble group in the molecule.
Formula (1) (a2) / (a1) ≧ 0.3


[In General Formula (A1), X ^A1 represents a linking group formed by polymerization, L ^A1 represents a single bond or a divalent linking group, and Dye represents a dye obtained by removing one arbitrary hydrogen atom from a dye compound. Represents a residue. In general formula (A2), X ^A2 represents a linking group formed by polymerization, L ^A2 represents a single bond or a divalent linking group, and R represents a hydrogen atom, an alkyl group, or an ethylenic group shown below. Represents a monovalent substituent containing a partial structure having an unsaturated double bond. A plurality of X ^A1 , L ^A1 and Dye present in the molecule of the dye multimer may be the same as or different from each other, and a plurality of X ^A2 , L ^A2 and R may be the same or different from each other. It may be. ]

  The dye multimer has a dispersion degree [Mw (weight average molecular weight) / Mn (number average molecular weight)] in the range of 1.0 <Mw / Mn <2.0, and the weight average molecular weight measured by GPC method. The coloring composition according to claim 1, which is a dye multimer having (Mw) of 5,000 to 20,000. Dye in the general formula (A1) is represented by a dye residue in which one arbitrary hydrogen atom is removed from the dipyrromethene-based metal complex compound represented by the following general formula (5), or the following general formula (6). The dye residue in which one hydrogen atom of any ^one of R ^{11 to} R ¹⁷ , X ¹ , and Y ^{1 to} Y ² of the dipyrromethene metal complex compound is deviated is described in claim 1 or claim 2. Coloring composition.


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


[In General Formula (6), R ¹¹ and R ¹⁶ each independently represents 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. ] All monomers including a dye monomer capable of forming the structural unit represented by the general formula (A1) and a monomer capable of forming the structural unit represented by the general formula (A2) in the charging solution. The coloring composition according to any one of claims 1 to 3, wherein the concentration is 15% by mass or more and 100% by mass or less.   The coloring composition according to any one of claims 1 to 4, wherein the dye multimer is a dye multimer produced by radical polymerization.   The colored composition according to claim 5, wherein the dye multimer is a dye multimer produced by living radical polymerization.   A colored radiation-sensitive composition comprising the colored composition according to any one of claims 1 to 6, a polymerizable compound, and a polymerization initiator.   A color filter provided with the coloring pattern formed using the colored radiation-sensitive composition of Claim 7. Applying the colored radiation-sensitive composition according to claim 7 on a support to form a colored radiation-sensitive composition layer;
Exposing the formed colored radiation-sensitive composition layer to a pattern; and
Developing the exposed colored radiation-sensitive composition layer to form a colored pattern; and
The manufacturing method of the color filter which has these in this order.     An inkjet ink comprising the colored composition according to any one of claims 1 to 6 and a polymerizable compound.   A color filter provided with the coloring pattern formed using the inkjet ink of Claim 10. Preparing a substrate having a recess partitioned by a partition;
A method for producing a color filter, comprising: forming a colored pixel of a color filter by applying the ink-jet ink droplet according to claim 10 to the concave portion by an ink-jet method.   The solid-state image sensor provided with the color filter of Claim 8 or Claim 11.   A display device comprising the color filter according to claim 8. A method for producing a dye multimer comprising a structural unit represented by the following general formula (A1) and a structural unit represented by the following general formula (A2):
Synthesized using a dye monomer capable of forming a structural unit represented by the following general formula (A1) and a monomer capable of forming a structural unit represented by the following general formula (A2) ; The dye monomer necessary for the synthesis is a dye monomer capable of forming a structural unit represented by the following general formula (A1), and 15% by mass of the total of the dye monomers used for the synthesis of the dye multimer A monomer containing a dye monomer capable of forming a structural unit represented by the following general formula (A1) of 70% by mass or less and a monomer capable of forming a structural unit represented by the following general formula (A2). A charging solution in which a monomer is charged in advance is prepared, and then the remaining dye monomer capable of forming the structural unit represented by the following general formula (A1) and the following general formula (A2) are prepared in the charging solution. dropwise for dropping a liquid containing a monomer containing a monomer capable of forming a structural unit, the Manufacturing method of the dye polymer to conduct the case.


[In General Formula (A1), X ^A1 represents a linking group formed by polymerization, L ^A1 represents a single bond or a divalent linking group, and Dye represents a dye obtained by removing one arbitrary hydrogen atom from a dye compound. Represents a residue. In general formula (A2), X ^A2 represents a linking group formed by polymerization, L ^A2 represents a single bond or a divalent linking group, and R represents a hydrogen atom, an alkyl group, or an ethylenic group shown below. Represents a monovalent substituent containing a partial structure having an unsaturated double bond. A plurality of X ^A1 , L ^A1 and Dye existing in the molecule of the dye multimer may be the same or different from each other, and a plurality of X ^A2 , L ^A2 and R may be the same as each other. May be different. ]

All monomers including a dye monomer capable of forming the structural unit represented by the general formula (A1) and a monomer capable of forming the structural unit represented by the general formula (A2) in the charging solution . The method for producing a dye multimer according to claim 15, wherein the concentration is 15% by mass or more and 100% by mass or less.   The method for producing a dye multimer according to claim 15 or 16, wherein the dropping polymerization is radical polymerization.   The method for producing a dye multimer according to claim 17, wherein the dropping polymerization is living radical polymerization.