JP6862818B2 - Photosensitive coloring compositions, color filters, and organic EL display devices - Google Patents

Description

The present invention relates to a photosensitive coloring composition capable of obtaining a film or a fine pattern having excellent solvent resistance even in a curing process of low-temperature firing. The photosensitive coloring composition of the present invention can be used in applications such as a color liquid crystal display device, a color organic EL display device, a solid-state image sensor, a color filter used for quantum dots, and a black matrix.

Generally, an organic EL display device (particularly a W that combines a white light emitting organic EL and a color filter)
RGB method), liquid crystal display element, integrated circuit element, solid-state image sensor, etc.
A film such as a black matrix or a fine pattern is provided. While these films or fine patterns are required to have optical characteristics such as high saturation and high transparency, they are included in other members when they are formed by overlapping and applying them by a photolithography method or the like. Resistance to solvents is required. Therefore, it is known that a film or a fine pattern having excellent solvent resistance is formed by adding a photocuring agent or a thermosetting agent to the photosensitive composition in advance and performing both photocuring and thermosetting. .. (For example, Patent Documents 1 and 2)

Furthermore, in recent years, displays have become more flexible and wearable, and there is an increasing need to manufacture elements using flexible substrates without using the rigid glass substrates that have been used in the past. Since it is made of an organic material and has lower heat resistance than a glass substrate, it is necessary to lower the thermosetting temperature. For example, color filters have been heat-cured at about 200 to 230 ° C in the past, but when using a plastic flexible base material, it is necessary to lower the thermosetting temperature to about 80 to 150 ° C due to the problem of heat resistance. There is. In such a low-temperature curing process, thermal cross-linking is not sufficiently performed, and sufficient resistance to the solvent contained in the members in the subsequent step cannot be sufficiently obtained. In particular, in color filters, in order to obtain high saturation and high transparency, dyes and pigments are often contained in a very large amount, so that photocuring in the exposure process is difficult, and it is more difficult to impart resistance by photocrosslinking. difficult. In a color filter that requires a finer pattern, there is a limit to the improvement of the crosslinkability by adding a large amount of photocuring agent because the pattern becomes thicker.

In particular, a blue pigment having a phthalocyanine skeleton tends to have poor solvent resistance because it absorbs ultraviolet light, which is the absorption wavelength of the photoinitiator, and does not photocure deep into the coating film. If the thermosetting process is lowered to about 80 to 150 ° C., it will be further aggravated. Further, when the colorant contains a dye, the solubility in a solvent is high, so that the solvent resistance is further deteriorated as compared with the case where a blue pigment having a phthalocyanine skeleton is used. However, in order to obtain high saturation and high transparency of the coating film, it is necessary to use a large amount of blue pigment or dye having a phthalocyanine skeleton.

As described above, it is required to have high transparency and form a fine pattern while imparting solvent resistance to the photosensitive coloring composition, and this is especially required in the case of a low temperature curing process. strong. Until now, the degree of cross-linking of the coating film has been improved by using a high-sensitivity initiator as the photocuring agent or by using a sensitizer in combination, and the thermosetting agent has been described in Patent Documents 1 and 2. By using such epoxy resins, blocked isocyanates, and melamine resins, cross-linking at low temperatures was improved to impart solvent resistance. However, the above technology has the following problems.

When a large amount of a high-sensitivity initiator such as an oxime ester initiator is added to the photosensitive composition, according to the studies by the present inventors, a fine pattern cannot be formed and only the coating film surface is cured. The swelling, peeling, and dissolution of the end face of the coating film due to solvent immersion did not improve.
The same results as above were obtained when a sensitizer was used in combination.

When the epoxy resin is added, as described in Patent Document 2, the photosensitive composition is 18
It is possible to impart chemical resistance by thermosetting at 0 ° C. or higher, but it cannot be expected to be thermosetting at a lower temperature. According to the study by the present inventors, it is impossible to impart solvent resistance at a low temperature of 80 to 150 ° C. without a catalyst, and by adding a tertiary amine or a quaternary ammonium salt as a catalyst, the temperature is 150 ° C. or lower. It can be cured at temperature. However, due to the influence of the added catalyst, depending on the type and amount of the catalyst, the reaction proceeds little by little even at room temperature, causing problems such as poor storage stability and poor solubility of the catalyst, causing lumps in the coating solution. In some cases.

When blocked isocyanate is added, as described in Patent Documents 1 and 2, as described in Patent Documents 1 and 2.
It is possible to impart chemical resistance by thermosetting the photosensitive composition at 180 ° C. or higher. According to the studies by the present inventors, it is possible to impart solvent resistance even at low temperature curing of 150 ° C. or lower, but the blocking agent remains in the cured product, which adversely affects the insulating property. There is. Further, depending on the type of the blocking agent, there is a concern that the blocking agent may be scattered in the air during heat curing, which may adversely affect the operator or the environment, or may deteriorate the optical characteristics. Further, many blocked isocyanates have poor compatibility with acrylic photosensitive compositions, and whitening may occur.

Similar to blocked isocyanate, melamine resin can be imparted with chemical resistance even when cured at a low temperature of 150 ° C or lower, but formaldehyde is generated during and after heat curing, which adversely affects workers and the environment. There is a concern. In addition, most of the low-temperature curable melamines have high polarity and have poor compatibility with acrylic photosensitive compositions, which may cause whitening.

Japanese Unexamined Patent Publication No. 2013-5 / 95956 Japanese Unexamined Patent Publication No. 2011-93955 Japanese Unexamined Patent Publication No. 2000-23351

The present invention has been made in view of the above situation, and an object of the present invention is to provide a photosensitive coloring composition having high solvent resistance, high transparency, and excellent photolithography characteristics.

As a result of diligent studies, the present inventors have found a colorant (A), an alkali-soluble resin (B) having a radically polymerizable group, a polyfunctional (meth) acrylate monomer (C), and a photopolymerization initiator (D). A photosensitive coloring composition contained therein.
The photopolymerization initiator (D) is a carbazole-based oxime compound (D1) having an absorption maximum wavelength in the range of 350 to 400 nm, and a phenyl-based oxime compound and acetophenone having an absorption maximum wavelength in the range of 300 to 350 nm. Containing at least one compound (D2) selected from the compounds,
The weight ratio of the compound (D1) to (D2) is (D1) / (D2) = 5/95 to 11/89.
The colorant (A) contains at least one selected from a blue pigment (A1) having a phthalocyanine skeleton and a dye (A2) .
The total content of the blue pigment (A1) and the dye (A2) is, in the colorant (A), in der Rukoto 65 wt% to 100 wt% or less, found that an aspect of the present invention Has been completed.

That is, the uniform of the present invention contains a colorant (A), an alkali-soluble resin (B) having a radically polymerizable group, a polyfunctional (meth) acrylate monomer (C), and a photopolymerization initiator (D). A photosensitive coloring composition
The photopolymerization initiator (D) is a carbazole-based oxime compound (D1) having an absorption maximum wavelength in the range of 350 to 400 nm, and a phenyl-based oxime compound and acetophenone having an absorption maximum wavelength in the range of 300 to 350 nm. Containing at least one compound (D2) selected from the compounds,
The weight ratio of the compound (D1) to (D2) is (D1) / (D2) = 5/95 to 11/89.
The colorant (A) contains at least one selected from a blue pigment (A1) having a phthalocyanine skeleton and a dye (A2) .
The total content of the blue pigment (A1) and the dye (A2) is, in the colorant (A), relates to a photosensitive coloring composition, characterized in der Rukoto 65 wt% to 100 wt% or less.

Further, one aspect of the present invention relates to the above-mentioned photosensitive coloring composition, wherein the carbazole-based oxime compound (D1) is a compound having a nitro group.

Further, one aspect of the present invention is characterized in that the total content of the blue pigment (A1) and the dye (A2) is 65% by weight or more and 100% by weight or less in the colorant (A). The present invention relates to a photosensitive coloring composition.

Further, one aspect of the present invention is characterized in that the colorant (A) contains the dye (A2) and the content of the dye (A2) is 15% by weight or more in the colorant (A). The present invention relates to the above-mentioned photosensitive coloring composition.

Further, one aspect of the present invention relates to a photosensitive coloring composition used for a color filter for an organic EL display device manufactured by a manufacturing method including the following steps (i), (ii), (iii) and (iv). ..

<Process>
(I): A step of obtaining a coating film by applying the above-mentioned photosensitive coloring composition on a substrate (ii): After the step (i), a step of exposing the coating film with ultraviolet rays through a mask (iii). : After step (ii), a pattern is obtained by developing the exposed coating film with an alkaline developer. Step (iv): After step (iii), a step of post-baking the pattern at 80 ° C. to 150 ° C.

Further, one aspect of the present invention relates to a color filter characterized in that a cured product formed of the above-mentioned photosensitive coloring composition is provided on a base material.

Further, one aspect of the present invention relates to an organic EL display device including the above-mentioned color filter.

Further, the uniform state of the present invention is a method for manufacturing a color filter for an organic EL display device, which comprises the following steps (i), (ii), (iii) and (iv).
The following photosensitive coloring composition contains a colorant (A), an alkali-soluble resin (B) having a radically polymerizable group, a polyfunctional (meth) acrylate monomer (C), and a photopolymerization initiator (D). A sex coloring composition
The photopolymerization initiator (D) is a carbazole-based oxime compound (D1) having an absorption maximum wavelength in the range of 350 to 400 nm, and a phenyl-based oxime compound and acetophenone having an absorption maximum wavelength in the range of 300 to 350 nm. Containing at least one compound (D2) selected from the compounds,
The weight ratio of the compound (D1) to (D2) is (D1) / (D2) = 5/95 to 11/89.
The colorant (A) contains at least one selected from a blue pigment (A1) having a phthalocyanine skeleton and a dye (A2) .
The total content of the blue pigment (A1) and the dye (A2) is, in the colorant (A), an organic EL display, which is a Der Ru photosensitive coloring composition 65 wt% to 100 wt% The present invention relates to a method for manufacturing a color filter for an apparatus.
<Process>
(I): Step of obtaining a coating film by applying the photosensitive coloring composition on a substrate (ii): Step (i): After step (i), a step of exposing the coating film with ultraviolet rays via a mask (iii): Step. (Ii) After that, a pattern is obtained by developing the exposed coating film with an alkaline developing solution (iv): After step (iii), a step of post-baking the pattern at 80 ° C. to 150 ° C.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a photosensitive coloring composition having photolithography, which can impart solvent resistance even at a low curing temperature, has high transmittance, and can form a fine pattern. It was.

Shows an example of an emission spectrum of an organic EL device.

Hereinafter, embodiments of the present invention will be described in detail. In addition, in this specification (meta)
Acrylate means acrylate and / or methacrylate, and (meth) acrylic acid means acrylic acid and / or methacrylic acid.

<< Curing method and components of photosensitive composition >>
First, an example of a curing method for the photosensitive composition of the present embodiment and a combination of constituent elements will be described. The photosensitive coloring composition of the present embodiment contains an essential component of a colorant (A), an alkali-soluble resin (B) having a radically polymerizable group, a polyfunctional (meth) acrylate monomer (C), and an initiator (D). The colorant (A) contains at least one selected from a blue pigment (A1) having a phthalocyanine skeleton or a dye (A2), and the initiator (D) has a maximum absorption within the range of 350 to 400 nm. It contains a carbazole-based oxime compound (D1) having a wavelength, and further contains at least one of a phenyl-based oxime compound or an acetophenone compound (D2) having an absorption maximum wavelength in the range of 300 to 350 nm.
The photosensitive composition of the present embodiment may satisfy the above-mentioned constitution and is not limited to the action and the curing process. For example, the solvent resistance can be improved by performing photo-curing and then thermosetting. Can be raised. Its action is presumed as follows.

First, the reaction in photocuring is radical polymerization by irradiation with active energy rays such as ultraviolet rays, and it is widely known that the reaction rate of photopolymerizable functional groups does not reach 100% at this stage. This is one of the reasons why the solvent resistance of the cured product is not sufficient.
In the subsequent thermosetting stage, the unreacted photopolymerizable functional group is cleaved and polymerized during thermosetting, and the carboxylic acid group and the hydroxyl group in the resin undergo an ester reaction to improve the crosslink density of the coating film. However, when the calcination curing temperature is low, the above reaction does not occur sufficiently. This causes insufficient solvent resistance of the cured product at low firing temperatures.

The radical polymerization reaction occurs when radicals are generated from the photopolymerization initiator by ultraviolet rays and the photopolymerizable functional group is radically polymerized. However, when the colorant contains a blue pigment having a phthalocyanine skeleton, it is in the ultraviolet region. The absorption is strong, radical generation of the photopolymerization initiator is unlikely to occur, and sufficient resistance cannot be obtained. Alternatively, when the colorant contains a dye, it is difficult for the photopolymerization initiator to generate radicals due to absorption in the ultraviolet region, and because of its nature, it easily dissolves in the solvent, so that sufficient resistance cannot be obtained. Causes.
The present inventors contain a carbazole-based oxime compound having an absorption maximum wavelength in the range of 350 to 400 nm in the initiator, and further, a phenyl-based oxime compound or acetophenone having an absorption maximum wavelength in the range of 300 to 350 nm. It has been found that having at least one of the compounds has the effect of promoting radical generation in the ultraviolet region, improving the cross-linking density, and improving the solvent resistance.

The use of the photosensitive coloring composition of the present embodiment is not particularly limited, but it can be used as a negative photoresist by imparting developability, and a fine pattern can be produced by photolithography. In that case, the photosensitive coloring composition is partially photocured by performing pattern exposure using a photomask, the uncured portion is dissolved with an organic solvent or the like to develop, and the remaining photocured portion is heated. It may be heat-cured. An organic solvent or an alkaline aqueous solution can be used in the photolithography development process.

When the photosensitive composition of the present embodiment is used as a negative type photoresist, both the resolution of the pattern and the solvent resistance can be achieved regardless of whether the photosensitive composition is alkali-developed or solvent-developed.
In the case of a photosensitive coloring composition that does not contain the above-mentioned initiators (D1) and (D2) in the initiator, the concentration of the photopolymerizable functional group or the photopolymerization initiator is increased or the exposure amount is increased in order to increase the solvent resistance. Therefore, it is necessary to increase the cross-linking density in photocuring. However, in these designs, when the pattern is exposed, the photopolymerization reaction diffuses outside the opening of the mask and photocures in a range larger than the mask size. Therefore, a pattern larger than the mask size is obtained after development. The tendency to be exposed becomes stronger. In addition, photopolymerizable functional groups that have not reacted in the photocuring process do not sufficiently undergo thermosetting at low temperatures such as 80 to 150 ° C. even in the thermosetting process following exposure and development, and thus are resistant to solvents in thermosetting. It is difficult to obtain the effect of improvement. Therefore, in order to improve the solvent resistance, it is necessary to rely on a design that promotes the photopolymerization reaction, and there is a trade-off between the resolution of the pattern and the solvent resistance. In particular, a photosensitive composition for a color filter is required to have excellent developability, but on the other hand, it is difficult for photocuring to proceed because it contains a colorant, and excellent chemical resistance is obtained especially under low temperature curing conditions. It is difficult. Therefore, it is very difficult to achieve both developability and solvent resistance.

Therefore, at least one of the phenyl-based oxime compounds or acetophenone compounds containing a carbazole-based oxime compound having an absorption maximum wavelength in the range of 350 to 400 nm and further having an absorption maximum wavelength in the range of 300 to 350 nm is contained in the initiator. Having one can break the trade-off between pattern resolution and solvent resistance. Therefore, the photosensitive composition of the present embodiment can be applied to a wide range of applications, and among them, it can be preferably used for a photosensitive composition for a color filter.
Next, each component of the photosensitive coloring composition of the present embodiment will be described.

<Colorant (A)>
The photosensitive coloring composition of the present invention contains a colorant (A).
Hereinafter, a colorant preferably used in the photosensitive coloring composition of the present invention will be described.

As the colorant contained in the photosensitive coloring composition of the present invention, organic or inorganic pigments and dyes can be used alone or in combination of two or more. Among the pigments, pigments having high color development and high heat resistance are preferable, and organic pigments are usually used, but the pigments are not limited thereto.
The photosensitive coloring composition of the present invention contains at least one selected from a blue pigment (A1) having a phthalocyanine skeleton or a dye (A2).

<Blue pigment with phthalocyanine skeleton (A1)>
Examples of the blue pigment (A1) having a phthalocyanine skeleton include C.I. I. It is preferable to use Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17: 1, and an aluminum phthalocyanine pigment represented by the following formula (1).

General formula (1)

[In the general formula (1), X _{1 to} X ₄ independently have an alkyl group which may have a substituent, an aryl group which may have a substituent, and a cyclo which may have a substituent. An alkyl group, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or Represents an arylthio group that may have a substituent.
Y _{1 to Y 4} independently represent a halogen atom, a nitro group, a phthalimide methyl group which may have a substituent, or a sulfamoyl group which may have a substituent.
Z represents a hydroxyl group, a chlorine atom, -OP (= O) R ₁ R ₂ , or -O-Si R _{3 R 4} R ₅ . Here, R _{1 to} R ₅ are independently hydrogen atoms, hydroxyl groups, an alkyl group which may have a substituent, an aryl group which may have a substituent, and an alkoxyl group which may have a substituent. , Or an aryloxy group which may have a substituent, and Rs may be bonded to each other to form a ring. m _{1 to} m ₄ and n _{1 to} n ₄ independently represent integers 0 to 4, and m ₁ + n ₁ , m ₂ + n ₂ , m ₃ + n ₃ , and m ₄ + n ₄ are 0 to 0, respectively. In 4, it may be the same or different. ]

The pigment used in the photosensitive coloring composition of the present invention can be refined by salt milling or acid pacing. The primary particle size of the pigment is preferably 10 nm or more, more preferably 20 nm or more, because it is well dispersed in the colorant carrier. Further, since a filter segment having a high contrast ratio can be formed, it is preferably 100 nm or less. A preferred range is 15 to 85 nm, and a particularly preferred range is 25 to 85 nm. The primary particle size of the pigment was determined by a method of directly measuring the size of the primary particle from an electron micrograph of the pigment by a TEM (transmission electron microscope). Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle size of the pigment particles. Next, for 100 or more pigment particles, the volume of each particle is obtained by approximating it to a cube having a obtained particle size, and the volume average particle size is defined as the average primary particle size.

The salt milling treatment is a kneader of a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent, or a mixture of a pigment, a compound represented by the general formula (X), a water-soluble inorganic salt and a water-soluble organic solvent. This is a process of mechanically kneading while heating using a kneader such as a two-roll mill, a three-roll mill, a ball mill, an attritor, or a sand mill, and then washing with water to remove water-soluble inorganic salts and water-soluble organic solvents. .. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution, and a sharp particle size distribution.

As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of price. From the viewpoint of both treatment efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by weight, most preferably 300 to 1000% by weight, based on the total weight of the pigment (100% by weight).

The water-soluble organic solvent has a function of wetting the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, 2-ethyl-1,3-hexanediol, liquid Polyprolen glycol or the like is used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000% by weight, most preferably 50 to 500% by weight, based on the total weight of the pigment (100% by weight).

When the pigment is subjected to salt milling treatment, a resin may be added if necessary. The type of resin used is not particularly limited, and a natural resin, a modified natural resin, a synthetic resin, a synthetic resin modified with a natural resin, or the like can be used. The resin used is preferably solid at room temperature, water-insoluble, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200% by weight based on the total weight of the pigment (100% by weight).

The acid pacing method is a method for producing a treated pigment by co-dissolving an organic pigment in a strongly acidic solvent and taking out the solution in water. As the strongly acidic solvent, sulfuric acid, polyphosphoric acid, chlorosulfonic acid and the like can be used. Industrially, it is desirable to use sulfuric acid from the viewpoint of cost.
When preparing a strongly acidic solvent solution containing a blue pigment (A1) having a phthalocyanine skeleton, each powder may be added to the strongly acidic solvent and dissolved, or after each is dissolved in the strongly acidic solvent. , Each strong acid solvent solution may be mixed. The order of addition of each powder in a strongly acidic solvent is not limited.

The amount of the strongly acidic solvent needs to be increased or decreased depending on the concentration of the strongly acidic solvent, but is not particularly limited as long as it can completely dissolve them. For example, when 98% by weight of sulfuric acid is used, it is preferably 3 to 100 times by weight, more preferably 5 to 30 times by weight, based on the total weight of the blue pigment (A1) having a phthalocyanine skeleton. If the amount of sulfuric acid is less than this range, it may be difficult to completely dissolve the blue pigment (A1) having a phthalocyanine skeleton at a low temperature. Moreover, even if it is used more than this range, there is no merit in giving quality, and productivity is lowered, which is uneconomical.

The temperature at which the blue pigment (A1) having a phthalocyanine skeleton is dissolved in a strongly acidic solvent is not particularly limited, but for example, when 98% by weight sulfuric acid is used, it is preferably 3 ° C. or higher and 60 ° C. or lower, and further. It is preferably 3 ° C. or higher and 40 ° C. or lower. If the temperature is less than 3 ° C., sulfuric acid solidifies and it becomes difficult to stir uniformly, which is not preferable. Further, when it is dissolved at a temperature higher than the above temperature, the blue pigment (A1) having a phthalocyanine skeleton may be decomposed.

In the present invention, the temperature at which a strongly acidic solvent solution of a blue pigment (A1) having a phthalocyanine skeleton is mixed with water and precipitated is not particularly limited. However, in many cases, the particles tend to be finer at low temperatures than when precipitated at high temperatures, so it is preferable to carry out at 0 ° C. or higher and 60 ° C. or lower. As the water used at that time, any industrially usable water such as tap water, well water, and hot water can be used, but in order to reduce the temperature rise at the time of precipitation, pre-cooled water can be used. It is preferable to use.

The method for mixing the strong acid solvent solution and water is not particularly limited, and any method may be used as long as the blue pigment (A1) having a phthalocyanine skeleton can be completely precipitated. For example, it can be precipitated by a method of injecting a strong acid solvent solution into ice water prepared in advance, or a method of continuously injecting into running water using an device such as an aspirator.

The pigment composition of the present invention can be obtained by filtering and washing the slurry obtained by the above method to remove acidic components, and then drying and pulverizing the slurry.
In the photosensitive coloring composition of the present invention, it is preferable that the blue pigment (A1) having a phthalocyanine skeleton is contained in the colorant (A) in an amount of 65% by mass to 100% by mass because good transmittance can be obtained. It is more preferably contained in an amount of 70% by mass to 100% by mass.

<Dye>
There are no particular restrictions on what is generally called a dye, but among the dyes (A2), triphenylmethane dyes, triphenylmethane lake pigments, diphenylmethane dyes, diphenylmethane lake pigments, quinoline dyes, etc. Kinolin-based pigments, thiazine-based dyes, thiazole-based dyes, xanthene-based dyes, xanthene-based lake pigments, diketopyrrolopyrrole-based pigments and the like can be used.

Among these, xanthene dyes, xanthene dyes that are xanthene lake pigments, quinoline dyes, quinoline dyes that are quinoline pigments, triphenylmethane dyes, and triphenylmethane dyes that are triphenylmethane lake pigments. , It is preferable to use a diketopyrrolopyrrole pigment which is a diketopyrrolopyrrole pigment.
In particular, when a dye that emits fluorescence in the visible light region is used, it is excellent in the effect of forming a color filter having a high contrast ratio.

The dye (A2) that can be preferably used in the present invention is any one of various dyes such as an oil-soluble dye, an acidic dye, a direct dye, a basic dye, a medium dye, and an acidic medium dye in the form of a dye. It is preferable that it has the form of.
Examples of the pigment in the form include a fluorescent pigment and a rake pigment obtained by rake-forming the dye.
When the colorant is a dye, it is preferable to use an oil-soluble dye, an acid dye, a direct dye, or a basic dye because the hue is excellent.

[Oil-soluble dye]
As an oil-soluble dye, C.I. Those classified as I. Solvent, as basic dyes, C.I. Those classified as I. Basic, acid dyes include C.I. Those classified as I. Acid, as direct dyes, C.I. I. It is classified directly. Here, the direct dye has a sulfonic acid group (-SO ₃ H, -SO ₃ Na) in the structure, and in the present invention, the direct dye is regarded as an acid dye.
Hereinafter, the preferred dye (A2) will be specifically described.

(Xanthene type)
(Xanthene dyes: xanthene dyes, their lake pigments)
In the case of a xanthene dye, the transmittance is 90% or more in the region of 650 nm, the transmittance is 75% or more in the region of 600 nm, the transmittance is 5% or less in the region of 500 to 550 nm, and the region of 400 nm in the transmission spectrum. It is preferable that the transmittance is 70% or more. More preferably, the transmittance is 95% or more in the 650 nm region, the transmittance is 80% or more in the 600 nm region, the transmittance is 10% or less in the 500 to 550 nm region, and the transmittance is 75% in the 400 nm region. That is all. Among them, xanthene-based basic dyes and xanthene-based acid dyes have spectral characteristics having high transmittance at 400 to 450 nm.

Further, among xanthene dyes, rhodamine dyes are preferable because they are excellent in color development and resistance.

(Form of xanthene dye as oil-soluble dye)
Specifically, the xanthene-based oil-soluble dyes include CI Solvent Red 35, CI Solvent Red 36, CI Solvent Red 42, CI Solvent Red 43, and CI Solvent Red. Red 44, CI Solvent Red 45, CI Solvent Red 46, CI Solvent Red 47, CI Solvent Red 48, CI Solvent Red 49, CI Solvent Red 72 , CI Solvent Red 73, CI Solvent Red 109, CI Solvent Red 140, CI Solvent Red 141, CI Solvent Red 237, CI Solvent Red 246, C. Examples thereof include I. Solvent Violet 2 and CI Solvent Violet 10.
Among them, CI Solvent Red 35, CI Solvent Red 36, CI Solvent Red 49, CI Solvent Red 109, and CI Solvent Red, which are rhodamine-based oil-soluble dyes with high color development. Red 237, CI Solvent Red 246, and CI Solvent Violet 2 are more preferred.

(Form of xanthene dye as acid dye)
Examples of the xanthene-based acid dye (xanthene-based acid dye) include C.I. I. Acid Red 51 (erythrosine (edible red No. 3)), C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 87 (Eosin G (Edible Red No. 103)), C.I. I. Acid Red 92 (Acid Phloxine PB (Edible Red No. 104)), C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B (Edible Red No. 5), Acid Rhodamine G, C.I. I. It is preferable to use Acid Violet 9.
Among them, C.I., which is a xanthene-based acid dye, has heat resistance and light resistance. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 388 or C.I., a rhodamine-based acid dye. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 289, Acid Rhodamine G, C.I. I. It is more preferable to use Acid Violet 9.
Among these, C.I., a rhodamine-based acid dye, is particularly excellent in color development, heat resistance, and light resistance. I. Acid Red 52, C.I. I. Most preferably, Acid Red 289 is used.

(Form of xanthene dye as basic dye)
Examples of the xanthene-based basic dye include C.I. I. Basic Red 1 (Rhodamine 6 GCP), 8 (Rhodamine G), C.I. I. Basic Violet 10 (Rhodamine B) and the like can be mentioned. Among them, C.I. I. Basic Red 1, C.I. I. It is preferable to use Basic Violet 10.

(Form of xanthene dye as a lake pigment)
Metal lake pigments of xanthene dyes include CI Pigment Red 81, CI Pigment Red 81: 1, CI Pigment Red 81: 2, CI Pigment Red 81: 3, C.I. I. Pigment Red 81: 4, CI Pigment Red 81: 5, CI Pigment Red 169, CI Pigment Violet 1, CI Pigment Violet 1: 1, CI Pigment Violet 1: 2, CI Pigment Violet 2 and the like.

(Diphenyl and triphenylmethane dyes: triphenylmethane dyes, diphenylmethane dyes, and their lake pigments)
For diphenyl and triphenylmethane dyes
Blue-based (blue) triarylmethane-based basic dyes have spectral properties with high transmittance at 400 to 440 nm.

(Forms of diphenyl and triphenylmethane dyes as acid dyes)

Acid dyes for diphenyl and triphenylmethane dyes include Edible Blue No. 101 (CI Acid Blue 1), Acid Pure Blue (CI Acid Blue 3), and Lake Blue I (CI Acid Blue 3). 5), Lake Blue II (CI Acid Blue 7) Edible Blue No. 1 (CI Acid Blue 9), C.I. I. Acid Blue 22, C.I. I. Acid Blue 83, C.I. I. Acid Blue 90, C.I. I. Acid Blue 93, C.I. I. Acid Blue 100, C.I. I. Acid Blue 103, C.I. I. Acid Blue 104, C.I. I. It is preferable to use Acid Blue 109.

(Forms of diphenyl and triphenylmethane dyes as basic dyes)
The triphenylmethane-based basic dye and the diphenylmethane-based basic dye develop a color when the NH2 or OH group located at the para position with respect to the central carbon takes a quinone structure by oxidation.
It _{is classified into the following three types according to the number of NH 2} and OH groups, and among them, the form of a triaminotriphenylmethane-based basic dye is preferable in that it develops good blue, red, and green colors. ..
a) Diaminotriphenylmethane-based basic dye b) Triaminotriphenylmethane-based basic dye c) Rosolic acid-based basic dye having an OH group Triaminotriphenylmethane-based basic dye, diaminotriphenylmethane-based basic dye The dye has a clear color tone and is more preferable than other dyes because it has excellent sunlight-hardening and waxing properties. Further, a diphenylnaphthylmethane basic dye and / or a triphenylmethane basic dye is preferable.

Specifically, C.I. I. Basic Blue 1 (Basic Cyanine 6G), 5 (Basic Cyanine EX), 7 (Victoria Pure Blue BO), 25 (Basic Blue GO), 26 (Victoria Blue B conc.) And the like.
C. I. Basic Green 1 (Brilliant Green GX), 4 (Malachite Green), etc.
C. I. Basic violet 1 (methyl violet), 3 (crystal violet), 14 (Magenta) and the like can be mentioned.

(Forms of diphenyl and triphenylmethane dyes as lake pigments)
Specifically, as a triarylmethane-based lake pigment, C.I. I. Pigment Blue 1, C.I. I. Pigment Blue 2, C.I. I. Pigment Blue 9, C.I. I. Pigment Blue 10, C.I. I. Pigment Blue 14, C.I. I. Pigment Blue 62, CI Pigment Violet 3, CI Pigment Violet 27, CI Pigment Violet 39 and the like.
More specifically, more preferable ones
C. I. Pigment Blue 1.
C. I. Basic Blue 26, C.I. I. Basic Blue 7 is raked with phosphotungsten and molybdic acid.
C. I. Pigment Violet 3.
C. I. Basic Violet 1 is raked with phosphotungsten and molybdate.
C. I. Pigment Violet 39.
C. I. Basic Violet 3 (Crystal Violet) is raked with phosphotungsten and molybdate.
Above all, C.I. I. Pigment Blue 1 is preferably used.

(Quinoline dyes: quinoline dyes, quinoline pigments)
Examples of the quinoline dye include dyes commercially available with color indexes such as Solvent Yellow 33, Solvent Yellow 98, Solvent Yellow 157, Disperse Yellow 54, Disperse Yellow 160, and Acid Yellow 3.
Examples of quinoline pigments include C.I. I. Pigment Yellow 138 (Pariotor Yellow K0961-HD manufactured by BASF Co., Ltd.) and the like can be mentioned.

(Thiazine dye)
Thiazine dyes include Laut's Violet, methylene blue, methylene green B, CI basic blue 9, 17, 24, obtained by oxidizing P-phenylenediamine in the presence of hydrogen sulfide under FeCl _2. 25, Solvent Blue 8, CI Basic Green 5, CI Direct Red 70, etc.

(Thiazole dye)
As the thiazole dye, a dye having a thiazole ring is used as a thiazole dye.
Specifically, CI Basic Yellow 1, CI Basic Violet 44, 46, CI Basic Blue 116, CI Acid Yellow 186, Direct Yellow 7, 8, 9, 14, 17, 18, 22, 28, 29, 30, 54, 59, 165, CI Direct Orange 18, CI Direct Red 11, and the like.

<Chloride>
The dye (A2) has good spectral characteristics and excellent color development, but has problems in light resistance and heat resistance, and is suitable for use in an image display device using a color filter that requires high reliability. Its properties may not be sufficient.
Therefore, in order to improve these drawbacks, in the case of the basic dye form, it is preferable to use a salt-forming compound (Z1) chlorinated with an organic acid or perchloric acid. As the organic acid, it is preferable to use an organic sulfonic acid or an organic carboxylic acid. Of these, it is preferable to use naphthalene sulfonic acid such as tobias acid and perchloric acid in terms of resistance.
In the case of anionic dyes such as acid dyes,
A salt-forming compound (Z2) obtained by chloride using a cationic compound typified by a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, a primary amine compound, or the like.
Alternatively, a salt-forming compound (Z3), which is sulfonamided to form a sulfonic acid amide compound,
It is preferable to use it in terms of resistance.

Among these, (Z2) and (Z3) are particularly preferable because they are excellent in resistance and compatibility with pigments, and (Z2) is more preferable.
In (Z2), as the cationic compound represented by the quaternary ammonium salt compound, the tertiary amine compound, the secondary amine compound, and the primary amine compound,
A resin component having a cationic group represented by a quaternary ammonium base, a tertiary amino group, a secondary amino group, and a primary amino group can be preferably used.

Above all, as the dye (A2), it is particularly preferable to use a salt-forming resin compound (Z4) obtained by chlorinating an anionic dye using a resin component having a cationic group typified by a quaternary ammonium salt.

(Anionic dye)
Next, an anionic dye for obtaining the salt-forming compound of the present invention will be described. The anionic dye may be any coloring compound having an anionic group that ionic bonds with the above-mentioned cationic group. The coloring compound is not particularly limited as long as it has a carboxylic acid group, a sulfonic acid group, a phenolic hydroxyl group, a phosphoric acid group, a metal salt thereof, or the like in the molecule, and is not particularly limited, and is an organic solvent or a developing compound. It can be appropriately selected in consideration of all required performances such as solubility in a liquid, salt forming property, absorbance, interaction with other components in the present composition, light resistance, and heat resistance.

Examples of anionic dyes include anthraquinone-based anionic dyes, monoazo-based anionic dyes, disazo-based anionic dyes, oxazine-based anionic dyes, aminoketone-based anionic dyes, xanthene-based anionic dyes, and quinoline-based anionic dyes. Examples thereof include triphenylmethane-based anionic dyes. Specific examples of anionic dyes that can be used for the synthesis of salt-forming compounds are shown below by color index numbers.

Examples of red dyes include C.I. I. Acid Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 23, 24, 25, 25: 1, 26, 26: 1, 26: 2, 27, 29, 30, 31, 32, 33, 34, 35, 36, 37, 39, 40, 41, 42, 43, 44, 45, 47, 50, 52, 53, 54, 55, 56, 57, 59, 60, 62, 64, 65, 66, 67, 68, 70, 71, 73, 74, 76, 76: 1, 80, 81, 82, 83, 85, 86, 87, 88, 89, 91, 92, 93, 97, 99, 102, 104, 106, 107, 108, 110, 111, 113, 114, 115, 116, 120, 123, 125, 127, 128, 131, 132, 133, 134, 135, 137, 138, 141, 142, 143, 144, 148, 150, 151, 152, 154, 155, 157, 158, 160, 161, 163, 164, 167, 170, 171, 172, 173, 175, 176, 177, 181, 229, 231, 237, 239, 240, 241, 242, 249, 252, 253, 255, 257, 260, 263, 264, 266, 267, 274, 276, 280, 286, 289, 299, 306, 309, 311, 323, 333, 324, 325, 326, 334, 335, 336, 337, 340, 343, 344, 347, 348, 350, 351, 353, 354, 356, 388 and the like can be mentioned.

In addition, C.I. I. Direct Red 1, 2, 2: 1, 4, 5, 6, 7, 8, 10, 10: 1, 13, 14, 15, 16, 17, 18, 21, 22, 23, 24, 26, 26: 1, 28, 29, 31, 33, 33: 1, 34, 35, 36, 37, 39, 42, 43, 43: 1, 44, 46, 49, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 67, 67: 1, 68, 72, 72: 1, 73, 74, 75, 77, 78, 79, 81, 81: 1, 85, 86, 88, 89, 90, 97, 100, 101, 101: 1, 107, 108, 110, 114, 116, 117, 120, 121, 122, 122: 1, 124, 125, 127, 127: 1, 127: 2, 128, 129, 130, 132, 134, 135, 136, 137, 138, 140, 141, 148, 149, 150, 152, 153, 154, 155, 156, 169, 171 and 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 186, 189, 204, 211, 213, 214, 217, 222, 224, 225, 226, 227, 228, 232, 236, 237, 238 and the like can also be used.

Examples of yellow dyes include C.I. I. Acid Yellow 2,3,4,5,6,7,8,9,9: 1,10,11,11: 1,12,13,14,15,16,17,17: 1,18,20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40: 1, 41, 42, 42: 1, 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 190, 191 and 192, 199 and the like can be mentioned.

In addition, C.I. I. Direct Yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44: 1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 126, 127, 129, 132, 133, 134 and the like can also be used.

Examples of orange dyes include C.I. I. Acid Orange 1, 1: 1, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 17, 18, 19, 20, 20: 1, 22, 23, 24, 24: 1, 25, 27, 28, 28: 1, 30, 31, 33, 35, 36, 37, 38, 41, 45, 49, 50, 51, 54, 55, 56, 59, 79, 83, 94, 95, 102, 106, 116, 117, 119, 128, 131, 132, 134, 136, 138 and the like can be mentioned.
In addition, C.I. I. Direct Orange 1, 2, 3, 4, 5, 6, 7, 8, 10, 13, 17, 19, 20, 21, 24, 25, 26, 29, 29: 1, 30, 31, 32, 33, 43, 49, 51, 56, 59, 69, 72, 73, 74, 75, 76, 79, 80, 83, 84, 85, 87, 88, 90, 91, 92, 95, 96, 97, 98, 101, 102, 102: 1, 104, 108, 112, 114 and the like can also be used.

As a blue dye, C.I. I. Acid Blue 1, 2, 3, 4, 5, 6, 7, 8, 9, 11, 13, 14, 15, 17, 19, 21, 22, 23, 24, 25, 26, 27, 29, 34, 35, 37, 40, 41, 41: 1, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 62, 62: 1, 63, 64, 65, 68, 69, 70, 73, 75, 78, 79, 80, 81, 83, 8485, 86, 88, 89, 90, 90: 1, 91, 92, 93, 95, 96, 99, 100, 103, 104, 108, 109, 110, 111, 112, 113, 114, 116, 117, 118, 119, 120, 123, 124, 127, 127: 1, 128, 129, 135, 137, 138, 143, 145, 147, 150, 155, 159, 169, 174, 175, 176, 183, 198, 203, 204, 205, 206, 208, 213, 227, 230, 231, 232, 233, 235, 239, 245, 247, 253, 257, 258, 260, 261 and 262, 264, 266, 269, 271, 272, 273, 274, 277, 278, 280 and the like.

In addition, C.I. I. Direct Blue 1, 2, 3, 4, 6, 7, 8, 8: 1, 9, 10, 12, 14, 15, 16, 19, 20, 21, 21: 1, 22, 23, 25, 27, 29, 31, 35, 36, 37, 40, 42, 45, 48, 49, 50, 53, 54, 55, 58, 60, 61, 64, 65, 67, 79, 96, 97, 98: 1, 101, 106, 107, 108, 109, 111, 116, 122, 123, 124, 128, 129130, 130: 1, 132, 136, 138, 140, 145, 146, 149, 152, 153, 154, 156, 158, 158: 1, 164, 165, 166, 167, 168, 169, 170, 174, 177, 181, 184, 185, 188, 190, 192, 193, 206, 207, 209, 213, 215, 225, 226, 229, 230, 231 and 242, 243, 244, 253, 254, 260, 263 and the like can also be used.

As a purple dye, C.I. I. Acid Violet 1, 2, 3, 4, 5, 5: 1, 6, 7, 7: 1, 9, 11, 12, 13, 14, 15, 16, 17, 19, 20, 21, 23, 24, 25, 27, 29, 30, 31, 33, 34, 36, 38, 39, 41, 42, 43, 47, 49, 51, 63, 67, 72, 76, 96, 97, 102, 103, 109, etc. Can be mentioned.

In addition, C.I. I. Direct Violet 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, 17, 18, 21, 22, 25, 26, 27, 28, 29, 30, 31, 32, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 51, 52, 54, 57, 58, 61, 62, 63, 64, 71, 72, 77, 78, 79, 80, 81, 82, 83, 85, 86, 87, 88, 93, 97 and the like can also be used.

As a green dye, C.I. I. Acid Green 2, 3, 5, 6, 7, 8, 9, 10, 11, 13, 14, 15, 16, 17, 18, 19, 20, 22, 25, 25: 1, 27, 34, 36, Examples thereof include 37, 38, 40, 41, 42, 44, 54, 55, 59, 66, 69, 70, 71, 81, 84, 94 and 95.
In addition, C.I. I. Direct greens 11, 13, 14, 24, 30, 34, 38, 42, 49, 55, 56, 57, 60, 78, 79, 80 and the like can also be used.

Hereinafter, the form of the dye (A2) used in the present invention will be described in detail.

[Salt-forming compounds of anionic dyes and / or sulfonic acid amide compounds of anionic dyes]
Acidic dyes preferably used as anionic dyes are chloride-forming using quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, primary amine compounds, and resin components having these functional groups, and acidic dyes. It is preferable to use the salt-forming compound of the above, or to sulfoamide the salt-forming compound of the sulfonic acid amide compound, because high heat resistance, light resistance, and solvent resistance can be imparted.

Primary amine compounds include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine (laurylamine), tridodecylamine, tetra. Examples thereof include aliphatic unsaturated primary amines such as decylamine (myristylamine), pentadecylamine, cetylamine, stearylamine, oleylamine, cocoalkylamine, beef alkylamine, hardened beef alkylamine and allylamine, aniline and benzylamine. ..

Examples of the secondary amine compound include aliphatic unsaturated secondary amines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine and diallylamine, methylaniline, ethylaniline, dibenzylamine, diphenylamine and dicocoalkyl. Examples include amines, di-cured beef fat alkylamines, distearylamines, etc.

Examples of the tertiary amine compound include trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, dimethylaniline, diethylaniline, tribenzylamine and the like.

As the dye (A2) used in the present invention, it is particularly preferable to use an anionic dye by chlorination using a cationic compound or sulfonamided by an anionic dye. Therefore, these two forms are described below. It will be described in detail.

(Salt-forming compound consisting of anionic dye and cationic compound)
The dye (A2) used in the present invention is preferably used as a salt-forming compound composed of the above-mentioned anionic dye and cationic compound from the viewpoint of heat resistance, light resistance, and solvent resistance.

(Cationic compound)
The cationic compound is not particularly limited as long as it has at least one onium base, but a suitable onium salt structure is an ammonium salt, an iodonium salt, a sulfonium salt, or a diazonium from the viewpoint of availability. It is preferably a salt and a phosphonium salt, and more preferably an ammonium salt, an iodonium salt, and a sulfonium salt in consideration of storage stability (thermal stability). More preferably, it is a quaternary ammonium salt compound.
As the quaternary ammonium salt compound, a resin component having a quaternary ammonium base can be preferably used.

(Resin having a quaternary ammonium base)
The resin having a quaternary ammonium base is preferably a vinyl resin containing a quaternary ammonium salt structural unit. A vinyl resin containing a quaternary ammonium salt structural unit can be obtained by polymerizing an ethylenically unsaturated monomer having a quaternary ammonium base and other ethylenically unsaturated monomers by a known method, if necessary. After polymerizing an ethylenically unsaturated monomer having an amino group with another ethylenically unsaturated monomer by a known method, a quaternary ammonium chloride is reacted with an onium chloride agent. It can be obtained by the method of

Specific examples of the ethylenically unsaturated monomer having a quaternary ammonium base, the ethylenically unsaturated monomer having an amino group, the onium chloride agent, and other ethylenically unsaturated monomers are shown below. In the present specification, when either or both of "acrylic, methacrylic" is indicated, it may be described as "(meth) acrylic". Similarly, when indicating either or both of "acryloyl and methacryloyl", it may be described as "(meth) acryloyl".

Examples of the ethylenically unsaturated monomer having a quaternary ammonium base include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, and (meth). ) Acryloyloxyethylmethylmorpholinoammonium chloride and other alkyl (meth) acrylate-based quaternary ammonium salts, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloylaminoethyltriethylammonium chloride, (meth) acryloylaminoethyldimethylbenzyl Examples thereof include alkyl (meth) acryloylamide-based quaternary ammonium salts such as ammonium chloride, dimethyldialylammonium methylsulfate, and trimethylvinylphenylammonium chloride.

Examples of the ethylenically unsaturated monomer having an amino group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, diisopropylaminoethyl (meth) acrylate, and dibutylamino. Ethyl (meth) acrylate, diisobutylaminoethyl (meth) acrylate, dit-butylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) acrylamide, diisopropyl (Meta) acrylic acid ester or (meth) having a dialkylamino group such as aminopropyl (meth) acrylamide, dibutylaminopropyl (meth) acrylamide, diisobutylaminopropyl (meth) acrylamide, dit-butylaminopropyl (meth) acrylamide, etc. Examples include acrylamide, styrenes having a dialkylamino group such as dimethylaminostyrene and dimethylaminomethylstyrene, diallylamine compounds such as diallylmethylamine and diallylamine, and amino such as N-vinylpyrrolidin, N-vinylpyrrolidone and N-vinylcarbazole. Group-containing aromatic vinyl-based monomers can be mentioned.

Examples of the onium chloride agent include alkyl sulphates such as dimethyl sulphate, diethyl sulphate, or dipropyl sulphate, sulfonic acid esters such as methyl p-toluene sulfonate, or methyl benzene sulfonate, methyl chloride, ethyl chloride, propyl chloride, or. Examples thereof include alkyl chlorides such as octyl chloride, methyl bromide, ethyl bromide, propyl bromide, alkyl bromides such as octyl chloride, benzyl chloride, benzyl bromide and the like.

In the reaction between an ethylenically unsaturated monomer having an amino group and an onium chloride agent, an onium chloride agent having an equimolar amount or less with respect to the amino group is usually added dropwise to an ethylenically unsaturated monomer solution having an amino group. Can be done by doing. The temperature during the ammonium chloride reaction is about 90 ° C. or lower, particularly preferably about 30 ° C. or lower when the vinyl monomer is ammonium chloride, and the reaction time is about 1 to 4 hours.

Alternatively, an alkoxycarbonylalkyl halide can be used as the onium chloride agent. The alkoxycarbonylalkyl halide is represented by the following general formula (102).

Z-R ^206- COOR ²⁰⁷ General formula (102)

(In the general formula (102), Z is a halogen such as chlorine or bromine, preferably bromine, and R ²⁰⁶ is an alkylene group having 1 to 6, preferably 1 to 5, and more preferably 1 to 3 carbon atoms. R ²⁰⁷ is a lower alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.)

In the reaction of an ethylenically unsaturated monomer having an amino group with an alkoxycarbonylalkyl halide, an equimolar or less alkoxycarbonylalkyl halide is reacted with the amino group in the same manner as the above onium chloride agent, and then -COOR ²⁰⁷ is added. obtained by converting the - carboxylate ions by hydrolysis ^(-COO). As a result, an ethylenically unsaturated monomer having a carboxybetaine structure represented by the general formula (102) and having an ammonium base can be obtained.

The other ethylenically unsaturated monomer is particularly limited as long as it is a monomer copolymerizable with an ethylenically unsaturated monomer having a quaternary ammonium base or an ethylenically unsaturated monomer having an amino group. However, it can be appropriately selected according to the intended use.
From the viewpoint of heat resistance and developability, the other ethylenically unsaturated monomer may have a hydroxyl group, a carboxyl group, an oxetanyl group, a t-butyl group, an isocyanate group, and a (meth) acrylic group. It is preferable to have a hydroxyl group and / or a carboxyl group in particular.

Examples of the ethylenically unsaturated monomer having a hydroxyl group are not particularly limited, but for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Examples thereof include glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl acrylate, and caprolactone adducts of these monomers (the number of addition moles is preferably 1 to 5).

Examples of the ethylenically unsaturated monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid and the like, and the ethylenically having a carboxylic acid anhydride group. Examples of the unsaturated monomer include maleic anhydride, itaconic anhydride and the like.

Examples of the ethylenically unsaturated monomer having an oxetanyl group include 3- (acryloyloxymethyl) 3-methyloxetane, 3- (methacryloyloxymethyl) 3-methyloxetane, 3- (acryloyloxymethyl) 3-ethyloxetane, and the like. 3- (methacryloyloxymethyl) 3-ethyloxetane, 3- (acryloyloxymethyl) 3-butyloxetane, 3- (methacryloyloxymethyl) 3-butyloxetane, 3- (acryloyloxymethyl) 3-hexyloxetane and 3- (Methacryloxymethyl) 3-hexyloxetane and the like can be mentioned.

Examples of the ethylenically unsaturated monomer having a t-butyl group include t-butyl acrylate and t-butyl methacrylate.

Examples of the ethylenically insatiable monomer having an isocyanate group include 2-isocyanate ethyl methacrylate, 2-isocyanate ethyl acrylate, 4-isocyanate butyl methacrylate, 4-isocyanate butyl acrylate and the like.

The isocyanate group in the present invention also includes a blocked isocyanate group and can be preferably used. The blocked isocyanate group can be deprotected by heating to regenerate an active isocyanate group while suppressing the reactivity of the isocyanate group by protecting the isocyanate group with another functional group under normal conditions. Indicates an isocyanate block body.

Commercially available products of such an ethylenically unsaturated monomer having a blocked isocyanate group include, for example, 2-[(3,5-dimethylpyrazolyl) carboxyamino] ethyl methacrylate (Carens MOI-BP, manufactured by Showa Denko KK); 2-(0- [1'methylprovideneamino] carboxyamino) ethyl methacrylate (Karenzu MOI-BM, manufactured by Showa Denko) and the like can be mentioned.

Further, as the ethylenically unsaturated monomer having a blocked isocyanate group, a commercially available product can be used, or it can be prepared and used by a known method. For example, an isocyanate compound having an ethylenically unsaturated bond and a blocking agent are stirred in a solvent at a temperature of about 0 to 200 ° C., and known separation and purification means such as concentration, filtration, extraction, crystallization and distillation are used. It can be obtained by using and separating.

The amount of the quaternary ammonium base present in the resin having the quaternary ammonium base is not particularly limited, but the ammonium salt value of the resin is preferably 10 to 200 mgKOH / g, and 20 to 130 mgKOH / g. Is more preferable.
In order for the ammonium salt value of the resin to satisfy the above range, the preferable content of the structural unit having a quaternary ammonium base is 4 to 74% by weight based on 100% by weight of the total structural units constituting the resin. A more preferable range is 8 to 48% by weight.

The molecular weight of the resin having a quaternary ammonium base used in the present invention is not particularly limited, but the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) is 1,000 to 500,000. It is preferably 3,000 to 15,000, and more preferably 3,000 to 15,000.

A quaternary ammonium salt compound other than a resin having a quaternary ammonium base A preferable form of a quaternary ammonium salt compound other than a resin having a quaternary ammonium base is colorless or white. Here, colorless or white means a so-called transparent state, and is defined as a state in which the transmittance is 95% or more, preferably 98% or more in the entire wavelength region of 400 to 700 nm in the visible light region. It is a thing. That is, it is necessary that the dye component does not hinder the color development and does not cause a color change.

As the quaternary ammonium salt compound other than the resin having a quaternary ammonium base, a compound represented by the following general formula (11) can be used.

[一般式（１１）中、Ｒ¹⁰¹〜Ｒ¹⁰⁴は、それぞれ独立に、炭素数１〜２０のアルキル基またはベンジル基を示し、Ｒ¹⁰¹、Ｒ¹⁰²、Ｒ¹⁰³、又はＲ¹⁰⁴の少なくとも２つ以上が、Ｃの数が５〜２０個である。Ｙは無機または有機のアニオンを表す。] General formula (11)

[In the general formula (11), R ^{101 to} R ¹⁰⁴ independently represent an alkyl group or a benzyl group having 1 to 20 carbon atoms, and at least two or more of ^{R 101} , R ¹⁰² , R ¹⁰³ , or R ^104. However, the number of C is 5 to 20. Y represents an inorganic or organic anion. ]

By setting the number of Cs in at least two or more side chains of ^{R 101 to} R ^{104 to 5 to 20, the solubility in a solvent becomes good.} If ^{the number of alkyl groups in R 101 to} R ¹⁰⁴ is less than 5 and the number of alkyl groups is 3 or more, the solubility in a solvent is deteriorated, and foreign matter in the coating film is likely to be generated. Further, if an alkyl group having more than 20 Cs is present in the side chain, the color-developing property of the salt-forming compound may be impaired.

The Y- component constituting the anion of the quaternary ammonium salt compound other than the resin having a quaternary ammonium base may be an inorganic or organic anion, but is preferably a halogen and is usually chlorine.

Specifically, as such a quaternary ammonium salt compound, tetramethylammonium chloride (molecular weight of the cation moiety is 74), tetraethylammonium chloride (molecular weight of the cation moiety is 122), and monostearyltrimethylammonium chloride (molecular weight of the cation moiety is 122). 312), distearyldimethylammonium chloride (cationic moiety has a molecular weight of 550), tristearyl monomethylammonium chloride (cationic moiety has a molecular weight of 788), cetyltrimethylammonium chloride (cationic moiety has a molecular weight of 284), and trioctylmethylammonium chloride (cationic moiety has a molecular weight of 284). The molecular weight of the cation part is 368), dioctyldimethylammonium chloride (the molecular weight of the cation part is 270), monolauryltrimethylammonium chloride (the molecular weight of the cation part is 228), dilauryldimethylammonium chloride (the molecular weight of the cation part is 382), and tri. Laurylmethylammonium chloride (cationic moiety has a molecular weight of 536), triamylbenzylammonium chloride (cationic moiety has a molecular weight of 318), trihexylbenzylammonium chloride (cationic moiety has a molecular weight of 360), and trioctylbenzylammonium chloride (cationic moiety has a molecular weight of 360). Molecular weight 444), trilaurylbenzylammonium chloride (cationic moiety molecular weight 612), benzyldimethylstearylammonium chloride (cationic moiety molecular weight 388), and benzyldimethyloctylammonium chloride (cationic moiety molecular weight 248), or dialkyl It is preferable to use (alkyl is C _{14 to} C ₁₈ ) dimethylammonium chloride (hardened beef fat) (molecular weight of cation portion is 438 to 550) or the like.

Products include Kao's Coatamine 24P, Coatamine 86P Conch, Coatamine 60W, Coatamine 86W, Coatamine D86P, Sanizol C, Sanizol B-50, etc., Lion's Alucard 210-80E, 2C-75, 2HT-75, Examples thereof include 2HT flakes, 2O-75I, 2HP-75, and 2HP flakes, among which coatamine D86P (distearyldimethylammonium chloride) or alucard 2HT-75 (dialkyl (alkyl is C _{14 to} C ₁₈ ) dimethylammonium chloride). Etc. are preferable.

The molecular weight of the cation moiety of the quaternary ammonium salt compound other than the resin having a quaternary ammonium base is preferably in the range of 190 to 900. The cation portion corresponds to the portion ^{of (NR 101} R ¹⁰² R ¹⁰³ R ¹⁰⁴ ) ^{+ in} the general formula (11). If the molecular weight is smaller than 190, the light resistance and heat resistance are lowered, and the solubility in a solvent may be further lowered. Further, when the molecular weight is larger than 900, the ratio of the color-developing component in the molecule decreases, so that the color-developing property may decrease and the brightness may also decrease. More preferably, the molecular weight of the cation moiety is in the range of 240 to 850, and particularly preferably in the range of 350 to 800.
Here, the molecular weight was calculated based on the structural formula, and the atomic weight of C was 12, the atomic weight of H was 1, and the atomic weight of N was 14.

(Manufacturing method of salt-forming compound)
The salt-forming compound of the anionic dye and the cationic compound can be produced by a conventionally known method. A specific method is disclosed in JP-A-11-72969.
As an example, after dissolving the anionic dye in water, the chlorination treatment may be performed while adding a cationic compound and stirring. Wherein sulfonic acid group in the anionic dyes (-SO ₃ H), salt formation compound moiety is bound to sodium sulfonate group (-SO ₃ Na) portion and an ammonium group of the cationic compound (NH ₄ ⁺⁾ is can get. In addition, instead of water, methanol and ethanol are also solvents that can be used during chloride formation.

The ratio of the cationic compound to the anionic dye is as long as the molar ratio of the total cation unit of the cationic compound to the total anionic group of the anionic dye is in the range of 10/1 to 1/4. The salt compound can be suitably adjusted, and it is more preferable if it is in the range of 2/1 to 1/2.

As the salt-forming compound, particularly excellent solvent solubility is achieved by using a salt-forming compound of an anionic dye (CI Acid Red 289, CI Acid Red 52, etc.) and a quaternary ammonium salt compound. When used in combination with a pigment described later, it becomes more excellent in heat resistance, light resistance, and solvent resistance. Further, it is presumed that the reason why the salt-forming compound becomes favorable when used in combination with the pigment is that it is adsorbed on the pigment while being dissolved and dispersed in the solvent. At this time, the primary particle size of the pigment is preferably 20 to 100 nm.
The coloring composition of the present invention will be described later, but in the form of a blue coloring composition used in combination with a blue pigment, a red coloring composition used in combination with a red pigment, a yellow coloring composition used in combination with a yellow pigment, and a green coloring composition. Is preferable.

[Sulfonic acid amide compound of acid dye]
The sulfonic acid amide compound of the acid dye that can be preferably used for the dye (C) is obtained by chlorinating _{an acid dye having -SO 3} H and -SO ₃ Na by a conventional method to make -SO ₃ H -SO ₂ Cl. , This compound can be produced by reacting with an amine having _{-NH 2 groups.}
Specific examples of the amine compound that can be preferably used in sulfonamide formation include 2-ethylhexylamine, dodecylamine, 3-decyloxypropylamine, 3- (2-ethylhexyloxy) propylamine, and 3-ethoxypropyl. It is preferable to use amine, cyclohexylamine and the like.
To give an example, C.I. I. When a sulfonic acid amide compound obtained by modifying Acid Red 289 with 3- (2-ethylhexyloxy) propylamine is obtained, C.I. I. Acid Red 289 was sulfonyl chlorided and then reacted with a theoretical equivalent of 3- (2-ethylhexyloxy) propylamine in dioxane to give C.I. I. The sulfonic acid amide compound of Acid Red 289 may be obtained.
In addition, C.I. I. When a sulfonic acid amide compound obtained by modifying Acid Red 52 with 3- (2-ethylhexyloxy) propylamine is also obtained, C.I. I. Acid Red 52 was sulfonyl chlorided and then reacted with a theoretical equivalent of 3- (2-ethylhexyloxy) propylamine in dioxane to give C.I. I. The sulfonic acid amide compound of Acid Red 52 may be obtained.

[Salt-forming compounds consisting of basic dyes and compounds of organic and inorganic acids]
The basic dye has poorer light resistance and heat resistance, and its characteristics are not sufficient for use in an image display device using a color filter that requires high reliability. Therefore, in order to improve the drawbacks of these dyes, it is preferable to chlorinate the basic dye with an organic acid or an inorganic acid. As the organic acid, it is preferable to use an organic sulfonic acid or an organic carboxylic acid, and it is particularly preferable to use naphthalene sulfonic acid. Tobias acid is particularly preferable. Further, it is particularly preferable to use perchloric acid as the inorganic acid.

In the photosensitive coloring composition of the present invention, it is preferable that the dye (A2) is contained in the colorant (A) in an amount of 15% by mass to 100% by mass because good color characteristics can be obtained. It is more preferable that it is contained in an amount of 20% by mass to 60% by mass from the viewpoint of solvent resistance and coloring power.
In the photosensitive coloring composition of the present invention, the total content of the blue pigment (A1) and the dye (A2) having a phthalocyanine skeleton is 65% by mass to 100% by mass in the colorant (A). It is preferable because good coloring power can be obtained. It is more preferably contained in an amount of 70% by mass to 100% by mass.

<Other pigments>
Specific examples of other organic pigments that can be used for producing other color filter segments and black matrices are shown below by color index numbers.

Examples of the red photosensitive composition for forming the red filter segment include C.I. I. P
ignent Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4
, 81: 1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 166, 1
68, 176, 177, 178, 179, 180, 184, 185, 187, 192, 2
00, 202, 207, 208, 209, 210, 215, 216, 217, 220, 2
21,223,224,226,227,228,240,242,246,254, 2
Red pigments such as 55, 264, 269, 272, 279 can be used. A yellow pigment and an orange pigment can be used in combination with the red photosensitive composition.
Further, as the azo pigment, a naphthol azo pigment represented by the following general formula (2) is preferable.

［一般式（２）中、Ａは、水素原子、ベンズイミダゾロン基、置換基を有してもよいフェ
ニル基または置換基を有してもよい複素環基を表す。Ｒ^１は、水素原子、トリフルオロメ
チル基、炭素数１〜４のアルキル基、−ＯＲ^７または−ＣＯＯＲ^８を表す。Ｒ^２〜Ｒ^６は
、それぞれ独立して、水素原子、ハロゲン原子、シアノ基、ニトロ基、トリフルオロメチ
ル基、炭素数１〜４のアルキル基、−ＯＲ^９、−ＣＯＯＲ^１０、−ＣＯＮＨＲ^１１、−Ｎ
ＨＣＯＲ^１２または−ＳＯ_２ＮＨＲ^１３を表す。Ｒ^７〜Ｒ^１３は、それぞれ独立して、水
素原子または炭素数１〜４のアルキル基を表す。
ただし、Ｒ^４が−ＮＨＣＯＲ^１２であり、Ａ、Ｒ^２、Ｒ^３、Ｒ^５、およびＲ^６が水素原子
、かつＲ^１がハロゲン原子の場合は除く。］ General formula (2)

[In the general formula (2), A represents a hydrogen atom, a benzimidazolone group, a phenyl group which may have a substituent or a heterocyclic group which may have a substituent. R ¹ represents a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, -OR ⁷ or -COOR ⁸ . R ² to R ⁶ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon ^{atoms, -OR 9, -COOR 10, -CONHR} 11, -N
Represents HCOR ¹² or -SO ₂ NHR ¹³ . R ^{7 to} R ¹³ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
However, this excludes cases where ^{R 4 is -NHCOR 12} , A, R ² , R ³ , R ⁵ and R ⁶ are hydrogen atoms, and R ¹ is a halogen atom. ]

Formula Among naphthol azo pigment represented by (2), ^preferably, the azo pigment at least one is a trifluoromethyl group of R 2 to R ^6, or at least one of ^R 2 to R ⁶ -NHCOR ^The azo pigment of 12 is preferable because the pigment particles can be easily refined and the contrast ratio is excellent.

The naphthol azo pigment represented by the general formula (2) includes a color index (CI).
) Indicated by number, C.I. I. Pigment Red 31, 32, 146, 147, 150,
184, 187, 188, 210, 238.245.247, 266, 268, 269,
C. I. Violet 25, 50 and the like can be mentioned. Among these, from the viewpoint of hue and lightness, C.I. I. Pigment Red 150, 170, 187, 266, 268, 269
Is preferable.

In the general formula (2), in A, the "substituent" of the phenyl group which may have a substituent includes a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, and a cyano. Monovalent of an acidic group selected from a group, a trifluoromethyl group, a nitro group, a hydroxyl group, a carbamoyl group, an N-substituted carbamoyl group, a sulfamoyl group, an N-substituted sulfamoyl group, a carboxyl group, a sulfo group, a carboxyl group or a sulfo group. Examples thereof include trivalent metal salts (for example, sodium salt, potassium salt, aluminum salt, etc.). Therefore, specific examples of the phenyl group which may have a substituent include a phenyl group, a p-methylphenyl group, a 4-tert-butylphenyl group, a p-nitrophenyl group, a p-methoxyphenyl group and an o-tri. Fluoromethylphenyl group, p-chlorophenyl group, p-bromophenyl group, 2,4-dichlorophenyl group, 3-carbamoylphenyl group, 2-chloro-4-carbamoylphenyl group, 2-
Methyl-4-carbamoylphenyl group, 2-methoxy-4-carbamoylphenyl group, 2
−Methoxy-4-methyl-3-sulfamoylphenyl group, 4-sulfophenyl group, 4-
Examples thereof include, but are not limited to, a carboxyphenyl group and a 2-methyl-4-sulfophenyl group.

Further, in A, the "substituted group" of the heterocyclic group which may have a substituent includes a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a cyano group and a trifluoro. A monovalent to trivalent metal of an acidic group selected from a methyl group, a nitro group, a hydroxyl group, a carbamoyl group, an N-substituted carbamoyl group, a sulfamoyl group, an N-substituted sulfamoyl group, a carboxyl group, a sulfo group, a carboxyl group or a sulfo group. Examples include salts (eg, sodium salt, potassium salt, aluminum salt, etc.). Further, the "heterocycle" means an atom containing one or more heteroatoms other than carbon atoms among the atoms constituting the ring system, and may be a saturated ring or an unsaturated ring. Further, it may be a monocyclic ring or a fused ring. Therefore, the heterocycles include pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, isooxazole ring, and isothiazole ring. , Pyrazole ring, thiazazole ring, oxazole ring, quinoline ring, benzofuran ring, indole ring, morpholin ring,
Examples thereof include a pyrrolidine ring, a piperidine ring, and a tetrahydrofuran ring. Therefore, the heterocyclic group means a monovalent free group derived by removing a hydrogen atom from these heterocycles, and therefore, as a specific example of a heterocyclic group which may have a substituent, 2- Pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrrolill group, 3-pyrrolill group, 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, 2-imidazolyl group, 2- Oxazolyl group, 2-thiazolyl group, piperidino group, 4-piperidyl group, morpholino group, 2-morpholinyl group, N
-Indrill group, 2-Indrill group, 2-benzofuryl group, 2-benzothienyl group, 2-
Examples thereof include a quinolino group and an N-carbazolyl group.

Further, ^{examples of the halogen atom in R 2 to} R ⁶ and R ¹⁴ include fluorine, chlorine, bromine and iodine.

The alkyl group having 1 to 4 carbon atoms in R ^{1 to} R ¹⁴ may be linear or branched, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or an isobutyl group. , The sec-butyl group and the tert-butyl group.

As the pigment, from the viewpoint of lightness, A is preferably a phenyl group which may have a substituent. Further, from the viewpoint of lightness and dispersibility, R ¹ is preferably an alkyl group having 1 to 4 carbon atoms or −OR ⁷ and more preferably R ¹ is a methyl group or a methoxy group.

The azo pigment used in the present invention may have a chemical structure of the general formula (2) or a homovariant thereof, or may be a pigment having any crystal form, and is called a so-called polymorph. It may be a mixed crystal of pigments having any crystal morphology. The crystal morphology of these pigments can be confirmed by powder X-ray diffraction measurement and X-ray crystal structure analysis.

The naphthol azo pigment is a water-insoluble pigment having excellent fastness to a solvent and to light, and by using this pigment, a coloring composition for a color filter having excellent both brightness and contrast ratio. Can be obtained.
The naphthol azo pigment may be used alone or in combination of two or more.

Examples of the yellow pigment include C.I. I. Pigment Yellow 1, 2, 3, 4
5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32
, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53,
55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 9
4, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 1
13, 114, 115, 116, 117, 118, 119, 120, 123, 125, 1
26, 127, 128, 129, 137, 138, 139, 147, 148, 150, 1
51, 152, 153, 154, 155, 156, 161, 162, 164, 166, 1
67, 168, 169, 170, 171, 172, 173, 174, 175, 176, 1
77, 179, 180, 181, 182, 185, 187, 188, 193, 194, 1
99, 213, 214 and the like can be used.
Among the above, isoindoline pigments and quinophthalone pigments are preferable. Among these, especially C.I. I. Pigment Yellow 138, C.I. I. Pigment Y
allow 139, C.I. I. When Pigment Yellow 185 or a quinophthalone compound represented by the following general formula (3) is contained, it is preferable because it is excellent in lightness and coloring power.
The quinophthalone compound represented by the general formula (3) will be described.

［一般式（３）中、Ｘ１〜Ｘ１３は、それぞれ独立に、水素原子、ハロゲン原子、置換基
を有しても良いアルキル基、置換基を有しても良いアルコキシル基、置換基を有しても良
いアリール基、酸性基、あるいはその金属塩、アルキルアンモニウム塩、置換基を有して
も良いフタルイミドメチル基、または置換基を有しても良いスルファモイル基を示す。Ｘ
１〜Ｘ４、および／または、Ｘ１０〜Ｘ１３の隣接した基は、一体となって、置換基を有
してもよい芳香環を形成する。］ General formula (3)

[In the general formula (3), X1 to X13 each independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, and a substituent. Indicates a aryl group, an acidic group, or a metal salt thereof, an alkylammonium salt, a phthalimidemethyl group which may have a substituent, or a sulfamoyl group which may have a substituent. X
Adjacent groups of 1-X4 and / or X10-X13 together form an aromatic ring that may have a substituent. ]

Here, examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Further, among the alkyl groups which may have a substituent, the number of carbon atoms of the alkyl group (excluding the number of carbon atoms of the substituent) is preferably 1 to 10. Examples of the substituent include a halogen atom, an alkoxy group having 1 to 10 carbon atoms, a nitro group, an aryl group having 6 to 18 carbon atoms, and the like, and may have two or more kinds of substituents. Examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-ptyl group, a neopentyl group, an n-hexyl group and an n-octyl group. In addition to linear or branched alkyl groups such as stearyl group and 2-ethylhexyl group, trichloromethyl group, trifluoromethyl group,
2,2,2-trifluoroethyl group, 2,2-dibromoethyl group, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, Examples thereof include an alkyl group having a substituent such as a benzyl group, a 4-methylbenzyl group, a 4-tert-ptylbenzyl group, a 4-methoxypentyl group, a 4-nitrobenzyl group and a 2,4-dichlorobenzyl group.

Further, among the alkoxyl groups which may have a substituent, the number of carbon atoms of the alkoxyl group (excluding the number of carbon atoms of the substituent) is preferably 1 to 10. Examples of the substituent include a halogen atom, an alkoxy group having 1 to 10 carbon atoms, a nitro group, and an aryl group having 6 to 18 carbon atoms, and may have two or more kinds of substituents. As an alkoxy group which may have a substituent,
Methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isoptyloxy group, tert-ptyloxy group, neopentyloxy group, 2,3-dimethyl-3
-Pentoxy, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2
-In addition to linear or branched alkoxyl groups such as ethylhexyloxy group, trichloromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropyloxy group, Examples thereof include an alkoxyl group having a substituent such as a 2,2-ditrifluoromethylpropoxy group, a 2-ethoxyethoxy group, a 2-butoxyethoxy group, a 2-nitropropoxy group and a benzyloxy group.

Further, in the aryl group which may have a substituent, the number of carbon atoms of the aryl group (excluding the number of carbon atoms of the substituent) is preferably 6 to 18. As the substituent, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a nitro group, and the like.
Amino groups and the like may be mentioned and may have two or more kinds of substituents. Examples of the aryl group which may have a substituent include an aryl group such as a phenyl group, a naphthyl group and an anthranyl group, as well as p-.
Methylphenyl group, p-bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4 -Hydroxy-1-naphthyl group, 6-methyl-
2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthracinyl group, 2-
Aryl groups having a substituent such as an aminoanthraquinonyl group can be mentioned.

As the acidic group, for _example, -SO 3 H, -COOH, and examples of the monovalent to trivalent metal salt thereof acidic groups, sodium salts, potassium salts, magnesium salts, calcium salts, iron salts, Examples include aluminum salts. Examples of the alkylammonium salt of the acidic group include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine and stearylamine, and quaternary alkyls such as palmityltrimethylammonium, dilauryldimethylammonium and distearyldimethylammonium salt. Ammonium salts can be mentioned.

A "substituent" in a phthalimidomethyl group (C ₆ H ₄ (CO) ₂ N-CH _2- ) which may have a substituent and a sulfamoyl group (H ₂ NSO _2- ) which may have a substituent. Examples thereof include the above-mentioned halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryl group which may have a substituent and the like.

Adjacent groups of X1 to X4 and / or X10 to X13 of the general formula (3) together form at least one aromatic ring which may have a substituent. Examples of the aromatic ring here include a hydrocarbon aromatic ring and a heteroaromatic ring. Examples of the hydrocarbon aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring, and the heteroaromatic ring includes a heteroaromatic ring.
Examples thereof include a pyridine ring, a pyrazine ring, a pyrrol ring, a quinoline ring, a quinoxalin ring, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, an oxazole ring, a thiazole ring, an imidazole ring, a pyrazole ring, an indole ring, and a carbazole ring.
In addition, these yellow pigments can be used alone or in combination of two or more.

Examples of the orange pigment include C.I. I. Pigment orange 36, 38, 43, 51, 55, 59, 61, 71, 73 and the like can be used.
In addition, these orange pigments can be used alone or in combination of two or more.

Examples of the green pigment include C.I. I. Pigment Green 7, 10, 36, 37 and 58, aluminum phthalocyanine pigments and the like can be used. The above-mentioned yellow pigment can also be used in combination.

For blue pigments, for example, C.I. I. Blue pigments such as Pigment Blue 16, 22, 60, 64, 80 can be used.
For purple pigments, C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 and the like can be used. Furthermore, C.I. I. Pigment Red 81, 81: 1, 81: 2, 81: 3, 81: 4, 8
A metal lake pigment of a rhodamine dye such as 1: 5 can be used in combination. Further, the above-mentioned yellow pigment can be used in combination for adjusting the chromaticity.

Black pigments include, for example, carbon black, aniline black, anthraquinone-based black pigments, perylene-based black pigments, specifically C.I. I. Pigment Black 1, 6, 7, 12, 20, 31 and the like can be used.
A mixture of a red pigment, a blue pigment, and a green pigment can also be used for the black photosensitive composition.
As the black pigment, carbon black is preferable from the viewpoint of price and light-shielding property, and carbon black may be surface-treated with a resin or the like. Further, in order to adjust the color tone, a blue pigment or a purple pigment can be used in combination with the black photosensitive composition.

Inorganic pigments include barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, dark blue, chromium oxide green, cobalt green, amber, and titanium black. , Synthetic iron black, titanium oxide, metal oxide powder such as iron tetroxide, metal sulfide powder, metal powder and the like. Inorganic pigments are preferably used in combination with organic pigments in order to ensure good coatability, sensitivity, developability, etc. while balancing saturation and lightness. Further, since the color is adjusted, the dye can be contained within a range that does not reduce the heat resistance.

Based on the total non-volatile components of the photosensitive composition (100% by mass), the concentration of the colorant (A) is preferably 5% by mass or more, more preferably 10% by mass or more, most preferably, from the viewpoint of obtaining sufficient color reproducibility. It is preferably 15% by mass or more. Further, since the stability of the photosensitive composition is improved, the concentration of the colorant component is preferably 90% by mass or less, more preferably 80% by mass or less, and most preferably 70% by mass or less.
Further, in one embodiment, the concentration of the colorant component is more preferably 25% by mass or more, particularly preferably 30% by mass or more, based on the total non-volatile components of the photosensitive composition as a reference (100% by mass). In some cases, 35% by mass or more is most preferable. According to this embodiment, there is an advantage that both solvent resistance and resolution can be achieved even when the concentration of the colorant component is high.
On the other hand, even when the concentration of the colorant component in the photosensitive composition for a color filter is lower than the above, photoradical polymerization may be inhibited depending on the type of coloring material, and it may be difficult to obtain good chemical resistance. According to the present invention, there is an advantage that good chemical resistance can be obtained even in this case.
<Alkali-soluble resin (B) having a radically polymerizable group>
The alkali-soluble resin (B) having a radically polymerizable group in the present invention is for imparting development solubility in an alkali developing step and has an acid group. Further, in order to further improve the photosensitivity, a resin having a radically polymerizable group is used.

In particular, by using an active energy ray-curable resin having a radically polymerizable group in the side chain, the colorant is fixed by three-dimensional cross-linking of the resin when exposed to active energy rays to form a coating film. The heat resistance is improved, and fading (deterioration of spectral characteristics) due to heat of the colorant can be suppressed. It also has the effect of suppressing aggregation and precipitation of pigment components in the developing process.

The alkali-soluble resin (B) having an aradically polymerizable group in the present invention is a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Is preferable.

The weight average molecular weight (Mw) of the alkali-soluble resin (B) having a radically polymerizable group in the present invention is 2000 or more and 10000 or less, preferably 3000 or more and 9000 or less, and 4000 or more in order to impart alkali development solubility. More preferably, it is 8000 or less. Further, the value of Mw / Mn is preferably 10 or less. If the weight average molecular weight (Mw) is less than 2000, the adhesion to the substrate is lowered and the exposure pattern is less likely to remain. If it exceeds 10000, the alkali development solubility is lowered, a residue is generated, and the linearity of the pattern is deteriorated.
The acid value of the alkali-soluble resin in the present invention is 50 or more and 200 or less (KOHmg / g) in order to impart alkali development solubility, preferably in the range of 100 or more and 180 or less, and more preferably 110 or more and 170 or less. The range. If the acid value is less than 50, the alkali development solubility is lowered, a residue is generated, and the linearity of the pattern is deteriorated. If it exceeds 200, the adhesion to the substrate is lowered and the exposure pattern is less likely to remain.
The range of the above parameters is optimal for balancing substrate adhesion and alkali development solubility in combination with a dispersant for dispersing the pigment and a surfactant described later.

Since the alkali-soluble resin (B) having a radically polymerizable group in the present invention has good film forming properties and various resistances, the amount is 20 parts by weight or more with respect to 100 parts by weight of the total weight of the colorant (A). It is preferable to use it, and it is preferable to use it in an amount of 1000 parts by weight or less because the pigment concentration is high and good color characteristics can be exhibited.

The alkali-soluble resin (B) having a radically polymerizable group of the present invention has at least one radically polymerizable group compound (B1) (excluding (B2)), an epoxy group and an unsaturated bond in one molecule. The compound (B2) is copolymerized to obtain a copolymer (B6), and the epoxy group of the obtained copolymer (B6) is reacted with the compound (B4) having an unsaturated monobasic acid to obtain an epoxy. A resin (B5) obtained by obtaining a copolymer (B7) having a hydroxyl group formed by opening a ring of a group, and further reacting the hydroxyl group of the obtained copolymer (B7) with a polybasic acid anhydride (B5). b1) is preferable.
The resin obtained by the reaction does not react with all the functional groups that can react in the reaction between the epoxy group and the acid and the reaction between the hydroxyl group and the acid anhydride, but becomes a mixture of various products. Therefore, since it is impossible or almost impractical to specify and describe the alkali-soluble resin (B) having a radically polymerizable group, it is described by the production method.

<< Resin (b1) >>
The resin (b1) is obtained by copolymerizing a compound (B1) having at least one unsaturated bond (excluding (B2)) and a compound (B2) having an epoxy group and an unsaturated bond in one molecule. The copolymer (B6) was obtained, and the obtained copolymer (B6) was reacted with the compound (B4) having an unsaturated monobasic acid to obtain a copolymer (B7), which was further obtained. It is a resin obtained by reacting a copolymer (B7) with a polybasic acid anhydride (B5).

The content of the resin (b1) is preferably 5 to 70% by weight, more preferably 10 to 60% by weight, in the photosensitive coloring composition from the viewpoint of film forming property.

<Compound having at least one unsaturated bond (B1)>
Examples of the compound (B1) having at least one unsaturated bond include the following (a), (b), (c), and (d), and a compound having an epoxy group and an unsaturated bond in one molecule. It is something other than (B2).

一般式（１２）：

[一般式（１１）及び（１２）中、Ｒ_１は、水素原子、またはベンゼン環を有していてもよい炭素数１〜２０のアルキル基である。] (A) A compound having an aromatic ring group represented by the general formula (11) or the general formula (12):

General formula (11):

General formula (12):

[In the general formulas (11) and (12), R ₁ is an alkyl group having 1 to 20 carbon atoms which may have a hydrogen atom or a benzene ring. ]

化学式（１５）：

(B) Compound having an aliphatic ring group represented by the chemical formula (14) or the chemical formula (15):

Chemical formula (14):

Chemical formula (15):

(C) Other compounds (f2)

Hereinafter, compound (a), compound (b), and compound (c) will be described in order. In the present specification, the content weight% of each compound is the weight% of the precursor that brings each compound to the resin (C1).

一般式（１２）：

[一般式（１１）及び（１２）中、Ｒ_１は、水素原子、またはベンゼン環を有していてもよい炭素数１〜２０のアルキル基である。] [Compound (a)]
Compound (a) has a cyclic structure composed of aromatic ring groups represented by the general formulas (11) and (12), and contributes to the improvement of hardness. Based on the weight of all the structural units of the resin (a1), the structural unit (a) is preferably 2 to 80% by weight from the viewpoint of developability. If it is less than 2% by weight, the developability is lowered. On the other hand, if it exceeds 80% by weight, the dissolution rate in the alkaline developer becomes slow, the development time becomes long, and the productivity deteriorates.

General formula (11):

General formula (12):

[In the general formulas (11) and (12), R ₁ is an alkyl group having 1 to 20 carbon atoms which may have a hydrogen atom or a benzene ring. ]

Examples of the precursor of compound (a) include styrene, α-methylstyrene, divinylbenzene, inden, acetylnaphthene, benzyl acrylate, benzyl methacrylate, bisphenol A diglycidyl ether di (meth) acrylate, and (meth) acrylic of methylolated melamine. Examples thereof include monomers / oligomers such as acid esters, and ethylenically unsaturated monomers represented by the general formula (13).

（一般式（１３）中、Ｒ_６は、水素原子、またはメチル基であり、Ｒ_７は、炭素数２若しくは３のアルキレン基であり、Ｒ_８は、ベンゼン環を有していてもよい炭素数１〜２０のアルキル基であり、ｎは、１〜１５の整数である。） General formula (13):

(In the general formula (13), R ₆ is a hydrogen atom or a methyl group, R ₇ is an alkylene group having 2 or 3 carbon atoms, and R ₈ is a carbon which may have a benzene ring. It is an alkyl group of the number 1 to 20, and n is an integer of 1 to 15.)

Examples of the ethylenically unsaturated monomer represented by the general formula (13) include
New Frontier CEA manufactured by Daiichi Kogyo Seiyaku Co., Ltd. [EO-modified cresol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : methyl group, n = 1 or 2,], NP-2 [n-nonylphenoxy polyethylene Glycol acrylate, R ₆ : Hydrogen atom, R ₇ : Ethylene group, R ₈ : n-nonyl group, n = 2], N-177E [n-nonylphenoxy polyethylene glycol acrylate, R ₆ : Hydrogen atom, R ₇ : Ethylene Group, R ₈ : n-nonyl group, n = 16-17], or PHE [phenoxyethyl acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1],
Dycel, IRR169 [ethoxylated phenyl acrylate (EO 1 mol), R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1], or Ebeclyl110 [ethoxylated phenyl acrylate (EO 2 mol), R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 2],
Aronix M-101A [phenol EO modified (n ≈ 2) acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n ≈ 2], M-102 [phenol EO modified (phenol EO modified (n ≈ 2)) n ≈ 4) acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n ≈ 4], M-110 [paracumylphenol EO modified (n ≈ 1) acrylate, R ₆ : hydrogen atom , R ₇ : ethylene group, R ₈ : paracumyl, n≈1], M-111 [n-nonylphenol EO modified (n≈1) acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : n- Nonyl group, n≈1], M-113 [n-nonylphenol EO modified (n≈4) acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : n-nonyl group, n≈4], or M-117 [n- nonylphenol PO-modified (n ≒ 2.5) acrylate, _{R 6:} a hydrogen atom, _{R 7:} a propylene _group, R 8: n- nonyl, n ≒ 2.5],
Kyoei Co., Ltd. Light acrylate PO-A [Phenoxyethyl acrylate, R ₆ : Hydrogen atom, R ₇ : Ethylene group, R ₈ : Hydrogen atom, n = 1], P-200A [Phenoxy polyethylene glycol acrylate, R ₆ : Hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n≈2], NP-4EA [nonylphenol EO adduct acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : n-nonyl group, n≈4 ], Or NP-8EA [[Nonylphenol EO adduct acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : n-nonyl group, n≈8], or light ester PO [phenoxyethyl methacrylate, R _6]. : Methyl group, R ₇ : Propylene group, R ₈ : Hydrogen atom, n = 1],
Manufactured by NOF Corporation Blemmer ANE-300 [nonylphenoxy polyethylene glycol acrylate, _{R 6:} a hydrogen atom, _{R 7:} an ethylene group, _{R 8:} - nonyl group, n ≒ 5], ANP-300 [nonylphenoxy polypropylene glycol acrylate, R ₆ : Hydrogen atom, R ₇ : Propropylene group, R ₈ : n-Nonyl group, n≈5], 43ANEP-500 [Nonylphenoxy-polyethylene glycol-polypropylene glycol-acrylate, R ₆ : Hydrogen atom, R ₇ : Ethylene group And propylene group, R ₈ : -nonyl group, n≈5 + 5], 70ANEP-550 [nonylphenoxy-polyethylene glycol-polypropylene glycol-acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group and propylene group, R ₈ : n -Nonyl group, n≈9 + 3], 75ANEP-600 [Nonylphenoxy-polyethylene glycol-polypropylene glycol-acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group and propylene group, R ₈ : n-nonyl group, n≈5 + 2 ], AAE-50 [Phenoxypolyethylene glycol acrylate, R ₆ : Hydrogen atom, R ₇ : Ethylene group, R ₈ : Hydrogen atom, n = 1], AAE-300 [Phenoxy polyethylene glycol acrylate, R ₆ : Hydrogen atom, R ₇ : Ethylene group, R ₈ : Hydrogen atom, n≈5.5], PAE-50 [Phenoxypolyethylene glycol methacrylate, R ₆ : Methyl group, R ₇ : Ethylene group, R ₈ : Hydrogen atom, n = 1], PAE-100 [Phenoxypolyethylene glycol methacrylate, R ₆ : Methyl group, R ₇ : Ethylene group, R ₈ : Hydrogen atom, n = 2], or 43PAPE-600B [Phenoxy-polyethylene glycol-polypropylene glycol-methacrylate, R ₆ : Methyl group, R ₇ : ethylene group and propylene group, R ₈ : hydrogen atom, n≈6 + 6],
Shin-Nakamura Chemical Co., Ltd. NK ESTER AMP-10G [phenoxyethylene glycol acrylate (EO1 mol), R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1], AMP-20G [phenoxyethylene glycol acrylate] (EO2mol), _{R 6:} a hydrogen atom, _{R 7:} an ethylene group, _{R 8:} a hydrogen atom, n ≒ 2], AMP-60G [phenoxy ethyleneglycol acrylate (EO6mol), _{R 6:} a hydrogen atom, _{R 7:} an ethylene group , R ₈ : hydrogen atom, n≈6], PHE-1G [phenoxyethylene glycol methacrylate (EO 1 mol), R ₆ : methyl group, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1],
Viscoat # 192 manufactured by Osaka Organic Chemical Co., Ltd. [Phenoxyethyl acrylate, R ₆ : Hydrogen atom, R ₇ : Ethylene group, R ₈ : Hydrogen atom, n = 1], or
SR-339A [2-phenoxyethylene glycol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1] or SR-504 (ethoxylated nonylphenol acrylate, R _{6) manufactured by Nippon Kayaku.} : Hydrogen atom, R ₇ : Ethylene group, R ₈ : n-nonyl group] and the like, but the present invention is not limited to these, and two or more types can be used in combination.

In the ethylenically unsaturated monomer represented by the general formula (13), although the number of carbon atoms in the alkyl group of R ₈ is 1 to 20, more preferably 1 to 10. The alkyl group includes not only a linear alkyl group but also a branched alkyl group and an alkyl group having a benzene ring as a substituent. When _{the alkyl group of R 8} has 1 to 10 carbon atoms, the adhesion to the base material is enhanced, but when the carbon number exceeds 10, the long alkyl group tends to prevent the adhesion to the base material. This tendency _{becomes remarkable as the carbon chain length of the alkyl group of R 8} becomes longer, and when the number of carbon atoms exceeds 20, the adhesion to the base material is extremely lowered. Examples of the alkyl group having a benzene ring represented by R ₈ include a benzyl group and a 2-phenyl (iso) propyl group. Developability is improved by adding one side chain benzene ring.

In the ethylenically unsaturated monomer represented by the general formula (13), n is preferably an integer of 1 to 15. When n exceeds 15, the hydrophilicity is increased, the effect of solvation is reduced, the viscosity of the resin (A1) is increased, and the viscosity of the photosensitive composition using the resin (A1) is also increased, which affects the fluidity. May be given. From the viewpoint of solvation, n is particularly preferably 1 to 4.

The precursor of compound (a) may be styrene, α-methylstyrene, benzyl acrylate, benzyl methacrylate, or the general formula (7) from the viewpoint of copolymerizability with other precursors and chemical resistance. The ethylenically unsaturated monomer shown is preferred. These are particularly preferable because a benzene ring can be introduced into the side chain of the resin (A). By introducing a benzene ring into the side chain of the resin (A), the side chain benzene ring is effective in improving the developability. Further, benzyl acrylate and / or benzyl methacrylate are most preferable from the viewpoint of development residue.

[Compound (b)]
Compound (b) has a cyclic structure composed of the aliphatic ring groups represented by the chemical formulas (14) and (15), imparts hardness, and functions as a hydrophobic site for an alkaline developer. Based on the weight of all the constituent compounds of the resin (A), the compound (b) is preferably 2 to 40% by weight from the viewpoint of developability and imparting hardness. If it is less than 2% by weight, there may be a problem that the developability and hardness are insufficient and a high-quality touch panel coating film cannot be obtained. Further, since the hydrophobicity at the time of development is insufficient, there arises a problem of pattern peeling or chipping of the pixel portion. If it exceeds 40% by weight, the dissolution rate in the alkaline developer becomes slow, the development time becomes long, and the productivity of the coating film deteriorates.

Chemical formula (14):

Chemical formula (15):

Examples of the precursor of the compound (b) include an ethylenically unsaturated monomer represented by the general formula (16), an ethylenically unsaturated monomer represented by the general formula (17), and the like.
General formula (16):

[一般式（１６）、一般式（１７）中、Ｒ_９は、水素原子、またはメチル基であり、Ｒ_１０は、炭素数２若しくは３のアルキレン基であり、ｍは、１〜１５の整数である。] General formula (17):

[In the general formula (16) and the general formula (17), R ₉ is a hydrogen atom or a methyl group, R ₁₀ is an alkylene group having 2 or 3 carbon atoms, and m is an integer of 1 to 15. Is. ]

Examples of the ethylenically unsaturated monomer represented by the general formula (16) include
Hitachi Kasei Funkrill FA-513A [dicyclopentanyl acrylate, R ₉ : hydrogen atom, R ₁₀ : none, m = 0] or FA-513M [dicyclopentanyl methacrylate, R ₉ : methyl, R _10] : None, m = 0] and the like, but the present invention is not limited to these, and two or more types can be used in combination.

Examples of the unsaturated ethylene monomer represented by the general formula (17) include
Hitachi Kasei Funkrill FA-511A [dicyclopentenyl acrylate, R ₉ : hydrogen atom, R ₁₀ : none, m = 0], FA-512A [dicyclopentenyloxyethyl acrylate, R ₉ : hydrogen atom, R _10] : Ethylene group, m = 1], FA-512M [dicyclopentenyloxyethyl methacrylate, R ₉ : methyl group, R ₁₀ : ethylene group, m = 1], or FA-512MT [dicyclopentenyloxyethyl methacrylate, R ₉ : Methyl group, R ₁₀ : Ethylene group, m = 1] and the like can be mentioned, but the present invention is not limited to these, and two or more types can be used in combination.

[Compound (c)]
Compound (c) is an ethylenically unsaturated monomer other than compounds (a) and (b), and is a precursor of compounds (a) and (b). There is no particular limitation as long as it can be copolymerized. Of these, an ethylenically unsaturated monomer having a hydroxyl group, an ethylenically unsaturated monomer having a hydroxyl group, and a side chain type cyclic ether-containing monomer are preferable.

Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate and cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, a polyether mono (meth) acrylate obtained by addition-polymerizing the above hydroxyalkyl (meth) acrylate with ethylene oxide, propylene oxide, and / or butylene oxide, (poly) γ-valerolactone, and (poly) ε-caprolactone. , And / or (poly) ester mono (meth) acrylate to which (poly) 12-hydroxystearic acid or the like is added can also be used. 2-Hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable from the viewpoint of suppressing foreign matter in the coating film.

Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, but the present invention is limited thereto. However, two or more types can be used together.

The side chain type cyclic ether-containing monomer is, for example, an unsaturated compound containing at least one skeleton selected from the group of tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton, pyran skeleton, and lactone skeleton.
Tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, (meth) acrylic acid tetrahydrofuran-3-yl ester, etc. as the tetrahydrofuran skeleton;
The furan skeleton includes 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan-2-butyl-3-en-2-one, 1-furan. -2-Butyl-3-methoxy-3-en-2-one, 6- (2-furyl) -2-methyl-1-hexen-3-one, 6-furan-2-yl-hex-1-ene -3-one, 2-furan-2-yl-1-methyl-ethyl ester of acrylate, 6- (2-furyl) -6-methyl-1-hepten-3-one, etc.;
The tetrahydropyran skeleton includes (tetrahydropyran-2-yl) methyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -oct-1-en-3-one, and 2-tetrahydropyran methacrylate. -2-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one, etc .;
The pyran skeleton includes 4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyrone and 4- (1,5-dioxa-6-oxo-7-octenyl) -6. -Methyl-2-pyrone, etc .;
As the lactone skeleton, 2-methyl-tetrahydro-2-oxo-3-furanyl ester of 2-propenate and 2-methyl-7-oxo-6-oxabicyclo [3.2.1] oct-2-propenate are used. Ilester, 2-methyl-hexahydro-2-oxo-3,5-methano-2H-cyclopenta [b] furan-7-ylester, 2-methyl-tetrahydro-2-oxo-2-propenate 2H-Pyran-3-yl ester, 2-propenic acid (tetrahydro-5-oxo-2-furanyl) methyl ester, 2-propenic acid hexahydro-2-oxo-2,6-methanoflo [3,2-b]- 6-Il ester, 2-methyl-2-methyl-2-propenate (tetrahydro-5-oxo-3-furanyl) ethyl ester, 2-methyl-decahydro-8-oxo-5,9-methano-2H 2-propenate −Flo [3,4-g] -1-benzopyran-2-yl ester, 2-methyl-2-methyl-2-propenate [(hexahydro-2-oxo-3,5-methano-2H-cyclopenta [b] furan) -6-yl) oxy] ethyl ester, 2-propenate 3-oxo-3-[(tetrahydro-2-oxo-3-furanyl) oxy] propyl ester, 2-propenate 2-methyl-2-oxy-1 -Xusaspiro [4.5] deku-8-yl ester and the like can be mentioned.
Of these, tetrahydrofurfuryl (meth) acrylate is preferable from the viewpoint of coloring and availability. These side chain type cyclic ether-containing monomers may be used alone or in combination of two or more.

Other copolymerizable monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n (meth) acrylate. -Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-butyl (meth) acrylate (Meta) acrylic acid esters such as hydroxyethyl; aromatic vinyl compounds such as styrene, vinyltoluene and α-methylstyrene; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; Butadiene or substituted butadiene compounds; ethylene or substituted ethylene compounds such as ethylene, propylene, vinyl chloride, acrylic nitrile; vinyl esters such as vinyl acetate; and the like. Among these, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and styrene are preferable because they have good transparency and do not easily impair heat resistance. These other copolymerizable monomers may be used alone or in combination of two or more.

The method for the polymerization reaction of the monomer component is not particularly limited, and various conventionally known polymerization methods can be adopted, but a solution polymerization method is particularly preferable. The polymerization temperature and the polymerization concentration (polymerization concentration = [total weight of monomer components / (total weight of monomer components + solvent weight)] × 100) are the types and ratios of the monomer components used. Although it depends on the molecular weight of the target polymer, the polymerization temperature is preferably 40 to 150 ° C. and the polymerization concentration is 5 to 50%, and more preferably the polymerization temperature is 60 to 130 ° C. and the polymerization concentration is 10 to 40%. It is better to say.

The alkali-soluble resin (B) having a radically polymerizable group includes compounds (B1) having at least one unsaturated bond such as those in the above compounds (a) to (c), and compounds other than (B1) described later. A compound (B2) having an epoxy group and an unsaturated bond in one molecule is copolymerized to obtain a copolymer (B6), and the obtained copolymer (B6) and a compound having an unsaturated monobasic acid are obtained. It is obtained by reacting with (B4) to obtain a copolymer (B7), and further reacting the obtained copolymer (B7) with a polybasic acid anhydride (B5).

<Compound having an epoxy group and an unsaturated bond in one molecule (B2)>
Examples of the compound (B2) having an epoxy group and an unsaturated bond in one molecule include an ethylenically unsaturated monomer having an epoxy group, for example, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and the like. Examples thereof include 2-glycidoxyethyl (meth) acrylate, 3,4 epoxybutyl (meth) acrylate, and 3,4 epoxycyclohexyl (meth) acrylate, which may be used alone or in combination of two or more. It doesn't matter. From the viewpoint of reactivity with unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferable.

<Compound with unsaturated monobasic acid (B4)>
Examples of the unsaturated monobasic acid include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, and cyano-substituted products. Examples thereof include monocarboxylic acids, which may be used alone or in combination of two or more.

<Polybasic acid anhydride (B5)>
Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like, and these may be used alone or in combination of two or more. It doesn't matter. If necessary, such as by increasing the number of carboxyl groups, a tricarboxylic dianhydride such as trimellitic hydride is used, or a tetracarboxylic dianhydride such as pyromellitic dianhydride is used to obtain the remaining anhydride. The group can also be hydrolyzed. Further, when tetrahydrophthalic anhydride or maleic anhydride having a radically polymerizable double bond is used as the polybasic acid anhydride, the radically polymerizable double bond can be further increased.

The double bond equivalent of the resin (b1) is preferably 350 g / mol or more and 1300 g / mol or less, and most preferably 350 g / mol or more and 1000 g / mol or less. If the double bond equivalent of the resin (b1) is larger than 1300 g / mol, the developing speed becomes slow, and even if patterning is possible, the coating film has a large amount of residue. If the double bond equivalent is less than 350 g / mol, the cross-linking component is too large and the stability is poor, or the coating film becomes brittle.

<< Other resin (B6) >>
The photosensitive composition of the present invention may further contain other resins. When the other resin (B6) is a copolymer, a resin containing no radically polymerizable group or a resin containing no alkali-soluble group corresponds to the resin.
As the other resin (B6), a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region is preferable. Other resins include thermoplastic resins, thermosetting resins, and photosensitive resins, which can be used alone or in admixture of two or more.

Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl resin, polyvinyl chloride resin, polyvinylidene chloride resin, vinyl chloride-vinyl acetate copolymer, and poly. Vinyl acetate, polyurethane resin, polyester resin, acrylic resin, methacrylic resin, alkyd resin, polystyrene resin, silicone resin, fluororesin, polyamide resin, rubber resin, cyclized rubber resin, chloride rubber, rubber oxide, hydrochloric acid Examples thereof include rubber, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resin, petroleum resin, casein, cellac, nitrocellulose, cellulose acetate butyrate, etc., but are not necessarily limited thereto.

Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, melamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, rosin-modified maleic acid resin, rosin-modified phenol resin, urea resin, amino resin, phenol resin, and non-residual. Saturated polyester resin, drying oil, synthetic drying oil, and the like can be mentioned, but the present invention is not necessarily limited thereto. It can also be used in combination as a thermal cross-linking agent for the thermoplastic resin.

Photosensitive resins include (meth) acrylic compounds having reactive substituents such as isocyanate groups, aldehyde groups, and epoxy groups in linear polymers having reactive substituents such as hydroxyl groups, carboxyl groups, and amino groups, and Keihi. A resin in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the linear polymer by reacting an acid is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is made of a (meth) acrylic compound having a hydroxyl group such as a hydroxyalkyl (meth) acrylate. Half-esterified products are also used. However, it is not necessarily limited to these.

<Polyfunctional (meth) acrylate monomer (C)>
The photosensitive coloring composition in the present invention contains a polyfunctional (meth) acrylate monomer (C). The polyfunctional (meth) acrylate monomer (C) contains a monomer or an oligomer that is cured by ultraviolet rays, heat, or the like to form a transparent resin.
Among the polyfunctional (meth) acrylate monomers (C), trimethylolpropane triacrylate is preferable because it has excellent chemical resistance. Examples of commercially available products include M-309 (manufactured by Toagosei Co., Ltd.), Viscort # 295 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), and A-TMPT (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).

Other polyfunctional (meth) acrylate monomers (C) include, for example, trimethylolpropane trimethacrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, and ethylene oxide. Examples thereof include various acrylic acid esters such as modified trimethylolpropane tri (meth) acrylate and propylene oxide modified trimethylolpropane tri (meth) acrylate, and methacrylate esters.

Commercially available products include M-350 (trimethylolpropane ethylene oxide-modified triacrylate), M-450 (pentaerythritol tri and tetraacrylate), M-402 (dipentaerythritol penta and hexaacrylate) (all manufactured by Toa Synthetic Co., Ltd.). Examples thereof include Kayarad DPCA30 (caprolactone-modified dipentaerythritol hexaacrylate) (all manufactured by Nippon Kayaku Co., Ltd.).

Further, it is preferable to contain a polyfunctional monomer having an acidic group. For example, an esterified product of a free hydroxyl group-containing poly (meth) acrylate of a polyhydric alcohol and (meth) acrylic acid and a dicarboxylic acid; a polyvalent carboxylic acid. And an esterified product with monohydroxyalkyl (meth) acrylates. Specific examples include monohydroxyoligoacrylates such as trimethylolpropane diacrylate, trimethylolpropanedimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate, or monohydroxyoligomethacrylates. Free carboxyl group-containing monoesteride with dicarboxylic acids such as malonic acid, oxalic acid, glutaric acid, and terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarbaryl acid), butane-1,2,4 -Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, and 2-hydroxyethyl acrylate, 2- Examples thereof include monohydroxymonoacrylates such as hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, and oligoesterides containing a free carboxyl group with monohydroxymonomethacrylates.

Further, a compound represented by the following general formula (18) can also be preferably used.
General formula (18):
(H ₂ C = C (R ₅₁ ) COO) _h -X- (OCOCH (R ₉ ) CH ₂ S (R ₅₀ ) COOH) _i
[In the general formula (18), R ₅₁ is a hydrogen atom or a methyl group, R ₅₀ is a hydrocarbon group having 1 to 12 carbon atoms, X is an (h + i) -valent organic group having 3 to 60 carbon atoms, and h is 2 to 2. An integer of 18 and i indicate an integer of 1 to 3. ]

Here, the compound represented by the general formula (18) can be easily obtained by, for example, the following method.
(1) A method in which a compound giving an organic group represented by X is esterified with acrylic acid to be acrylicized, and then a mercapto compound is added to the obtained compound. (2) A compound giving an organic group represented by X Is modified with a polyisocyanate compound, the obtained compound is acrylicized with an acrylate compound having a hydroxyl group, and then a mercapto compound is added to the obtained compound. (3) An organic group represented by X is given. A method in which a compound is esterified with acrylic acid to be acrylicized, then modified with a polyisocyanate compound, and a mercapto compound is added to the obtained compound.

Examples of the compound giving an organic group represented by X include pentaerythritol, a caprolactone-modified product of pentaerythritol, a polyisocyanate-modified product of pentaerythritol, dipentaerythritol, a caprolactone-modified product of dipentaerythritol, and a polyisocyanate of dipentaerythritol. Modified products can be mentioned.

Examples of the mercapto compound include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, and mercaptosuccinic acid.

The content of the polyfunctional (meth) acrylate monomer (C) is preferably 5 to 40% by weight based on 100% by weight of the total solid content of the photosensitive resin composition. In this case, if the amount of the polyfunctional (meth) acrylate monomer (C) is less than 5% by weight, the effects of increasing the surface hardness and imparting solvent resistance cannot be obtained, and if it is more than 40% by weight, the resolution required for patterning can be obtained. I can't. More preferably, it is 5 to 30% by weight.

<< Photopolymerization Initiator (D) >>
The photosensitive coloring composition of the present invention contains a photopolymerization initiator (D), and the photopolymerization initiator (D) is a carbazole-based oxime compound (D1) having an absorption maximum wavelength in the range of 350 to 400 nm. Is contained as an essential ingredient.
<Carbazole-based oxime compound (D1) having an absorption maximum wavelength in the range of 350 to 400 nm>
Since the component (D1) has an absorption maximum wavelength in the wavelength region of 350 to 400 nm even in the presence of a blue pigment (A1) having a phthalocyanine skeleton or a dye (A2), radicals can be sufficiently generated. .. As a result, the curing of the coating film can be sufficiently advanced.
Further, it is more preferable that the component (D1) has a nitro group.
Examples of such (D1) component include NCI-831 (manufactured by ADEKA Corporation).
The carbazole-based oxime compound (D1) having an absorption maximum wavelength in the range of 350 to 400 nm in the present invention is in an amount of 0.01 to 5% by weight based on 100% by weight of the total solid content of the photosensitive resin composition. It is preferable to use it. In this case, if it is less than 0.01% by weight, the effect of imparting solvent resistance cannot be obtained, and if it is more than 5% by weight, the resolution required for patterning cannot be obtained. More preferably, it is 0.01 to 3% by weight.

Further, the photosensitive coloring composition of the present invention further serves as a photopolymerization initiator (D) at least one of a phenyl-based oxime compound or an acetophenone compound (D2) having an absorption maximum wavelength in the range of 300 to 350 nm. Contains.
<Phenyl-based oxime compound or acetophenone compound (D2) having an absorption maximum wavelength in the range of 300 to 350 nm>
The component (D2) usually cannot sufficiently cure the coating film in the presence of a blue pigment (A1) having a phthalocyanine skeleton or a dye (A2), but it should be used in combination with the component (D1). The curing progresses to the deep part of the coating film, and the chemical resistance becomes very good. (D1) When used alone, the film surface is easily cured, but it is not cured to a deep part and is easily eroded from the end face of the pattern due to chemical immersion. In the present invention, the chemical resistance is not good by using only one of (D1) and (D2), and a synergistic effect is produced by the combined use.
Further, it is preferable that the ratio of (D1) and (D2) used in combination is (D1) / (D2) = 5/95 to 30/70. More preferably, (D1) / (D2) = 5/95 to 20/80, and most preferably (D1) / (D2) = 5/95 to 10/90. If the component (D1) is not contained in a certain amount or more, the coating film does not cure sufficiently. On the other hand, if the component (D1) is used in excess, the color characteristics of the component (D1) itself due to the light absorption performance of the component (D1). This is because it will damage the.
As the component (D2), for example
1,2-Octadione-1- [4- (phenylthio)-, 2- (o-benzoyloxime)], phenyl-based oxime compounds such as etanone, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, Diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] Examples thereof include acetophenone compounds such as -1- [4- (4-morpholinyl) phenyl] -1-butanone.
The phenyl-based oxime compound or acetophenone compound (D2) having an absorption maximum wavelength in the range of 300 to 350 nm in the present invention is 0.1 to 10% by weight based on 100% by weight of the total solid content of the photosensitive resin composition. It is preferable to use the amount of. In this case, if it is less than 0.1% by weight, the effect of imparting solvent resistance cannot be obtained, and if it is more than 10% by weight, the resolution required for patterning cannot be obtained. More preferably, it is 0.5 to 5% by weight.

<Other photopolymerization initiator (D3)>
Other photopolymerization initiators can also be used in combination with the photosensitive coloring composition of the present invention. In particular,
Benzophenones such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone, 4-benzoyl- Benzophenone compounds such as 4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2, Thioxanthone compounds such as 4-diisopropylthioxanthone and 2,4-diethylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-( p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6- Bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloro Methyl (4'-methoxystyryl) -6-triazine, Triazine compounds such as those described in JP-A-59-1281, JP-A-61-9621, JP-A-60-60104, 1,2-octanedione, 1- [4- (Phenylthio) phenyl-, 2- (O-benzoyloxime)], JP-A-2001-264530, JP-A-2001-261716, JP-A-2000-80068, JP-A-2001-233842, JP-A-2004-534977, Open 2006-342166, JP-A-2008-09470, JP-A-2009-40762, JP-A-2010-15025, JP-A-2010-189279, JP-A-2010-189280, Special Table 2010-526846, Special Table 2010-527338, Special Table 2010 -527339, USP3558309 (1971), USP4202697 (1980), Japanese Patent Application Laid-Open No. 61-245 58, Oxym ester compounds such as the compounds described in Japanese Patent Application Laid-Open No. 2012-516191, Special Table 2012-526185, Special Table 2013-543875, Japanese Patent Application Laid-Open No. 2011-209710, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide. , 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and other phosphine compounds, 2,2'-bis (o-chlorophenyl) -4,5,4', 5'-tetraphenyl-1,2'- Biimidazole, 2,2'-bis (o-methoxyphenyl) -4,4', 5,5'-tetraphenyl biimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5, 5'-tetra (p-methylphenyl) biimidazole, imidazole compounds such as the compounds described in JP-A-55-127550 and JP-A-60-202437, 9,10-phenanthrene quinone, camphorquinone, ethylanthraquinone. Kinone-based compounds such as JP-A-2-157760, carbazole-based compounds, titanosen-based compounds such as compounds described in JP-A-61-151197, JP-A-59-1504, JP-A. Organic peroxides such as the compounds described in 61-243807, diazonium compounds such as the compounds described in Japanese Patent Publication No. 43-23684, Japanese Patent Publication No. 44-6413, Japanese Patent Publication No. 47-1604, USP No. 3567453, USP No. 2848328. No., USP 2852379, USP 2940853, and other organic azide compounds, Tokusho 36-22062, Tokusho 37-13109, Tokukou 38-18015, Tokukou 45-9610. Ortho-quinone diazides such as the compounds described in the above, Japanese Patent Application Laid-Open No. 55-39162, JP-A-59-140203, "MACROMOLECULES", Vol. 10, p. 1307 (1977). Various onium compounds including, azo compounds such as the compounds described in JP-A-59-142205, JP-A-1-54440, European Patent No. 109851, European Patent No. 126712, "Journal. Of Imaging Science (J. IMAG. SCI. ) ”, Vol. 30, pp. 174 (1986), metal allen complexes such as compounds,“ Coordination Chemistry Review ”, Vol. 84, pp. 85-277 (1988). ), Transition metal complexes containing transition metals such as ruthenium described in JP-A-2-182701, aluminate complexes such as compounds described in JP-A-3-209477, carbon tetrabromide and JP-A-59-107344. Examples thereof include organic halogen compounds such as the above compounds, sulfonium complexes and oxosulfonium complexes described in JP-A-5-255347.

These photopolymerization initiators (D) can be used alone or in admixture of two or more at any ratio, if necessary. The photopolymerization initiator (D) is preferably 0.01 to 60 parts by mass, more preferably 0.01 to 10 parts by mass, and even more preferably 0. It is 03 to 7 parts by mass. From the viewpoint of photopolymerizability, that is, the progress of the polymerization reaction, it is preferably 0.01 part by mass or more, suppressing the decrease in transparency due to the influence of yellowing of the initiator, and the pattern resolution due to excessive photopolymerization during exposure. It is preferably 10 parts by mass or less from the viewpoint of suppressing the decrease in the amount of light.

Further, the photosensitive coloring composition of the present invention may contain a sensitizer. As a sensitizer, for example
Unsaturated ketones such as chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene. Polymethine dyes such as derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives, acrydin derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indolin derivatives,
Azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative , Naphthalocyanine derivative, Subphthalocyanine derivative, Pyrylium derivative, Thiopyrylium derivative, Tetraphyllin derivative, Anurene derivative, Spiropyran derivative, Spiroxazine derivative, Thiospiropirane derivative, Metal allene complex, Organic ruthenium complex, Michler ketone derivative, Biimidazole derivative and the like. Be done.

More specific examples include Nobu Ogawara et al., "Dye Handbook" (1986, Kodansha), Nobu Ogawara et al., "Chemistry of Functional Dyes" (1981, CMC), Chuzaburo Ikemori et al., "
Examples thereof include, but are not limited to, the sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet to the near infrared region can also be contained. The sensitizer may contain two or more kinds of sensitizers in an arbitrary ratio.

The sensitizer is preferably used in an amount of 0.1 to 150 parts by mass, preferably 1 to 100 parts by mass, based on 100 parts by mass of the photopolymerization initiator (D) in the photosensitive coloring composition. Is more preferable.

<< Other materials >>
In the photosensitive coloring composition of the present invention, the following materials can be further added as long as the object of the invention is not impaired.

<Organic solvent>
An organic solvent may be used to improve the handling when the photosensitive coloring composition is applied. For example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, benzene, toluene, ethyl benzene. , Xylene, cyclohexane, hexane, octane, cyclolomethane, chloroform, dimethylformamide, dimethylacetamide, acetonitrile, dimethylsulfoxide, and the like. These can be used alone or in combination of two or more.
Above all, it is preferable to use a ketone-based, ester-based, or ether-based solvent because the solubility of other components is good.

The amount of the organic solvent used is preferably such that the solid content concentration of the photosensitive coloring composition is 5 to 50% by mass. By setting the solid content concentration of the photosensitive coloring composition in such a range, it is possible to provide a film or a fine pattern having a more uniform thickness and high smoothness. That is, when the solid content concentration is 50% by mass or less, it is preferable from the viewpoint of leveling property when the photosensitive composition is applied, smoothness of the obtained film or fine pattern, and transparency, while the solid content concentration. When is 5% by mass or more, a film and a pattern having a predetermined thickness can be easily obtained.

When a colorant is added to the photosensitive coloring composition of the present invention to obtain a photosensitive coloring composition for a color filter described later, and a color filter segment or a black matrix is produced, it is dried on a transparent substrate such as a glass substrate or a film substrate. Apply so that the film thickness is 0.2 to 10 μm. Organic solvents are used to facilitate this, for example 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1, 4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexene-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate , 3-Methyl-1,3-butanol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m -Xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-Chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol di Butyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotersial butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether , Ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol,
Cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, Tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether , Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester, etc. Is preferably used. These can be used alone or in combination.

In particular, considering the drying property of the organic solvent, it is preferable to contain a high boiling point solvent of 160 ° C. or higher in the die coating method, the screen printing method, the offset printing method, the gravure printing method and the like. For example, 3-methoxy-3-methyl- 1-butanol (bp 174 ° C), 1,3-butanediol (bp 203 ° C), 3-methyl-1,3-butanediol (bp 203 ° C), 2-methyl-1,3-propanediol (bp 213 ° C), diisobutyl Ketone (bp168.
1 ° C.), ethylene glycol monobutyl ether (bp171.2 ° C.), ethylene glycol monohexyl ether (bp208.1 ° C.), ethylene glycol monobutyl ether acetate (bp191.5 ° C.), ethylene glycol dibutyl ether (bp203).
.. 3 ° C.), Diethylene glycol monomethyl ether (bp194.0 ° C.), Diethylene glycol monoethyl ether (bp202.0 ° C.), Diethylene glycol diethyl ether (bp188.4 ° C.), Diethylene glycol monoisopropyl ether (bp2).
07.3 ° C), propylene glycol monobutyl ether (bp170.2 ° C), propylene glycol diacetate (bp190.0 ° C), dipropylene glycol monomethyl ether (bp187.2 ° C), dipropylene glycol monoethyl ether (bp19)
7.8 ° C.), Dipropylene glycol monopropyl ether (bp 212.0 ° C.), Dipropylene glycol dimethyl ether (bp 175 ° C.), Tripropylene glycol monomethyl ether (bp 206.3 ° C.), Ethyl 3-ethoxypropionate (bp 169.).
7 ° C.), 3-Methoxybutyl acetate (bp172.5 ° C.), 3-Methoxy-3-methylbutyl acetate (bp188 ° C.), γ-butyrolactone (bp204 ° C.), N, N-
Dimethylacetamide (bp166.1 ° C), N-methylpyrrolidone (bp202 ° C),
p-chlorotoluene (bp 162.0 ° C), o-diethylbenzene (bp 183.4 ° C)
, M-diethylbenzene (bp181.1 ° C), p-diethylbenzene (bp183.8)
℃), o-dichlorobenzene (bp180.5 ℃), m-dichlorobenzene (bp173)
.. 0 ° C.), n-butylbenzene (bp183.3 ° C.), sec-butylbenzene (bp1)
78.3 ° C.), tert-butylbenzene (bp169.1 ° C.), cyclohexanol (78.3 ° C.), cyclohexanol (
bp161.1 ° C.), cyclohexyl acetate (bp173 ° C.), methylcyclohexanol (bp174 ° C.) and the like, and the high boiling point solvent of 160 ° C. or higher is preferably 5 to 50% by mass based on the total amount of the solvent.

The organic solvent is preferably used in an amount of 100 to 10000 parts by mass, preferably 500 to 5000 parts by mass with respect to 100 parts by mass of the colorant in the photosensitive coloring composition for a color filter.

<Multifunctional thiol>
The photosensitive coloring composition of the present invention can contain a polyfunctional thiol. A polyfunctional thiol is a compound having two or more thiol (SH) groups.
When the polyfunctional thiol is used together with the above-mentioned photopolymerization initiator (D), it acts as a chain transfer agent in the radical polymerization process after light irradiation and generates chile radicals that are less susceptible to polymerization inhibition by oxygen. The sex coloring composition has high sensitivity.
In particular, a polyfunctional aliphatic thiol in which the SH group is bonded to an aliphatic group such as methylene or ethylene group is preferable.
For example, hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tris. Thioglycolate, trimethylolpropane tristhiopropionate, trimethylolethanetris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate)
3-Mercaptobutyrate), Trimethylol Propanthris (3-Mercaptopropionate), Pentaerythritol Tetrakisthioglycolate, Pentaerythritol Tetrakisthiopropionate, Pentaerythritol Tetrakis (3-Mercaptopropionate), Dipentaerythritol Hexakis (3-mercaptopropionate), tristrimercaptopropionate (2-hydroxyethyl) isocyanurate, 1,4-
Dimethyl mercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N)
, N-dibutylamino) -4,6-dimercapto-s-triazine and the like.
These polyfunctional thiols can be used alone or in admixture of two or more.

The content of the polyfunctional thiol is preferably 0.05 to 100 parts by mass, more preferably 1.0 to 50.0 parts by mass with respect to 100 parts by mass of the colorant. Better development resistance can be obtained by using 0.05 parts by mass or more of polyfunctional thiol. By using a thiol having a plurality of thiol (SH) groups, development resistance can be improved.

<UV absorber or polymerization inhibitor>
The photosensitive coloring composition of the present invention may contain an ultraviolet absorber or a polymerization inhibitor. By containing an ultraviolet absorber or a polymerization inhibitor, the shape and resolution of the pattern can be controlled.
Examples of the ultraviolet absorber include 2- [4-[(2-hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2).
, 4-Dimethylphenyl) -1,3,5-triazine, 2- (2-Hydroxy-4- [1
-Hydroxyphenyltriazines such as −octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2H-benzotriazole-2)
-Il) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (3-t)
Benzophenones such as butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2', 4,4'- Benzophenone such as tetrahydroxybenzophenone, phenylsalicylate, salicylate such as p-tert-butylphenylsalicylate, cyanoacrylate such as ethyl-2-cyano-3,3'-diphenylacrylate, 2,2 6,6,-Tetramethylpiperidin-1-oxyl (triacetone-amine-N-oxyl), bis (2,2,6,6-tetramethyl-4-piperidyl)
-Sebacate, poly [[6-[(1,1,3,3-tetrabutyl) amino] -1,3,5
-Triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidinyl) imino] and other hindered amines are mentioned, and these are used alone or in combination.
Examples of the polymerization inhibitor include methyl hydroquinone, t-butyl hydroquinone, 2,
5-di-t-butylhydroquinone, 4-benzoquinone, 4-methoxyphenol, 4-
Hydroquinone derivatives and phenolic compounds such as methoxy-1-naphthol, t-butylcatechol, phenothiazine, bis- (1-dimethylbenzyl) phenothiazine, 3
, Amine compounds such as 7-dioctylphenothiazine, copper and manganese salt compounds such as copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, manganese diphenyldithiocarbamate, 4-nitrosophenol, N-nitrosodiphenylamine, N-nitroso Examples thereof include nitroso compounds such as cyclohexyl hydroxylamine and N-nitrosophenyl hydroxylamine, and ammonium salts or aluminum salts thereof, which are used alone or in combination.

The amount of the ultraviolet absorber and the polymerization inhibitor is preferably 0.01 to 20 parts by mass, and more preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the colorant in the photosensitive coloring composition.
Better resolution can be obtained by using 0.01 part by mass or more of the ultraviolet absorber or the polymerization inhibitor.

<Storage stabilizer>
The photosensitive coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Examples of the storage stabilizer include 2,6-bis (1,1-dimethylethyl) -4-methylphenol and pentaerythtyryl-tetrax [3- (3,5-di-t-butyl-4-hydroxyphenyl). Propionate], hindered phenols such as 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) 1,3,5-triazine, tetraethylphosphine, tri Organic phosphine such as phenylphosphine and tetraphenylphosphine, phosphite such as zinc dimethyldithiophosphate, zinc dipropyldithiophosphate, molybdenum dibutyldithiophosphate, sulfur such as dodecylsulfide and benzothiophene, benzyltrimethyl chloride, Examples thereof include quaternary ammonium chloride such as diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, which are used alone or in combination.

The storage stabilizer is preferably used in an amount of 0.01 to 20 parts by mass, more preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the colorant in the photosensitive coloring composition.

<Adhesion improver>
It is preferable that the photosensitive coloring composition of the present invention contains an adhesion improver such as a silane coupling agent in order to enhance the adhesion to the transparent substrate. Adhesion improvers include vinyl trichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxy. Propylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane , 3-Methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltri Methoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl) − Butylidene) Propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltriethoxysilane, 3 -Propylpropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyandiapropyltriethoxysilane and the like can be mentioned.
Above all, it is preferable to include a silane-based additive because the adhesion with a glass substrate or the like is improved.
3-Methylmethacryloxypropyltrimethoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane are particularly preferable.

The silane coupling agent is preferably used in an amount of 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the colorant in the photosensitive coloring composition.

<Leveling agent>
It is preferable to add a leveling agent to the photosensitive coloring composition of the present invention in order to improve the leveling property of the composition on the transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of the dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning Co., Ltd. and BYK-330 manufactured by Big Chemie Co., Ltd. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by Big Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can also be used in combination.

A particularly preferable leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a hydrophilic group but has low solubility in water and is added to a photosensitive pigment composition. , It has a feature of low surface tension lowering ability, and it is useful to have good wettability to the glass plate despite its low surface tension lowering ability, and addition that does not cause defects in the coating film due to foaming. Those capable of sufficiently suppressing chargeability in terms of amount can be preferably used.
As a leveling agent having such preferable properties, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. The polyalkylene oxide unit includes a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the polyalkylene oxide unit is bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane. It may be any of the linear block copolymer types that are alternately and repeatedly bonded. Didimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130.
, FZ-2166, FZ-2191, FZ-2203, FZ-2207.
It is not limited to these.

Anionic, cationic, nonionic, or amphoteric surfactants can be added as an adjunct to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants to be added as an auxiliary to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalin sulfonate, and alkyldiphenyl ether disulfonic acid. Sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate,
Examples thereof include sodium stearate, sodium lauryl sulfate, monoethanolamine of a styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphoric acid ester.

Examples of the chaotic surfactant added as a supplement to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. Nonionic surfactants to be added as a supplement to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, and polyoxyethylene sorbitan monostearate. , Polyethylene glycol monolaurate and the like; alkyl betaines such as alkyldimethylaminoacetic acid betaine, amphoteric surfactants such as alkylimidazoline, and fluorine-based and silicone-based surfactants.

<Amine compounds>
It is preferable that the photosensitive composition for a color filter contains an amine compound having a function of reducing dissolved oxygen. Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminobenzoate. Examples thereof include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine and the like.

<Others>
If necessary, additives such as a curing agent, a light stabilizer, an antioxidant, an inorganic filler, an adhesive-imparting agent, and a surfactant used in combination with the thermosetting resin may be added. Any amount of these additives can be added as long as the purpose of the resin composition is not impaired.

<< Manufacturing method of photosensitive coloring composition >>
The photosensitive coloring composition of the present invention requires a colorant (A), an alkali-soluble resin (B) having a radically polymerizable group, a polyfunctional (meth) acrylate monomer (C), and a photopolymerization initiator (D). It can be produced by mixing and stirring with other components according to the above.

When the photosensitive coloring composition of the present embodiment is used as a color filter or the like, coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0, are used by means such as centrifugation, sintering filter, and membrane filter. It is preferable to remove coarse particles of .5 μm or more, mixed dust, and foreign matter.

<Manufacturing method of photosensitive coloring composition for color filter>
One aspect of the present invention relates to a photosensitive coloring composition for a color filter. Since the photosensitive coloring composition for a color filter contains a colorant, photocuring is difficult to proceed, and the problem that chemical resistance and photolithography are in a trade-off relationship is particularly remarkable. In particular, when low-temperature curing is desired, it is difficult to achieve both excellent chemical resistance and photolithography. According to the photosensitive composition for a color filter of the present embodiment, both chemical resistance and photolithography can be achieved even under low temperature curing conditions.
When a colorant is added to the photosensitive coloring composition of the present invention and used as a photosensitive coloring composition for a color filter, it can be prepared in the form of a solvent-developed or alkali-developed colored resist material. The photosensitive coloring composition disperses the coloring agent in a composition containing an alkali-soluble resin (B) having a radically polymerizable group, a polyfunctional (meth) acrylate monomer (C), and a photopolymerization initiator (D). It was made to. The photosensitive coloring composition for a color filter uses various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, and an attritor in a pigment carrier such as a resin and / or a solvent for a colorant such as a pigment or a dye. A pigment dispersion is produced by finely dispersing the pigment dispersion, and the pigment dispersion contains an alkali-soluble resin (B) having a radically polymerizable group, a polyfunctional (meth) acrylate monomer (C), and a photopolymerization initiator (D). ), An organic solvent, and in some cases, a silane compound, a sensitizer, a polyfunctional thiol, an ultraviolet absorber, a polymerization inhibitor, a storage stabilizer, and other components can be mixed and stirred. Further, the photosensitive coloring composition containing two or more kinds of pigments is an alkali-soluble resin in which each pigment dispersion is separately mixed in a dye carrier and / or a solvent and further has a radically polymerizable group. It can be produced by mixing and stirring (B), a polyfunctional (meth) acrylate monomer (C), a photopolymerization initiator (D), an organic solvent, and the like.
The alkali-soluble resin (B) and the polyfunctional (meth) acrylate monomer (C) having a radically polymerizable group may be used as a dye carrier in producing a pigment dispersion.

When the pigment is dispersed in a pigment carrier such as a resin and / or a solvent, a dispersion aid such as a resin-type pigment dispersant, a surfactant, or a pigment derivative can be appropriately contained. Dispersion aid is
Since the pigment is excellently dispersed and the effect of preventing the reaggregation of the pigment after dispersion is great, a photosensitive coloring composition for a color filter obtained by dispersing the pigment in a resin and / or a solvent using a dispersion aid is used. If so, a color filter having excellent transparency can be obtained.
The dispersion aid is preferably used in an amount of 0.1 to 40 parts by mass, more preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the pigment.

The resin-type pigment dispersant has a pigment-affinitive portion having a property of adsorbing to the pigment and a portion compatible with the pigment carrier, and has a function of adsorbing to the pigment and stabilizing the dispersion of the pigment on the pigment carrier. To do. Specific examples of the resin-type pigment dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products of these, amides formed by the reaction of poly (lower alkyleneimine) with polyesters having free carboxyl groups, and their amides. Oily dispersants such as salts, (meth) acrylic acid-
Styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, water-soluble resin such as polyvinyl alcohol and polyvinylpyrrolidone, water-soluble polymer compound, polyester-based, modified Polyacrylate-based, ethylene oxide / propylene oxide-added compound, phosphoric acid ester-based, etc. are used, and these can be used alone or in admixture of two or more.

As a commercially available resin-type dispersant, Disperbyk-1 manufactured by Big Chemie Japan Co., Ltd.
01, 103, 107, 108, 110, 111, 116, 130, 140, 154, 1
61, 162, 163, 164, 165, 166, 170, 171, 174, 180, 1
81, 182, 183, 184, 185, 190, 2000, 2001, 2020, 20
25, 2050, 2070, 2095, 2150, 2155 or Anti-Terra
-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykuman, etc., SOLPERSE-3000, 9000, 13000, 13240, 13 manufactured by Japan Lubrizol.
650, 13940, 16000, 17000, 18000, 20000, 21000,
24000, 26000, 27000, 28000, 31845, 32000, 3250
0, 32550, 33500, 32600, 34750, 35100, 36600, 38
500, 41000, 41090, 53095, 55000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 40 manufactured by Ciba Japan
15, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 44
01, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 43
30, 4340, 450, 451, 453, 4540, 4550, 4560, 4800,
5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 1
Ajinomoto Fine Techno's Ajispar PA such as 50, 1501, 1502, 1503, etc.
111, PB711, PB821, PB822, PB824 and the like can be mentioned.

Examples of the surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalin sulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, and lauryl. Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate; polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxy Nonionic surfactants such as ethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; alkyl 4
Chaotic surfactants such as quaternary ammonium salts and their ethylene oxide adducts; alkyl betaines such as alkyldimethylaminoacetic acid betaine and amphoteric surfactants such as alkylimidazolines, which may be used alone or in admixture of two or more. Can be used.

The pigment derivative is a compound in which a substituent is introduced into an organic pigment, and the organic pigment also includes a pale yellow aromatic polycyclic compound such as naphthalene-based or anthraquinone-based, which is not generally called a pigment. Examples of pigment derivatives include JP-A-63-305173 and JP-A-57-156.
No. 20, Gazette No. 59-40172, Gazette No. 63-17102, Gazette No. 5
Those described in Japanese Patent Application Laid-Open No. -9469 can be used, and these can be used alone or in combination of two or more.

<Step of obtaining a coating film by applying a photosensitive composition on a substrate>
The method of applying the photosensitive composition of the present invention to a glass substrate, ITO, a metal film, an organic film or the like is not particularly limited, and for example, a dipping method, a spray method, a roll coating method, a die coating method, a rotary coating method, etc. Etc. can be used, and in addition, it can be applied by a printing method such as a screen printing method, an offset printing method, or a gravure printing method. Patterns can also be formed by photolithography. Examples of the base material include glass, ceramic, polycarbonate, polyester, urethane, acrylic, polyacetate cellulose, polyamide, polyimide, polystyrene, epoxy resin, polyolefin, polycycloolefin, and polyvinyl. Examples include various metals such as alcohol and stainless steel.
The thickness of these display members when manufactured is preferably 0.005 to 30 μm in a dry state, more preferably 0.01 to 20 μm, and particularly preferably 0.1 to 10 μm. preferable. By setting the thickness in such a range, appropriate mechanical strength and heat resistance can be obtained, and there is little possibility that the light transmittance is impaired.

The drying method after applying the photosensitive composition of the present invention to the substrate is not particularly limited, and may be changed depending on the type of each component used in the photosensitive composition, the addition amount (blending amount), and the like. it can. For example, a vacuum dryer, an oven, an infrared heater, or the like can be used. In order to perform negative photolithography, it is preferable to use a vacuum dryer that is not heated during drying so as not to deteriorate the developability of the unexposed portion. When heating using an oven, an infrared heater, or the like, it is preferable to dry at a temperature of 40 to 80 ° C. for 1 minute to 1 hour.

<After step (i), the step of exposing the coating film with ultraviolet rays via a mask>
It is preferable to use a light source such as a high-pressure mercury lamp, a low-pressure mercury lamp, an electrodeless lamp, a xenon lamp, a metal halide lamp, or an excimer lamp for irradiating ultraviolet rays.
The photocuring method is also not particularly limited, but for example, it is possible to irradiate ultraviolet rays using a high-pressure mercury lamp, a metal halide lamp, or the like as a light source. The irradiation conditions can also be changed depending on the type of each component used in the photosensitive composition, the amount added (blending amount), etc., but the irradiation amount of ultraviolet rays is usually 10 to 500 mJ / cm ^2. Preferably, 20 to 300 mJ / cm ² is more preferable.

<Step of obtaining a pattern by developing the exposed coating film with an alkaline developer after step (ii)>
The development can be carried out by immersing in a solvent or an alkaline developer, or by spraying the developer with a spray or the like to remove the uncured portion and form a desired fine pattern. An aqueous solution of sodium carbonate, sodium hydroxide or the like is used as the alkaline developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developing solution.
As the development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid filling) development method and the like can be applied.

<Step of post-baking the pattern at 80 ° C to 150 ° C after step (iii)>
Although it is necessary to change the thermosetting temperature after photo-curing depending on the heat resistance of the base material used and other optical materials, photopolymerization in the alkali-soluble resin (A) and the photopolymerizable compound (B) is possible as much as possible. It is preferable to raise the temperature of the sex functional groups that remain unreacted in the photocuring step to a temperature at which the cross-linking reaction occurs, and the temperature is in the range of 80 to 150 ° C, more preferably in the range of 80 ° C to 120 ° C. More preferably, it is heat-cured in the range of 80 ° C. to 100 ° C. under the condition of 0.1 to 10 hours.

<Manufacturing method of color filter>
A method for producing a color filter using the photosensitive coloring composition for a color filter of the present invention will be described.
A color filter comprises a filter segment or a black matrix formed from a photosensitive coloring composition for a color filter on a transparent substrate, and a general color filter has at least one red filter segment and at least one green color. It comprises a filter segment and at least one blue filter segment, or at least one magenta color filter segment, at least one cyan color filter segment, and at least one yellow color filter segment.

According to the photolithography method, a filter segment and a black matrix with higher accuracy than printing methods such as a screen printing method, an offset printing method, and a gravure printing method can be formed. Each color filter segment and black matrix are formed by the photolithography method by the following method. That is, a photosensitive coloring composition for a color filter prepared as a solvent-developed or alkali-developed colored resist material is applied onto a transparent substrate by a spray coating, spin coating, slit coating, roll coating, or other coating method to achieve a dry film thickness. Apply so that the value is 0.2 to 10 μm. If necessary, the dried film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact with or without contact with the film.
After that, the filter segment and the black matrix can be formed by immersing in a solvent or an alkaline developer, or spraying the developer with a spray or the like to remove the uncured portion and form a desired pattern.
Further, in order to impart chemical resistance to the filter segment and the black matrix formed by the development, thermosetting is performed.

As the transparent substrate, a glass plate such as soda-lime glass, low-alkali borosilicate glass, or non-alkali aluminum borosilicate glass, or a resin plate such as polycarbonate, polymethylmethacrylate, or polyethylene terephthalate is used. Further, on the surface of the glass plate or the resin plate, a transparent electrode made of indium oxide, tin oxide or the like may be formed for driving the liquid crystal after the panelization.

The dry film thickness of the filter segment and the black matrix is preferably 0.2 to 10 μm, more preferably 0.2 to 5 μm.

When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate or the like may be used. The drying conditions can be changed depending on the type of each component used in the photosensitive composition for color filters, the amount added (blending amount), etc., but in order to perform negative photolithography, the unexposed portion is developed. It is preferable to use a vacuum dryer that is not heated during drying so as not to deteriorate the properties. When heating using an oven, an infrared heater, or the like, it is preferable to dry at a temperature of 40 to 80 ° C. for 1 minute to 1 hour.
From the viewpoint of suppressing the generation of development residue due to cross-linking of the photosensitive composition, the heating temperature is preferably 6.
It is 0 ° C. or lower, more preferably 50 ° C. or lower.

At the time of development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as the alkaline developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developing solution.
As the development processing method, shower development method, spray development method, dip (immersion) development method,
A paddle (liquid filling) development method or the like can be applied.

In order to increase the UV exposure sensitivity, a photosensitive coloring composition for a color filter is applied and dried, and then a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to prevent polymerization inhibition by oxygen. It is also possible to perform ultraviolet exposure after forming the film.

<Organic EL display device>
The organic EL display device in the present invention is a display device having a color filter formed by the photosensitive coloring composition of the present embodiment and a white light emitting organic EL element (hereinafter referred to as an organic EL element) as a light source. preferable.

(Organic EL element (white light emitting organic EL element))
The organic EL element used in the present invention has a wavelength of at least 430 nm to 485 n.
Peak wavelength (λ) at which the emission intensity is maximized in the range of m and the wavelength range of 560 nm to 620 nm.
_{1), (λ 2)} has a light emission intensity _{I 2} in the light-emitting intensity _{I 1} and the wavelength lambda ₂ at a wavelength lambda ₁
The ratio (I ₂ / I ₁ ) is preferably 0.4 or more and 0.9 or less, and more preferably 0.5 or more and 0.8 or less. Particularly preferably, it is 0.5 or more and 0.7 or less.
When the ratio of emission intensity I _{2 (I 2} / I ₁ ) has an emission spectrum of 0.4 or more and 0.9 or less, high brightness and wide color reproducibility can be obtained, which is preferable.

Further, it is preferable to have a maximum value of emission intensity or a shoulder in the wavelength range of 530 nm to 650 nm.
The wavelength range of 430 nm to 485 nm is preferable when a color display device including the color filter displays blue with good color reproducibility. More preferably from 430 nm
It is in the range of 475 nm.
By using an organic EL element satisfying these configurations and the color filter, a color display device having a wide color reproduction region and high brightness can be obtained.

An organic EL device is composed of a device in which a single layer or a multi-layered organic layer is formed between an anode and a cathode. Here, the single-layer organic EL element refers to an element composed of only a light emitting layer between the anode and the cathode, while the multi-layer organic EL element includes holes in the light emitting layer in addition to the light emitting layer. Hole injection layer, hole transport layer, hole blocking layer, electron injection for the purpose of facilitating the injection of electrons and facilitating the recombination of holes and electrons in the light emitting layer. Refers to a stack of layers and the like. Therefore, typical element configurations of the multilayer organic EL element are (1) anode / hole injection layer / light emitting layer / cathode, and (2) anode / hole injection layer / hole transport layer / light emitting layer / cathode. , (3) Electron / hole injection layer / light emitting layer / electron injection layer / cathode, (4) anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode, (5) anode / positive Hole injection layer / light emitting layer / hole blocking layer / electron injection layer / cathode, (6
) Anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron injection layer / cathode, (7) anode / light emitting layer / hole blocking layer / electron injection layer / cathode, (8) anode An element configuration in which layers are laminated such as / light emitting layer / electron injection layer / anode is mentioned. However, the organic EL element used in the present invention is not limited to these.

Further, each of the above-mentioned organic layers may be formed by a layer structure of two or more layers, or several layers may be repeatedly laminated. As such an example, in recent years, for the purpose of improving light extraction efficiency, "multi-photons" in which some layers of the above-mentioned multi-layer organic EL element are multi-layered.
An element configuration called "emission" has been proposed. This is, for example, in an organic EL device composed of a glass substrate / anode / hole transport layer / electron transporting light emitting layer / electron injection layer / charge generating layer / light emitting unit / cathode, of the charge generating layer and the light emitting unit. A method of laminating a plurality of layers of the portions can be mentioned.

First, the materials that can be used for each of these layers will be specifically illustrated. However, the materials that can be used in the present invention are not limited to these.

As a material that can be used for the hole injection layer, a phthalocyanine compound is effective, and copper phthalocyanine (abbreviation: CuPc), vanadyl phthalocyanine (abbreviation: VOPc) and the like can be used. In addition, there is also a material in which a conductive polymer compound is chemically doped, and polyethylene dioxythiophene (abbreviation: PEDOT) is mixed with polystyrene sulfonic acid (abbreviation: P).
A material doped with SS), polyaniline (abbreviation: PANI), or the like can also be used.
In addition, thin films of inorganic semiconductors such as molybdenum oxide (abbreviation: MoO _x ), vanadium oxide (abbreviation: VO _x ), nickel oxide (abbreviation: NiO _x ), and inorganic insulation such as _{aluminum oxide (abbreviation: Al 2} O _3). Ultra-thin films of the body are also effective. In addition, 4,4', 4''-tris (N, N-diphenyl-amino) -triphenylamine (abbreviation: TDATA), 4,4', 4''-tris [
N- (3-Methylphenyl) -N-Phenyl-Amino] -Triphenylamine (abbreviation: MT)
DATA), N, N'-bis (3-methylphenyl) -N, N'-diphenyl-1,1'
-Biphenyl-4,4'-diamine (abbreviation: TPD), 4,4'-bis [N- (1-naphthyl) -N-phenyl-amino] -biphenyl (abbreviation: α-NTPD), 4,4' -Bis [N
Aromatic amine compounds such as − (4- (N, N-di-m-tolyl) amino) phenyl-N-phenylamino] biphenyl (abbreviation: DNTPD) can also be used. Further, a substance exhibiting acceptability for these aromatic amine compounds may be added to the aromatic amine compounds, and specifically, 2,3,5,6-tetrafluoro-, which is an acceptor for VOPc.
Addition of 7,7,8,8-tetracyanoquinodimethane (abbreviation: F4-TCNQ),
You may use α-NPD to which MoO _{x which is an acceptor is added.}

As a material that can be used for the hole transport layer, an aromatic amine compound is suitable.
TDATA, MTDATA, TPD, α-NPD, DNTPD and the like described in the hole injection material can be used.

As an electron transporting material that can be used for the electron transporting layer, Tris (8-quinolinolato)
Aluminum (abbreviation: Alq3), Tris (4-methyl-8-quinolinolato) Aluminum (abbreviation: Almq3), Bis (10-hydroxybenzo [h] -quinolinato) Beryllium (
Abbreviation: BeBq2), bis (2-methyl-8-quinolinolato) (4-phenylphenolato)
Aluminum (abbreviation: BAlq), bis [2- (2-hydroxyphenyl) benzoxazolate] zinc (abbreviation: Zn (BOX) 2), bis [2- (2-hydroxyphenyl) benzothiazolate] zinc (abbreviation: Zn) Examples thereof include metal complexes such as (BTZ) 2). Furthermore, in addition to the metal complex, 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,
3,4-Oxadiazole (abbreviation: PBD), 1,3-bis [5- (p-tert-butylphenyl) -1,3,4-oxadiazole-2-yl] benzene (abbreviation: OXD- Oxadiazole derivatives such as 7), 3- (4-tert-butylphenyl) -4-phenyl-
5- (4-biphenylyl) -1,2,4-triazole (abbreviation: TAZ), 3- (4-te
rt-Butylphenyl) -4- (4-ethylphenyl) -5- (4-biphenylyl) -1
, 2,4-Triazole derivatives such as triazole (abbreviation: p-EtTA Z), 2,2'
, 2 "-(1,3,5-benzenetriyl) Tris [1-phenyl-1H-benzimidazole] (abbreviation: TPBI) and other imidazole derivatives, basophenanthroline (abbreviation: B)
Phenanthroline derivatives such as Phen) and vasocuproin (abbreviation: BCP) can be used.

Examples of the materials that can be used for the electron injection layer include Alq3 and Almq3 described above.
BeBq2, BAlq, Zn (BOX) ₂ , Zn (BTZ) ₂ , PBD, OXD-7, T
Electron transport materials such as AZ, p-EtTAZ, TPBI, BPhen, BCP can be used. In addition, ultra-thin films of insulators such as alkali metal halides such as LiF and CsF, alkaline earth halides such as _{CaF 2 , and alkali metal oxides such as Li 2 O are often used.} In addition, lithium acetylacetone (abbreviation: Li (acac))
Alkali metal complexes such as 8-quinolinolato-lithium (abbreviation: Liq) are also effective. Further, a substance exhibiting donor property with respect to these electron injection materials may be added to the electron injection material.
As the donor, an alkali metal, an alkaline earth metal, a rare earth metal, or the like can be used. Specifically, a BCP to which lithium as a donor is added, or an Alq ₃ to which lithium as a donor is added can be used.

Further, as the hole blocking layer, a hole blocking material that can prevent holes that have passed through the light emitting layer from reaching the electron injection layer and can form a layer having excellent thin film forming property is used. Examples of such hole blocking materials include aluminum complex compounds such as bis (8-hydroxyquinolinate) (4-phenylphenolate) aluminum and bis (2-methyl-8-hydroxyquinolina). -G)
(4-Phenylphenolate) gallium complex compound such as gallium, 2,9-dimethyl-4
, 7-Diphenyl-1,10-Phenanthroline (abbreviation: BCP) and other nitrogen-containing condensed aromatic compounds.

The light emitting layer that obtains white light emission is not particularly limited, and for example, the following can be used. That is, an element that defines the energy level of each layer of the organic EL laminated structure and emits light by using tunnel injection (European Patent No. 0390551), and a white light emitting element as an example of an element that also uses tunnel injection. Described (Japanese Patent Laid-Open No. 3-2305
No. 84), a light emitting layer having a two-layer structure (Japanese Patent Laid-Open No. 2-220390 and Japanese Patent Application Laid-Open No. 2-216790), the light emitting layer is divided into a plurality of materials having different emission wavelengths. Constructed (Japanese Patent Laid-Open No. 4-51491), blue illuminant (fluorescent peak 3)
80 to 480 nm) and a green light emitter (480 to 580 nm) are laminated, and a red phosphor is further contained (Japanese Patent Laid-Open No. 6-207170). The blue light emitting layer contains a blue fluorescent dye. Examples thereof include a green light emitting layer having a region containing a red fluorescent dye and further containing a green fluorescent substance (Japanese Patent Laid-Open No. 7-142169).

Further, as the light emitting material used in the present invention, a material known as a conventionally light emitting material may be used. The following are examples of compounds preferably used for blue, green, orange to red emission. However, the light emitting material is not limited to the following concrete examples.

The blue emission is, for example, perylene, 2,5,8,11-tetra-t-butylperylene (
Abbreviation: TBP), 9,10-diphenylanthracene derivative and the like can be obtained by using as a guest material. In addition, styrylarylene derivatives such as 4,4'-bis (2,2-diphenylvinyl) biphenyl (abbreviation: DPVBi) and 9,10-di-2-naphthylanthracene (abbreviation: DNA), 9,10-bis. It can also be obtained from anthracene derivatives such as (2-naphthyl) -2-tert-butylanthracene (abbreviation: t-BuDNA). Further, a polymer such as poly (9,9-dioctylfluorene) may be used.

More preferable specific examples are shown in Table 1.

The green light is emitted by coumarin pigments such as coumarin 30 and coumarin 6, and bis [2- (2,2).
4-Difluorophenyl) pyridinato] picolinatolidium (abbreviation: FIrpic), bis (2-phenylpyridinato) acetylacetonatoiridium (abbreviation: Ir (ppy) (a)
It can be obtained by using cac)) or the like as a guest material. In addition, tris (8-hydroxyquinoline) aluminum (abbreviation: Alq ₃ ), BAlq, Zn (BTZ), bis (
It can also be obtained from a metal complex such as 2-methyl-8-quinolinolato) chlorogallium (abbreviation: Ga (mq) _{2 Cl).} Further, a polymer such as poly (p-phenylene vinylene) may be used.

More preferable specific examples are shown in Table 2.

Lubrene, 4- (dicyanomethylene) -2- [p- (dimethylamino) styryl] -6-methyl-4H-pyran (abbreviation: DCM1), 4- (dicyanomethylene) -2- Methyl-6- (9-juloridyl) ethynyl-4H-pyran (abbreviation: DCM2)
), 4- (Dicyanomethylene) -2,6-bis [p- (dimethylamino) styryl] -4
H-pyran (abbreviation: BisDCM), bis [2- (2-thienyl) pyridinato] acetylacetonatoiridium (abbreviation: Ir (thp) 2 (acac)), bis (2-phenylquinolinato) acetylacetonatoiridium Abbreviation: Obtained by using Ir (pq) (acac)) or the like as a guest material. Bis (8-kinokirinorato) Zinc (abbreviation: Znq2)
) And bis [2-cinnamoyl-8-quinolinolato] zinc (abbreviation: Znsq2) can also be obtained from metal complexes. Further, a polymer such as poly (2,5-dialkoxy-1,4-phenylene vinylene) may be used.

More preferable specific examples are shown in Table 3.

Further, as the material used for the anode of the organic EL element used in the present invention, a metal having a large work function (4 eV or more), an electrically conductive compound, or a mixture thereof as an electrode material is preferably used. Specific examples of such electrode materials include metals such as Au and Cu.
Conductive materials such as I, ITO, SNO ₂ , and ZNO can be mentioned. To form this anode
A thin film can be formed of these electrode materials by a method such as a vapor deposition method or a sputtering method. When the light emitted from the light emitting layer is taken out from the anode, it is desirable that the anode has a characteristic that the transmittance of the anode with respect to the light emitted is larger than 10%. Also, the anode sea
The resistance is preferably several hundred Ω / cm ² or less. Further, the film thickness of the anode is usually selected in the range of 10 nm to 1 μm, preferably 10 to 200 nm, although it depends on the material.

Further, as the material used for the cathode of the organic EL element used in the present invention, a metal having a small work function (4 eV or less), an alloy, an electrically conductive compound, or a mixture thereof is used as an electrode material. Specific examples of such electrode materials include sodium, sodium-potassium alloys, magnesium, lithium, magnesium / silver alloys, aluminum / aluminum oxide, aluminum / lithium alloys, indium, rare earth metals and the like. This cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. Here, when the light emitted from the light emitting layer is taken out from the cathode, the transmittance of the cathode with respect to the light emitted is preferably larger than 10%. The sheet resistance of the cathode ^{is preferably several hundred Ω / cm 2} or less, and the film thickness is usually 10 nm to 1 μm, preferably 50 to 200 Nm.

Regarding the method for producing the organic EL device used in the present invention, an anode, a light emitting layer, a hole injection layer if necessary, and an electron injection layer if necessary are formed by the above materials and methods.
Finally, the cathode may be formed. It is also possible to manufacture an organic EL device from the cathode to the anode in the reverse order of the above.

This organic EL element is manufactured on a translucent substrate. This translucent substrate is a substrate that supports an organic EL element, and its translucency is preferably such that the light transmittance in the visible region of 400 to 700 nm is 50% or more, preferably 90% or more. It is preferable to use a smoother substrate.

These substrates are not particularly limited as long as they have mechanical and thermal strength and are transparent, but for example, a glass plate, a synthetic plate, or the like is preferably used. As a glass plate, especially so
Examples thereof include plates formed of dalime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the synthetic resin plate include plates such as polycarbonate resin, acrylic resin, polyethylene terephthalate resin, polyether sulfide resin, and polysulfone resin.

As a method for forming each layer of the organic EL element used in the present invention, a dry film forming method such as vacuum deposition, electron beam irradiation, sputtering, plasma, ion plating, or spin coating, dipping, flow coating, inkjet. Wet film formation methods such as the method, methods for depositing a luminescent material on a donor film, and Japanese Patent Publication No. 2002-534782 and S.A. T. Lee, et al. , Proceedings of SID '02, p.
784 (2002) LITI (Laser Induced Ther)
Methods such as mal Imaging, laser thermal transfer), printing (offset printing, flexographic printing, gravure printing, screen printing), inkjet, and the like can also be applied.

The organic layer is particularly preferably a molecular deposition film. Here, the molecular deposition film is a thin film deposited and formed from a material compound in a gas phase state, or a film solidified and formed from a material compound in a solution state or a liquid phase state, and is usually this molecular deposition film. Can be classified by the difference in aggregated structure and higher-order structure from the thin film (molecular cumulative film) formed by the LB method, and the functional difference caused by the difference. Further, as disclosed in Japanese Patent Application Laid-Open No. 57-57181, a binder such as a resin and a material compound are dissolved in a solvent to form a solution, which is then thinned by a spin coat method or the like. Can also form an organic layer. The film thickness of each layer is not particularly limited, but if the film thickness is too thick, a large applied voltage is required to obtain a constant light output, resulting in inefficiency. On the contrary, if the film thickness is too thin, the pinhole Etc., and it becomes difficult to obtain sufficient emission brightness even when an electric field is applied. Therefore, the film thickness of each layer is preferably in the range of 1 nm to 1 μm, but more preferably in the range of 10 nm to 0.2 μm.

Further, in order to improve the stability of the organic EL element with respect to temperature, humidity, atmosphere and the like, a protective layer may be provided on the surface of the element, or the entire element may be coated or sealed with a resin or the like. In particular, when coating or sealing the entire device, a photocurable resin that is cured by light is preferably used.

The current applied to the organic EL element used in the present invention is usually direct current, but pulse current or alternating current may be used. The current value and voltage value are not particularly limited as long as they do not destroy the element, but considering the power consumption and life of the element, it is desirable to efficiently emit light with as little electric energy as possible.

The organic EL element used in the present invention can be driven not only by the passive matrix method but also by the active matrix method. Further, as a method of extracting light from the organic EL element of the present embodiment, it can be applied not only to a method of bottom emission which extracts light from the anode side but also to a method of top emission which extracts light from the cathode side.
These methods and techniques are described by Junji Kido, "All about Organic EL", Nihon Jitsugyo Publishing Co., Ltd. (2003).
(Issued in the year).

The main method of the full-color method of the organic EL element used in the present invention is the color filter method. In the color filter method, an organic EL element that emits white light is used to extract light of the three primary colors through a color filter. In addition to these three primary colors, some white light is extracted as it is and used for light emission. , It is also possible to increase the light emission efficiency of the entire element.

Further, the organic EL element used in the present invention may adopt a microcavity structure. This is because the organic EL element has a structure in which a light emitting layer is sandwiched between an anode and a cathode.
The emitted light causes multiple interference between the anode and the cathode, but the optical characteristics such as the reflectance and transmittance of the anode and the cathode and the thickness of the organic layer sandwiched between them should be appropriately selected. This is a technique of positively utilizing the multiple interference effect to control the emission wavelength extracted from the element. This also makes it possible to improve the emission chromaticity. Regarding the mechanism of this multiple interference effect, J. AM-LCD Digital of Technology by Yamada et al.
ical Papers, OD-2, p. 77-80 (2002).

An RGB color filter layer is produced by juxtaposing it on a glass substrate or the like as described above, and an ITO electrode layer and a light emitting layer (backlight) produced by using the organic EL element are placed on the color filter layer. As a result, color display becomes possible, and a color display device can be obtained. At that time, it is possible to realize a color display device having a high contrast ratio by controlling the current flow at the time of light emission by the TFT.

<< Other uses >>
The application of the photosensitive composition of the present invention is not particularly limited, and a color filter for an organic EL display device, a color filter for a quantum dot display device, a color filter for C-MOS, a black matrix, various coatings, etc. are manufactured. Can be used to

Hereinafter, embodiments of the present invention will be described in more detail with reference to Examples, but the following Examples do not limit the scope of rights of the present invention at all. In the examples, "parts" represents "parts by mass" and "%" represents "% by mass".
Further, in the following examples, the molecular weight of the resin is a polystyrene-equivalent weight average molecular weight measured by GPC (gel permeation chromatography), and is G of Tosoh Corporation.
By PC-8020, eluent uses tetrahydrofuran and column is TSKgel
Using 3 SuperHM-M (manufactured by Tosoh Corporation), the flow velocity is 0.6 ml / min, and the injection volume is 10 μl.
, The column temperature was measured at 40 ° C.
IR measurement was performed using a Spectum One manufactured by PerkinElmer.
The acid value was measured as follows. About 1 g of the compound solution for measuring the acid value was weighed, 30 g of methyl ethyl ketone and 1 g of water were added, and the mixture was stirred for 10 minutes, and then potentiometric titration was performed with a 0.1 N potassium hydroxide ethanol solution. In addition, a blank test was conducted in the same manner. 20 non-volatile components of the target
The measurement was carried out by heating at 0 ° C. for 10 minutes, and from the obtained titration value and the non-volatile content, the number of mg of the acid group (alkali-soluble functional group) contained in 1 g of the non-volatile content of the compound solution and the equivalent amount of potassium hydroxide was determined. ..
In the present specification, the non-volatile content means a value calculated from the mass of the sample after heating / the mass of the sample before heating when 1 g of the sample is heated at 200 ° C. for 10 minutes. However, in the case of a commercially available product, a value calculated based on a method specified by the manufacturer may be adopted. In the present specification, solid content and non-volatile content are synonymous.

In addition, Examples 1 to 8 are reference examples.
Subsequently, the organic EL element, the alkali-soluble resin solution, the resin for salt-forming dye, the colorant, the salt-forming compound, the photosensitive coloring composition, and the method for producing the photosensitive coloring composition used in Examples and Comparative Examples will be described. To do.

<Manufacturing example of organic EL element>
A specific example of manufacturing an organic EL device used as a white light source is shown below. In the production examples of organic EL devices, all mixing ratios indicate weight ratios unless otherwise specified. Thin-film deposition (vacuum vapor deposition) was performed in ^{a vacuum of 10-6} Torr under conditions such as substrate heating and cooling without temperature control. Further, in the evaluation of the light emitting characteristics of the element, the characteristics of the organic EL element having an electrode area of 2 mm × 2 mm were measured.

(Manufacturing of Organic EL Element 1 (EL-1))
The washed glass plate with ITO electrode was treated with oxygen plasma for about 1 minute, and then 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (α-NPD) was vacuum-deposited. A hole injection layer having a thickness of 150 nm was obtained. On the hole injection layer, the compound (R-2) and the compound (R-3) in Table 3 are further co-deposited at a composition ratio of 100: 2 to form a first light emitting layer having a film thickness of 10 nm. did. Further, the compound (B-1) and the compound (B-4) in Table 1 were co-deposited at a composition ratio of 100: 3 to form a second light emitting layer having a film thickness of 20 nm. A third light emitting layer was formed by further depositing α-NPD at 5 nm and the compound (G-3) in Table 2 at 20 nm on the light emitting layer. Further, a tris (8-hydroxyquinoline) aluminum complex is vacuum-deposited to form an electron-injected layer having a film thickness of 35 nm, and lithium fluoride is first deposited at 1 nm and then aluminum at 200 nm to form an electrode. , The organic EL element 1 was obtained.

Further, the organic EL element was hermetically sealed in a dry glove box filled with pure nitrogen in order to protect it from the surrounding environment. This element obtained white emission with a emission brightness of 950 (cd / m ² ), a maximum emission brightness of 55,000 (cd / m ² ), and a luminous efficiency of 3.9 (lm / W) at a DC voltage of 5 V. FIG. 1 shows the emission spectrum of the obtained organic EL element EL-1.

<Manufacture of alkali-soluble resin (B) having radically polymerizable group>
[Manufacturing Example 1]
Put 90.0 parts of propylene glycol monomethyl ether acetate in a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, and gas introduction tube, and heat to 60 ° C. while injecting nitrogen gas into the vessel to the same temperature. A mixture of 35.0 parts of glycidyl methacrylate, 45.0 parts of methyl methacrylate and 2.5 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours to carry out a polymerization reaction. After completion of the dropping, the mixture was further reacted at 60 ° C. for 1 hour, and then 0.5 part of 2,2'-azobisisobutyronitrile dissolved in 10.0 parts of propylene glycol monomethyl ether acetate was added, and then the mixture was added. Stirring was continued at the same temperature for 3 hours to obtain a copolymer. Subsequently, dry air was injected into the reaction vessel, 10.0 parts of acrylic acid, 30.2 parts of propylene glycol monomethyl ether acetate, 1.30 parts of dimethylbenzylamine, and 0.26 parts of methquinone were added, and the mixture was heated to 100 ° C. Then, stirring was continued for 20 hours, and the acid value was measured to confirm that the desired product was produced. Subsequently, 10.0 parts of tetrahydrophthalic anhydride and 27.7 parts of propylene glycol monomethyl ether acetate were placed in a reaction vessel, and stirring was continued at 60 ° C. for 3 hours, and IR measurement was performed to confirm that the desired product was produced. confirmed. After cooling to room temperature, the mixture was diluted with propylene glycol monomethyl ether acetate to obtain an alkali-soluble resin (B-1) solution A-1 having a radically polymerizable group having a non-volatile content of 40%. The weight average molecular weight was 8000.

表４中の略語について以下に示す。なお、表４中の有機溶剤の量は、合成中に使用した量であって、室温に冷却後に不揮発分を調整するために使用したものは含まれていない。
ＢｚＭＡ：ベンジルメタクリレート
ＭＭＡ：メチルメタクリレート
ｎ-ＢＭＡ：ｎ-ブチルメタクリレート
ＧＭＡ：グリシジルメタクリレート：ブレンマーＧ（日油社製）
ＡＡ：アクリル酸
ＴＨＰＡ：１，２，３，６−テトラヒドロ無水フタル酸：リカシッドＴＨ（新日本理化社製）
＜分散剤（Ｘ）の製造＞
［製造例４］
(第一工程）
ガス導入管、温度計、コンデンサー、攪拌機を備えた反応容器に、ＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート）４４．０部、メタクリル酸（ＭＡＡ）５．０部、ベンジルメタクリレート（ＢｚＭＡ）１０．０部、ｔｅｒｔ-ブチルメタクリレート（ｔ-ＢＡ）１０。０部、メチルメタクリレート（ＭＭＡ）７０。０部を仕込み、窒素ガスで置換した。反応容器内を８０℃に加熱して、３−メルカプト−１,２−プロパンジオール４．０部、２，２‘−アゾビスイソブチロニトリル０．１２部、ＰＧＭＥＡ４５．４部を添加して、１２時間反応した。固形分測定により９５％が反応したことを確認した。
（第二工程）
次に、第一工程で得られた溶液に、ピロメリット酸無水物（ＰＭＡ）６．４６部、触媒として１，８−ジアザビシクロ−［５．４．０］−７−ウンデセン（ＤＢＵ）０．２部を仕込み、１２０℃で７時間反応させた。酸価の測定で９８％以上の酸無水物がハーフエステル化するまで反応させた。
反応溶液を冷却して、ＰＧＭＥＡで固形分調整することにより不揮発分５０％の溶液を調整し、重量平均分子量８１００、酸価は６０ｍｇＫＯＨ／ｇ、の分散剤Ｘ−１溶液を得た。

＜＜感光性組成物＞＞
＜着色剤（Ａ）の製造方法＞
＜顔料の製造方法＞
（青色顔料（ＰＢ−１））
Ｃ．Ｉ．ピグメントブルー１５：６（ＰＢ１５：６）（トーヨーカラー社製「リオノールブルーＥＳ」）１００部、粉砕した食塩８００部、およびジエチレングリコール１００部をステンレス製１ガロンニーダー（井上製作所製）に仕込み、７０℃で１２時間混練した。この混合物を温水３０００部に投入し、７０℃に加熱しながら１時間攪拌してスラリー状とし、濾過、水洗をくりかえして食塩および溶剤を除いた後、８０℃で一昼夜乾燥し、９８部の青色着色剤（ＰＢ−１）を得た。平均一次粒子径は２８．３ｎｍであった。
（紫色顔料（ＰＶ−１））
Ｃ．Ｉ．ピグメントバイオレット２３（ＰＶ２３）（クラリアント社製「Ｆａｓｔ ＶｉｏｌｅｔＲＬ」）１２０部、粉砕した食塩１６００部、およびジエチレングリコール１００部をステンレス製１ガロンニーダー（井上製作所製）に仕込み、９０℃で１８時間混練した。この混合物を温水５０００部に投入し、７０℃に加熱しながら１時間攪拌してスラリー状とし、濾過、水洗をくりかえして食塩および溶剤を除いた後、８０℃で一昼夜乾燥し、１１８部の紫色着色剤（ＰＶ−１）を得た。平均一次粒子径は２６．４ｎｍであった。
＜染料の製造方法＞
（紫色染料（ＰＶ−２））
下記の手順でＣ．I．アシッド レッド ２８９と側鎖にカチオン性基を有する下記樹脂Ｙ−１とからなる紫色染料（ＰＶ−２）を製造した。
水２０００部に５１部の側鎖にカチオン性基を有する下記樹脂Ｂ−１を添加し、十分に攪拌混合を行った後、６０℃に加熱する。一方、９０部の水に１０部のＣ．I．アシッド レッド ２８９を溶解させた水溶液を調製し、先ほどの樹脂溶液に少しずつ滴下していく。滴下後、６０℃で１２０分攪拌し、十分に反応を行う。反応の終点確認としては濾紙に反応液を滴下して、にじみがなくなったところを終点として、造塩化合物が得られたものと判断した。攪拌しながら室温まで放冷した後、吸引濾過と水洗によって側鎖にカチオン性基を有する樹脂の対アニオンとＣ．I．アシッド レッド ２８９の対カチオンとからなる塩を除去した後、濾紙上に残った造塩化合物を乾燥機にて水分を除去して乾燥し、３２部のＣ．I．アシッド レッド ２８９と側鎖にカチオン性基を有する下記樹脂Ｙ−１との紫色染料（ＰＶ−２）を得た。ＰＶ−２の固形分量は２０重量％であり、全固形分中のＣ．I．アシッド レッド ２８９の含有量は５０重量％であった。 [Manufacturing Examples 2-3]
Synthesis was carried out in the same manner as in Production Example 1 except that the raw materials and the amount charged shown in Table 4 were used to obtain alkali-soluble resins B-2 to B-3 having a non-volatile content of 40%.

The abbreviations in Table 4 are shown below. The amount of the organic solvent in Table 4 is the amount used during the synthesis, and does not include the amount used for adjusting the non-volatile content after cooling to room temperature.
BzMA: Benzyl methacrylate MMA: Methyl methacrylate n-BMA: n-Butyl methacrylate GMA: Glycidyl methacrylate: Blemmer G (manufactured by NOF CORPORATION)
AA: Acrylic acid THPA: 1,2,3,6-tetrahydrophthalic anhydride: Ricacid TH (manufactured by New Japan Chemical Co., Ltd.)
<Manufacturing of dispersant (X)>
[Manufacturing Example 4]
(First step)
44.0 parts of PGMEA (propylene glycol monomethyl ether acetate), 5.0 parts of methacrylic acid (MAA), 10.0 parts of benzyl methacrylate (BzMA), in a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer. 10.0 parts of tert-butyl methacrylate (t-BA) and 70.0 parts of methyl methacrylate (MMA) were charged and replaced with nitrogen gas. The inside of the reaction vessel is heated to 80 ° C., and 4.0 parts of 3-mercapto-1,2-propanediol, 0.12 parts of 2,2'-azobisisobutyronitrile, and 45.4 parts of PGMEA are added. , Reacted for 12 hours. It was confirmed by solid content measurement that 95% had reacted.
(Second step)
Next, in the solution obtained in the first step, 6.46 parts of pyromellitic anhydride (PMA) and 1,8-diazabicyclo- [5.4.0] -7-undecene (DBU) 0. Two parts were charged and reacted at 120 ° C. for 7 hours. The reaction was carried out until 98% or more of the acid anhydride was half-esterified by measuring the acid value.
The reaction solution was cooled and the solid content was adjusted with PGMEA to prepare a solution having a non-volatile content of 50% to obtain a dispersant X-1 solution having a weight average molecular weight of 8100 and an acid value of 60 mgKOH / g.

<< Photosensitive composition >>
<Manufacturing method of colorant (A)>
<Pigment manufacturing method>
(Blue pigment (PB-1))
C. I. Pigment Blue 15: 6 (PB15: 6) (Toyo Color Co., Ltd. "Rionol Blue ES") 100 parts, crushed salt 800 parts, and diethylene glycol 100 parts are charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), 70 parts. Kneaded at ° C. for 12 hours. This mixture was poured into 3000 parts of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then dried at 80 ° C. for 24 hours, and 98 parts of blue color. A colorant (PB-1) was obtained. The average primary particle size was 28.3 nm.
(Purple pigment (PV-1))
C. I. Pigment Violet 23 (PV23) (“Fast VioletRL” manufactured by Clariant), 1600 parts of crushed salt, and 100 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 90 ° C. for 18 hours. This mixture was put into 5000 parts of warm water and stirred for 1 hour while heating at 70 ° C. to form a slurry, which was repeatedly filtered and washed with water to remove salt and solvent, and then dried at 80 ° C. for 24 hours and 118 parts of purple. A colorant (PV-1) was obtained. The average primary particle size was 26.4 nm.
<Dye manufacturing method>
(Purple dye (PV-2))
Follow the procedure below to C.I. I. A purple dye (PV-2) composed of Acid Red 289 and the following resin Y-1 having a cationic group in the side chain was produced.
The following resin B-1, which has a cationic group in the side chain of 51 parts, is added to 2000 parts of water, and after sufficient stirring and mixing, the mixture is heated to 60 ° C. On the other hand, 90 parts of water and 10 parts of C.I. I. An aqueous solution in which Acid Red 289 is dissolved is prepared, and the solution is gradually added dropwise to the resin solution. After the dropping, the mixture is stirred at 60 ° C. for 120 minutes to sufficiently react. To confirm the end point of the reaction, it was judged that the salt-forming compound was obtained by dropping the reaction solution onto the filter paper and using the point where the bleeding disappeared as the end point. After allowing to cool to room temperature with stirring, the counter anion of the resin having a cationic group in the side chain and C.I. I. After removing the salt consisting of the counter cation of Acid Red 289, the salt-forming compound remaining on the filter paper was dried by removing water with a dryer, and 32 parts of C.I. I. A purple dye (PV-2) was obtained with Acid Red 289 and the following resin Y-1 having a cationic group in the side chain. The solid content of PV-2 is 20% by weight, and C.I. I. The content of Acid Red 289 was 50% by weight.

(Resin Y-1 having a cationic group in the side chain)
75.1 parts of isopropyl alcohol was placed in a 4-port separable flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, and the temperature was raised to 75 ° C. under a nitrogen stream. Separately, 18.2 parts of methyl methacrylate, 27.3 parts of n-butyl methacrylate, 27.3 parts of 2-ethylhexyl methacrylate, 15.0 parts of hydroxyethyl methacrylate, 12.2 parts of dimethylaminoethyl methyl chloride salt, and separately. After homogenizing 7.0 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) dissolved in 23.4 parts of methyl ethyl ketone, it was charged into a dropping funnel and attached to a four-neck separable flask for 2 hours. Dropped over. Two hours after the completion of the dropping, it was confirmed from the solid content that the polymerization yield was 98% or more and the weight average molecular weight (Mw) was 7330, and the mixture was cooled to 50 ° C. Then, 14.3 parts of methanol was added to obtain a resin Y-1 having a cationic group in the side chain having a resin component of 40% by weight. The ammonium salt value of the obtained resin was 32 mgKOH / g.

<Manufacturing method of colorant dispersion>
[Preparation of blue colorant dispersion DB-1]
The mixture having the following composition is uniformly stirred and mixed, dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. A blue colorant dispersion DB-1 was prepared.
Blue fine pigment (PB-1): 10.0 parts (PB15: 6)
Dispersant (X-1): 20.0 parts Solvent: 70.0 parts Propylene glycol monomethyl ether acetate (PGMEA)

[Preparation of purple colorant dispersion DV-1]
A purple colorant dispersion DV-1 was prepared in the same manner as the blue colorant dispersion DB-1 except that the colorant was changed to PV-1.

<Manufacturing of photosensitive coloring compositions for color filters>
[Example 1]
The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a blue photosensitive coloring composition (PB-1).
Pigment dispersion (DB-1): 15.0 parts (PB15: 6)
Pigment dispersion (DV-1): 15.0 parts (PV23)
Alkali-soluble resin with radically polymerizable group B-1: 16.9 parts Polyfunctional acrylate monomer: 1.5 parts ("Aronix M402" manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator 1: 0.37 parts (ADEKA "NCI-831" (absorption maximum wavelength 370 nm, ADEKA, nitro group-containing carbazole structure oxime initiator))
Photopolymerization initiator 2: 0.37 parts (BASF's "IRGACURE 379" absorption maximum wavelength 320 nm, BASF's acetophenone-based initiator))
Leveling agent: 1.0 part (2% PGMEA solution of "BYK-330" manufactured by Big Chemie)
Solvent: 49.9 parts (propylene glycol monomethyl ether acetate (PGMEA))

表５の各略号は以下のとおりである。
Ｍ３０９：アロニックスＭ―３０９（東亞合成社製）
Ｍ４０２：アロニックスＭ―４０２（東亞合成社製）
ＮＣＩ８３１：アデカクルーズＮＣＩ−８３１（吸収極大波長３７０ｎｍ、ＡＤＥＫＡ社製、ニトロ基含有カルバゾール構造オキシム系開始剤）
Ｉｒｇ.９０７：ＩＲＧＡＣＵＲＥ ９０７（吸収極大波長３５５ｎｍ、ＢＡＳＦ社製、アセトフェノン系開始剤）
Ｉｒｇ.３６９：ＩＲＧＡＣＵＲＥ ３６９（吸収極大波長３２０ｎｍ、ＢＡＳＦ社製、アセトフェノン系開始剤）
Ｉｒｇ.３７９：ＩＲＧＡＣＵＲＥ ３７９（吸収極大波長３２０ｎｍ、ＢＡＳＦ社製、アセトフェノン系開始剤）
ＯＸＥ−０１：ＩＲＧＡＣＵＲＥ ＯＸＥ０１（吸収極大波長３３０ｎｍ、ＢＡＳＦ社製、フェニル構造含有オキシム系開始剤）
ＤＥＴＸＳ：カヤキュアＤＥＴＸＳ（日本化薬社製）
ＥＡＢＦ：ＥＡＢ−Ｆ（保土ヶ谷化学社製） [Examples 2-29, Comparative Examples 1-8]
Each material was mixed and stirred according to the composition and the blending amount shown in Table 5, and filtered through a 1 μm filter to obtain each photosensitive coloring composition PB-2 to 35.

Each abbreviation in Table 5 is as follows.
M309: Aronix M-309 (manufactured by Toagosei Co., Ltd.)
M402: Aronix M-402 (manufactured by Toagosei Co., Ltd.)
NCI831: Adeka Cruise NCI-831 (absorption maximum wavelength 370 nm, manufactured by ADEKA, nitro group-containing carbazole structure oxime initiator)
Irg.907: IRGACURE 907 (absorption maximum wavelength 355 nm, manufactured by BASF, acetophenone-based initiator)
Irg.369: IRGACURE 369 (absorption maximum wavelength 320 nm, manufactured by BASF, acetophenone-based initiator)
Irg.379: IRGACURE 379 (absorption maximum wavelength 320 nm, manufactured by BASF, acetophenone-based initiator)
OXE-01: IRGACURE OXE01 (absorption maximum wavelength 330 nm, manufactured by BASF, phenyl structure-containing oxime-based initiator)
DETXS: Kayacure DETXS (manufactured by Nippon Kayaku Co., Ltd.)
EABF: EAB-F (manufactured by Hodogaya Chemical Co., Ltd.)

<Evaluation of photosensitive composition>
Using the obtained photosensitive composition, chemical resistance, brightness, and developed line width were evaluated by the following methods. The results are shown in Table 6.
[Evaluation of drug resistance]
The coating film prepared in the same procedure as the evaluation of appearance was heated at 100 ° C. or 150 ° C. for 20 minutes, allowed to cool, and peeled off from the glass substrate to obtain a film for evaluation.
The chromaticity of the obtained film was measured, and the film was immersed in propylene glycol monomethyl ether acetate at room temperature for 5 minutes, washed with ion-exchanged water, and air-dried. Then, the film was visually observed and the chromaticity was measured, and the color difference ΔE was calculated. The chromaticity was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.) using a C light source. The evaluation ranks are as follows.
◯: No change in appearance, ΔE ≦ 2.0
: Good level Δ: No change in appearance, ΔE ≦ 2.0 to 5.0
: Practical level ×: There is a change in appearance and / or 5.0 <ΔE
: Level not suitable for practical use

[Color characterization]
The color characteristics of the coating film prepared at the time of chemical resistance were measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). Table 6 shows the brightness Y when y = 0.06 using the organic EL white light source shown in FIG. The evaluation ranks are as follows.
⊚: Brightness Y 3.5 or more and very good level 〇: Brightness Y 3.2 or more and less than 3.5 Good level 〇 △: Brightness Y 3.0 or more and less than 3.2 Practically preferable level △: Brightness Y 2 .8 or more and less than 3.0 Practical level ×: Brightness Y less than 2.8 Level not suitable for practical use

[Evaluation of developed line width]
The photosensitive coloring compositions of Examples 2 to 29 and Comparative Examples 1 to 8 were dried under reduced pressure using a spin coater on a 100 mm × 100 mm, 250 μm thick polyethylene naphthalate film fixed on a glass substrate with an adhesive. It was applied so that the finished film thickness was 2.0 μm, and dried under reduced pressure. After cooling this film to room temperature, an ultrahigh pressure mercury lamp was used to irradiate ultraviolet rays with an illuminance of 20 mW / cm ² and an exposure amount of 50 mJ / cm ² through a photomask having a stripe pattern with a width of 50 μm (pitch 100 μm). Then, this film was spray-developed with an aqueous sodium carbonate solution at 23 ° C., washed with ion-exchanged water, air-dried, and heated at 100 ° C. for 20 minutes in a clean oven. After allowing to cool, it was peeled off from the glass substrate to obtain a film for evaluation. The spray development was carried out for the films using the respective photosensitive coloring compositions at a time extended by 10 seconds from the development time developed without residue. The obtained pattern film was observed with an optical microscope, and the width of the pattern at the 50 μm photomask portion was measured. The closer to the size of the photomask, the higher the definition and the better the photosensitive composition. The evaluation ranks are as follows.
⊚: 50 μm or more and less than 53 μm ○: 53 μm or more and less than 56 μm Δ: 56 μm or more and less than 65 μm ×: 65 μm or more Note that ◎ and ○ are practically preferable levels, △ is a practical level, and × is not suitable for practical use. It is a level.

表６に示すように、実施例１〜２９の感光性着色組成物はいずれも低温硬化条件においても優れた薬品耐性を示している。詳細に説明すると、実施例６〜１４においては成分（Ｄ１）と（Ｄ２）の比率が５／９５〜３０／７０の間にすることで薬品耐性に加えて高い明度と解像性を備えていることが分かる。さらに実施例１５〜２０においては青色顔料（Ａ１）が着色剤（Ａ）全体中で６５重量％以上となることで、さらに高い明度を兼ね備えることが出来ている。比較例４と５を比較すると分かるように、青色顔料（Ａ１）の量が増えると充分に光硬化が進まずに薬品耐性が低下するが、実施例１５〜２０においては青色顔料（Ａ１）量が増えても薬品耐性は低下していない。これが本発明における開始剤（Ｄ１）と（Ｄ２）を併用することの効果である。
また、実施例２１〜２９においては、染料（Ａ２）を１５重量％以上含有することで、さらに高い明度を兼ね備えることに成功している。
比較例１は、開始剤（Ｄ１）のみを使用した場合であるが、表面の効果のみが進み薬品耐性が悪化している上に明度が大きく低下してしまっている。比較例２〜４は開始剤（Ｄ２）のみを使用した場合だが、こちらも薬品耐性が低い。比較例５はアセトフェノン構造を有するが吸収極大波長が３００〜３５０ｎｍの範囲内ではない開始剤を用いていることで、（Ｄ１）開始剤との併用でも良好な効果を得ることが出来ていない。比較例６は青色顔料（Ａ１）量が少ないがために若干薬品耐性が良いが、１００℃硬化での薬品耐性は実用に耐えない。
比較例７〜８は増感剤を併用した場合だが、低温硬化での薬品耐性が良好ではない。

上記のように低温での薬品耐性が得られていることと、透過率（明度）が高いこと、解像性が良好であることから、液晶ディスプレイ、固体撮像素子、有機ＥＬディププレイ用のカラーフィルタに使用した場合にも、好適に使用することが可能であった。

As shown in Table 6, all of the photosensitive coloring compositions of Examples 1 to 29 show excellent chemical resistance even under low temperature curing conditions. More specifically, in Examples 6 to 14, the ratio of the components (D1) and (D2) is set to be between 5/95 and 30/70 to provide high brightness and resolution in addition to chemical resistance. You can see that there is. Further, in Examples 15 to 20, the blue pigment (A1) is 65% by weight or more in the whole colorant (A), so that even higher brightness can be obtained. As can be seen by comparing Comparative Examples 4 and 5, when the amount of the blue pigment (A1) is increased, the photocuring does not proceed sufficiently and the chemical resistance is lowered, but in Examples 15 to 20, the amount of the blue pigment (A1) is reduced. The drug resistance did not decrease even if the number increased. This is the effect of using the initiators (D1) and (D2) in combination in the present invention.
Further, in Examples 21 to 29, by containing 15% by weight or more of the dye (A2), it has succeeded in having even higher brightness.
Comparative Example 1 is a case where only the initiator (D1) is used, but only the surface effect is advanced, the chemical resistance is deteriorated, and the brightness is greatly reduced. Comparative Examples 2 to 4 are cases where only the initiator (D2) is used, but this also has low drug resistance. In Comparative Example 5, since an initiator having an acetophenone structure but having an absorption maximum wavelength not in the range of 300 to 350 nm is used, a good effect cannot be obtained even when used in combination with the (D1) initiator. In Comparative Example 6, since the amount of blue pigment (A1) is small, the chemical resistance is slightly good, but the chemical resistance at 100 ° C. curing is not practical.
Comparative Examples 7 to 8 are cases where a sensitizer is used in combination, but the chemical resistance at low temperature curing is not good.

As described above, chemical resistance at low temperatures is obtained, transmittance (brightness) is high, and resolution is good. Therefore, liquid crystal displays, solid-state image sensors, and color filters for organic EL dipplay. It was possible to use it suitably even when it was used in the above.

The photosensitive coloring composition of the present invention can be used for a color liquid crystal display device, a color organic EL display device, a solid-state image sensor, a color filter used for quantum dots, a black matrix, and the like.

Claims (7)

A photosensitive coloring composition containing a colorant (A), an alkali-soluble resin (B) having a radically polymerizable group, a polyfunctional (meth) acrylate monomer (C), and a photopolymerization initiator (D).
The photopolymerization initiator (D) is a carbazole-based oxime compound (D1) having an absorption maximum wavelength in the range of 350 to 400 nm, and a phenyl-based oxime compound and acetophenone having an absorption maximum wavelength in the range of 300 to 350 nm. Containing at least one compound (D2) selected from the compounds,
The weight ratio of the compound (D1) to (D2) is (D1) / (D2) = 5/95 to 11/89.
The colorant (A) contains at least one selected from a blue pigment (A1) having a phthalocyanine skeleton and a dye (A2) .
The total content of the blue pigment (A1) and the dye (A2) is, in the colorant (A), the photosensitive coloring composition, characterized in der Rukoto 65 wt% to 100 wt% or less. The photosensitive coloring composition according to claim 1 , wherein the carbazole-based oxime compound (D1) is a compound having a nitro group. The photosensitive according to claim 1 or 2 , wherein the colorant (A) contains the dye (A2), and the content of the dye (A2) is 15% by weight or more in the colorant (A). Sexual coloring composition. A photosensitive coloring composition used for a color filter for an organic EL display device produced by a production method including the following steps (i), (ii), (iii) and (iv).
<Process>
(I): Step of obtaining a coating film by applying the photosensitive coloring composition according to any one of claims 1 to 3 on a substrate (ii): After step (i), ultraviolet rays are passed through a mask. Step (iii) of exposing the coating film in (iii): After step (ii), a pattern is obtained by developing the exposed coating film with an alkaline developer. Step (iv): After step (iii), 80 ° C. to 150 ° C. The process of post-baking the pattern with A color filter comprising a cured product formed of the photosensitive coloring composition according to any one of claims 1 to 4 on a base material. An organic EL display device comprising the color filter according to claim 5. A method for manufacturing a color filter for an organic EL display device, which comprises the following steps (i), (ii), (iii) and (iv).
The following photosensitive coloring composition contains a colorant (A), an alkali-soluble resin (B) having a radically polymerizable group, a polyfunctional (meth) acrylate monomer (C), and a photopolymerization initiator (D). A sex coloring composition
The photopolymerization initiator (D) is a carbazole-based oxime compound (D1) having an absorption maximum wavelength in the range of 350 to 400 nm, and a phenyl-based oxime compound and acetophenone having an absorption maximum wavelength in the range of 300 to 350 nm. Containing at least one compound (D2) selected from the compounds,
The weight ratio of the compound (D1) to (D2) is (D1) / (D2) = 5/95 to 11/89.
The colorant (A) contains at least one selected from a blue pigment (A1) having a phthalocyanine skeleton and a dye (A2) .
The total content of the blue pigment (A1) and the dye (A2) is, in the colorant (A), an organic EL display, which is a Der Ru photosensitive coloring composition 65 wt% to 100 wt% Manufacturing method of color filter for equipment.
<Process>
(I): Step of obtaining a coating film by applying the photosensitive coloring composition on a substrate (ii): Step (i): After step (i), a step of exposing the coating film with ultraviolet rays via a mask (iii): Step. (Ii) After that, a pattern is obtained by developing the exposed coating film with an alkaline developing solution (iv): After step (iii), a step of post-baking the pattern at 80 ° C. to 150 ° C.

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