JP7124914B2 - Photosensitive coloring composition, color filter, and organic EL display device - Google Patents

Description

TECHNICAL FIELD 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 baking. The photosensitive coloring composition of the present invention can be used for applications such as color filters used in color liquid crystal display devices, color organic EL display devices, solid-state imaging devices, quantum dots, and the like, and black matrices.

In general, organic EL display devices (especially the WRGB system that combines white light emitting organic EL and color filters), liquid crystal display devices, integrated circuit devices, solid-state imaging devices, etc. are provided with films such as color filters, black matrices, and fine patterns. It is These films or fine patterns are required to have optical properties such as high saturation and high transparency. Resistance to solvents, etc. are required. Therefore, it is known to form a film or fine pattern having excellent solvent resistance by adding a photocuring agent or a thermal cross-linking 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 a growing need to fabricate elements using flexible substrates instead of the conventionally used rigid glass substrates. Since it is made of an organic material and has lower heat resistance than a glass substrate, it has become necessary to lower the thermosetting temperature. For example, color filters have conventionally been heat-cured at around 200-230°C, but when using flexible plastic substrates, it is necessary to lower the heat-curing temperature to around 80-150°C due to heat resistance issues. There is Such low temperature cure processes do not provide sufficient thermal cross-linking and are not sufficiently resistant to solvents contained in post-processed components. Especially in color filters, in order to obtain high chroma and high transmittance, dyes and pigments are often used in a very large amount. difficult. Furthermore, in a color filter that requires a fine pattern, there is a limit to the increase in crosslinkability due to the addition of a large amount of photo-curing agent because the pattern becomes thicker.

In particular, a blue pigment having a phthalocyanine skeleton absorbs ultraviolet light, which is the absorption wavelength of a photoinitiator, and does not photoharden deep into the coating film, and therefore tends to have poor solvent resistance. If the heat curing process is lowered to about 80 to 150°C, it will become even worse. In addition, when the coloring agent contains a dye, the solubility in the solvent is high, so that the solvent resistance becomes worse than when a blue pigment having a phthalocyanine skeleton is used. However, in order to obtain high chroma and high transparency of the coating film, it is necessary to use a large amount of a blue pigment or dye having a phthalocyanine skeleton.

As described above, while imparting solvent resistance to the photosensitive coloring composition, it is required to have high permeability and form a fine pattern, and in the case of a low temperature curing process, the request is particularly strong. Until now, as a photocuring agent, a highly sensitive initiator is used, or a sensitizer is used in combination to improve the degree of crosslinking of the coating film, and as a heat curing agent, it is described in Patent Documents 1 and 2. Solvent resistance was imparted by improving cross-linking at low temperature by using epoxy resin, blocked isocyanate, and melamine resin. However, the above technique has the following problems.

According to the studies of the present inventors, when a large amount of a highly sensitive initiator such as an oxime ester initiator is added to a photosensitive composition, fine patterns cannot be formed, and only the surface of the coating film is cured. There was no improvement in the swelling, peeling, or dissolution of the end surface of the coating film due to immersion in the solvent.
Similar results were obtained when a sensitizer was also used.

By adding an epoxy resin, as described in Patent Document 2, it is possible to impart chemical resistance by heat-curing the photosensitive composition at 180° C. or higher, but heat curing at lower temperatures is expected. Can not. According to the studies of the present inventors, it is impossible to impart solvent resistance at a low temperature of 80 to 150 ° C. without a catalyst. Curing at temperature is possible. However, due to the influence of the catalyst added, depending on the type and amount of the catalyst, the reaction proceeds little by little even at room temperature. Sometimes.

As described in Patent Documents 1 and 2, the addition of blocked isocyanate enables the photosensitive composition to be thermally cured at 180° C. or higher to impart chemical resistance. According to the studies of the present inventors, it is possible to impart solvent resistance even with low-temperature curing of 150° C. or less, but the blocking agent remaining in the cured product adversely affects the insulation properties. There is In addition, depending on the type of blocking agent, there is concern that the blocking agent may scatter in the air during heat curing, adversely affecting workers or the environment, or lowering optical properties. Furthermore, many blocked isocyanates have poor compatibility with acrylic photosensitive compositions and may cause whitening.

As with blocked isocyanate, melamine resin can be given chemical resistance even if it is cured at a low temperature of 150°C or less. There are concerns about In addition, many low-temperature curable melamines have high polarity and poor compatibility with acrylic photosensitive compositions, which may cause whitening.

JP 2013-5/95956 JP 2011-93955 A JP-A-2000-233581

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

One aspect of the present invention is a photosensitive resin 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) In the colored composition, the photopolymerization initiator (D) comprises a carbazole-based oxime compound (D1) having a maximum absorption wavelength in the range of 350 to 400 nm, and a maximum absorption wavelength in the range of 300 to 350 nm. at least one compound (D2) selected from phenyl-based oxime compounds and acetophenone compounds, wherein the colorant (A) is a blue pigment (A1) having a phthalocyanine skeleton and at least one selected from dyes (A2) It relates to a photosensitive coloring composition characterized by containing seeds.

In one aspect of the present invention, the weight ratio of compounds (D1) and (D2) is (D1)/(D2) = 5/95 to 30/70. Regarding.

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

Further, in one aspect of the present invention, 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). It relates to a photosensitive coloring composition.

In one aspect of the present invention, the coloring agent (A) contains a dye (A2), and the content of the dye (A2) is 15% by weight or more in the coloring agent (A). It relates to the above photosensitive coloring composition.

Another aspect of the present invention relates to a color filter comprising a substrate and a cured product formed from the photosensitive coloring composition.

Another aspect of the present invention relates to an organic EL display device including the color filter.

Further, one aspect of the present invention is a method for producing a color filter for an organic EL display device, comprising the following steps (i), (ii), (iii) and (iv), wherein the following photosensitive coloring composition is A photosensitive coloring composition containing a coloring agent (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) comprises a carbazole-based oxime compound (D1) having a maximum absorption wavelength in the range of 350 to 400 nm, and a phenyl-based oxime compound and acetophenone having a maximum absorption wavelength in the range of 300 to 350 nm. A photosensitive coloring composition containing at least one compound (D2) selected from compounds, wherein the colorant (A) contains at least one selected from a blue pigment (A1) having a phthalocyanine skeleton and a dye (A2). The present invention relates to a method for manufacturing a color filter for an organic EL display device, characterized by being a substance.

<Process>
(i): Step of obtaining a coating film by coating a photosensitive coloring composition on a substrate (ii): After step (i), exposing the coating film with ultraviolet light through a mask (iii): Step After (ii), the exposed coating film is developed with an alkaline developer to obtain a pattern (iv): After step (iii), the pattern is post-baked at 80° C. to 150° C.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide solvent resistance even at a low curing temperature, and it is possible to provide a photosensitive coloring composition having high transmittance and photolithography capable of forming a fine pattern. rice field.

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

Embodiments of the present invention are described in detail below. In this specification, (meth)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 method for curing the photosensitive composition of the present embodiment and a combination of constituent elements will be described. The photosensitive coloring composition of the present embodiment comprises a coloring agent (A), an alkali-soluble resin (B) having a radically polymerizable group, a polyfunctional (meth)acrylate monomer (C), and an initiator (D) as essential components. and the coloring agent (A) contains at least one selected from a blue pigment (A1) having a phthalocyanine skeleton or a dye (A2), and the initiator (D) has an absorption maximum in the range of 350 to 400 nm It contains a carbazole type oxime compound (D1) having a wavelength, and further contains at least one of a phenyl type oxime compound or an acetophenone compound (D2) having a maximum absorption wavelength within the range of 300 to 350 nm.
The photosensitive composition of the present embodiment only needs to satisfy the above configuration, and is not limited to the action or curing process. For example, by performing photocuring and then heat curing, solvent resistance 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 cured product has insufficient solvent resistance.
In the subsequent thermal curing stage, the unreacted photopolymerizable functional groups are cleaved and polymerized during thermal curing, and the carboxylic acid groups and hydroxyl groups in the resin undergo an ester reaction, thereby improving the crosslink density of the coating film. However, when the firing and curing temperature is low, the above reaction does not occur sufficiently. This is the cause of insufficient solvent resistance of the cured product when the baking temperature is low.

The radical polymerization reaction occurs when radicals are generated from the photopolymerization initiator by ultraviolet rays, and the photopolymerizable functional group is radically polymerized. Absorption is strong, radical generation of the photopolymerization initiator is difficult to occur, and sufficient resistance cannot be obtained. Alternatively, if the colorant contains a dye, it is difficult for the photopolymerization initiator to generate radicals due to the absorption in the ultraviolet region, and in addition, it is easy to dissolve in the solvent due to its nature, so sufficient resistance cannot be obtained. cause.
The present inventors have found that the initiator contains a carbazole-based oxime compound having a maximum absorption wavelength in the range of 350 to 400 nm, and a phenyl-based oxime compound or acetophenone having a maximum absorption wavelength in the range of 300 to 350 nm. It has been found that the presence of at least one of the compounds has the effect of promoting radical generation in the ultraviolet region, improving crosslink density, and improving solvent resistance.

The application of the photosensitive coloring composition of the present embodiment is not particularly limited, but by imparting developability, it can be used as a negative photoresist 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 and developed, and the remaining photocured portion is heated. It should be thermally cured. An organic solvent or an alkaline aqueous solution can be used in the development process of photolithography.

When the photosensitive composition of the present embodiment is used as a negative photoresist, both pattern resolution and solvent resistance can be achieved regardless of whether alkali development or solvent development is used.
In the case of a photosensitive coloring composition that does not contain the above initiators (D1) and (D2) in the initiator, the concentration of the photopolymerizable functional group or the photopolymerization initiator is increased in order to increase the solvent resistance, or the exposure amount is increased. Therefore, it is necessary to increase the crosslink density in photocuring. However, with these designs, when the pattern is exposed, the photopolymerization reaction spreads outside the opening of the mask, causing photocuring in an area larger than the mask size, resulting in a pattern larger than the mask size after development. There is a strong tendency to be In addition, the photopolymerizable functional groups that have not reacted in the photocuring process do not undergo sufficient thermal polymerization at low temperatures of 80 to 150°C even in the heat-curing process that follows exposure and development. It is difficult to obtain the effect of improvement. Therefore, in order to improve the solvent resistance, there is no choice but to rely on a design that promotes the photopolymerization reaction, resulting in a trade-off between pattern resolution and solvent resistance. In particular, photosensitive compositions for color filters are required to have excellent developability, but on the other hand, since they contain a coloring agent, photocuring is difficult to proceed, and excellent chemical resistance can be obtained, especially under low-temperature curing conditions. It is difficult. Therefore, it is very difficult to achieve both developability and solvent resistance.

Therefore, the initiator contains a carbazole-based oxime compound having a maximum absorption wavelength in the range of 350 to 400 nm, and at least a phenyl-based oxime compound or an acetophenone compound having a maximum absorption wavelength in the range of 300 to 350 nm. Having one eliminates 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 others, it can be suitably used as a photosensitive composition for color filters.
Next, each component of the photosensitive coloring composition of this embodiment will be described.

<Colorant (A)>
The photosensitive coloring composition of the present invention contains a coloring agent (A).
Colorants preferably used in the photosensitive coloring composition of the present invention are described below.

As the coloring agent contained in the photosensitive coloring composition of the present invention, organic or inorganic pigments and dyes can be used singly or in combination of two or more. Among the pigments, pigments having high color developability and high heat resistance are preferred, and organic pigments are usually used, but are not limited to these.
The photosensitive coloring composition of the present invention contains at least one selected from blue pigments (A1) having a phthalocyanine skeleton and dyes (A2).

<Blue Pigment Having Phthalocyanine Skeleton (A1)>
Examples of the blue pigment (A1) having a phthalocyanine skeleton include C.I. I. 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) are preferably used.

General formula (1)

[In general formula (1), X ₁ to X ₄ are each independently an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted cyclo an alkyl group, an optionally substituted heterocyclic group, an optionally substituted alkoxyl group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, or represents an optionally substituted arylthio group.
Y ₁ to Y ₄ each independently represent a halogen atom, a nitro group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group.
Z represents a hydroxyl group, a chlorine atom, -OP(=O)R ₁ R ₂ or -O-SiR ₃ R ₄ R ₅ . Here, R ₁ to R ₅ each independently represent a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxyl group. , or represents an aryloxy group which may have a substituent, and the R's may combine with each other to form a ring. m ₁ to m ₄ and _{n 1} to _{n 4 each independently} represent an _integer of ₀ to _{4 ;} 4, which may be the same or different. ]

The pigment used in the photosensitive coloring composition of the present invention can be made fine by salt milling or acid pasting. 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, the thickness is preferably 100 nm or less because a filter segment having a high contrast ratio can be formed. A preferred range is from 15 to 85 nm, and a particularly preferred range is from 25 to 85 nm. The primary particle size of the pigment was measured by directly measuring the size of the primary particles from an electron micrograph of the pigment taken by a TEM (transmission electron microscope). Specifically, the short axis diameter and long axis diameter of the primary particles of each pigment were measured, and the average was used 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 the cube of the obtained particle size, and the volume average particle size is taken as the average primary particle size.

The salt milling process is a process in which 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 is passed through a kneader. , 2-roll mill, 3-roll mill, ball mill, attritor, sand mill, or other kneader to mechanically knead while heating, followed by washing with water to remove water-soluble inorganic salts and water-soluble organic solvents. . The water-soluble inorganic salt functions as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment 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 width, and a sharp particle size distribution.

As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate, etc. can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. 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), from the viewpoint of both processing efficiency and production efficiency.

The water-soluble organic solvent has the function of moistening the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (miscible 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 Polypropylene glycol and the like are 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 salt milling the pigment, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resins used are preferably solid at room temperature, water-insoluble, and more preferably partially soluble in the above organic solvents. The amount of 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 pasting method is a method of producing a treated pigment by co-dissolving an organic pigment in a strongly acidic solvent and extracting the solution into water. Sulfuric acid, polyphosphoric acid, chlorosulfonic acid and the like can be used as the strongly acidic solvent. 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 and dissolved in a strongly acidic solvent, or after dissolving each in a strongly acidic solvent , the respective strongly acidic solvent solutions may be mixed. The order of addition when adding each powder to the strongly acidic solvent is not limited.

The amount of the strongly acidic solvent should be increased or decreased according to the concentration of the strongly acidic solvent, but is not particularly limited as long as it can dissolve them completely. 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 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 low temperatures. In addition, even if the amount is used in excess of this range, there is no merit in terms of quality and productivity is lowered, so it 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 of sulfuric acid is used, it is preferably 3° C. or higher and 60° C. or lower. The temperature is preferably 3°C or higher and 40°C or lower. If the temperature is less than 3° C., the sulfuric acid will solidify and it will be difficult to stir uniformly, which is not preferable. Moreover, when it melts at a temperature higher than the above temperature, the blue pigment (A1) having a phthalocyanine skeleton may decompose.

In the present invention, the temperature at which the strongly acidic solvent solution of the 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 when the temperature is lower than when the temperature is high, so it is preferable to carry out the precipitation at 0° C. or more and 60° C. or less. Any water that can be used industrially, such as tap water, well water, and hot water, can be used as the water used at that time. is preferred.

The method of mixing the strongly acidic 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 strongly acidic solvent solution into previously prepared ice water, or a method of continuously injecting it into running water using a device such as an aspirator.

The slurry obtained by the above method is filtered and washed to remove acidic components, and then dried and pulverized to obtain the pigment composition of the present invention.
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 coloring agent (A) in an amount of 65% by mass to 100% by mass in order to obtain good transmittance. More preferably, it is contained in an amount of 70% by mass to 100% by mass.

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

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

As the dye (A2) that can be preferably used in the present invention, when it is in the form of a dye, any of various dyes such as oil-soluble dyes, acid dyes, direct dyes, basic dyes, mordant dyes, and acid mordant dyes. It is preferable to have the form of
Moreover, pigments in the form of pigments include fluorescent pigments and lake pigments obtained by converting the above dyes into lakes.
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, since the hue is excellent.

[Oil-soluble dye]
Oil-soluble dyes include C.I. C.I. Those classified as I. basic and acid dyes include C.I. C.I. acid as a direct dye. It is classified as I. Direct. Here, the direct dye has a sulfonic acid group (--SO ₃ H, --SO ₃ Na) in its structure, and in the present invention, the direct dye is regarded as an acid dye.
Preferred dyes (A2) are specifically described below.

(Xanthene type)
(Xanthene dyes: xanthene dyes, their lake pigments)
In the case of xanthene-based dyes, the transmittance in the 650 nm region in the transmission spectrum is 90% or more, the transmittance is 75% or more in the 600 nm region, the transmittance is 5% or less in the 500 to 550 nm region, and the 400 nm region. and a transmittance of 70% or more is preferable. 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's it. Among them, xanthene-based basic dyes and xanthene-based acid dyes have spectral characteristics with high transmittance at 400 to 450 nm.

Among xanthene dyes, rhodamine dyes are preferable because they are excellent in color developability and durability.

(Form of xanthene dye as oil-soluble dye)
Specifically, xanthene oil-soluble dyes include C.I. Solvent Red 35, C.I. Solvent Red 36, C.I. Solvent Red 42, C.I. Solvent Red 43, C.I.
I. Solvent Red 44, C.I. Solvent Red 45, C.I. Solvent Red 46
, C.I. Solvent Red 47, C.I. Solvent Red 48, C.I. Solvent Red 49, C.I. Solvent Red 72, C.I. Solvent Red 73, C.I. Solvent Red 109, C C.I. Solvent Red 140, C.I. Solvent Red 141, C.I. Solvent Red 237, C.I. Solvent Red 246, C.I. Solvent Violet 2, C.I. Solvent Violet 10, etc. .
Among them, C.I. Solvent Red 35, C.I.
I. Solvent Red 36, C.I. Solvent Red 49, C.I. Solvent Red 10
9, C.I. Solvent Red 237, C.I. Solvent Red 246, and C.I. Solvent Violet 2 are more preferred.

(Form of xanthene dye as acid dye)
Acid dyes of xanthene dyes (xanthene acid dyes) include C.I. I. Acid Red 51 (erythrosine (food 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 preferred to use Acid Violet 9.
Among them, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 388, or C.I., which is a rhodamine acid dye. I. Acid Red 52 (acid rhodamine), C.I. I. Acid Red 289, Acid Rhodamine G, C.I. I. More preferably, Acid Violet 9 is used.
Among these, C.I. I. Acid Red 52, C.I. I. Most preferably, Acid Red 289 is used.

(Form of xanthene dye as basic dye)
Examples of xanthene-based basic dyes include C.I. I. Basic Red 1 (Rhodamine 6GCP), 8 (Rhodamine G), C.I. and I. Basic Violet 10 (Rhodamine B). Among them, C.I. I. Basic Red 1, C.I. I. Basic Violet 10 is preferably used.

(Form of xanthene dye as lake pigment)
Examples of 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, and CI Pigment Red 81:3. I. Pigment Red 81:4, C.I. Pigment Red 81:
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 characteristics with high transmittance at 400 to 440 nm.

(Form of diphenyl and triphenylmethane dyes as acid dyes)
Acid dyes of diphenyl and triphenylmethane dyes include Food Blue No. 101 (C.I. Acid Blue 1), Acid Pure Blue (C.I. Acid Blue 3), Lake Blue I (C.I. Acid Blue 5), Lake Blue II (C.I. Acid
Blue 7) Food Blue No. 1 (C.I. 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. Preferably Acid Blue 109 is used.

(Forms of Diphenyl and Triphenylmethane Dyes as Basic Dyes)
Triphenylmethane-based basic dyes and diphenylmethane-based basic dyes develop color by oxidation of NH2 or OH groups para to the central carbon to form a quinone structure.
It is classified into the following three types according to the number of NH ₂ and OH groups. Among them, triaminotriphenylmethane-based basic dyes are preferred in terms of developing good blue, red, and green colors. .
a) diaminotriphenylmethane-based basic dyes b) triaminotriphenylmethane-based basic dyes c) rosolic acid-based basic dyes having an OH group triaminotriphenylmethane-based basic dyes, diaminotriphenylmethane-based basic dyes Dyes are preferred because they have a vivid color tone and are superior to other dyes in light fastness. Diphenylnaphthylmethane basic dyes and/or triphenylmethane basic dyes are also preferred.

Specifically, C.I. I. Basic Blue 1 (Basic Cyanine 6G), Basic Cyanine 5 (Basic Cyanine EX), Basic Blue 7 (Victoria Pure Blue BO), Basic Blue 25 (Basic Blue GO), and Basic Blue 26 (Victoria Blue B conc.).
C. Examples include I. Basic Green 1 (Brilliant Green GX) and Basic Green 4 (Malachite Green).
C. I. Basic Violet 1 (Methyl Violet), I. Basic Violet 3 (Crystal Violet), I. Basic Violet 14 (Magenta) and the like.

(Form of Diphenyl and Triphenylmethane Dyes as Lake Pigments)
Specific examples of triarylmethane-based lake pigments include 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. Pigment Blue 62, CI Pigment Violet 3, CI Pigment Violet 27, CI Pigment Violet 39 and the like.
More specifically, preferred
C. I. Pigment Blue 1.
C. I. Basic Blue 26, C.I. Phosphotungsten I. Basic Blue 7
Laked with molybdic acid.
C. I. Pigment Violet 3.
C. I.Basic Violet 1 is made into a lake with phosphotungstic molybdic acid.
C. I. Pigment Violet 39;
C. I. Basic Violet 3 (Crystal Violet)
Laked with molybdic acid.
Among them, C.I. I. Pigment Blue 1 is preferably used.

(Quinoline dyes: quinoline dyes, quinoline pigments)
Quinoline dyes include Solvent Yellow 33, Solvent Yel
Low 98, Solvent Yellow 157, Disperse Yellow
54, Disperse Yellow 160, Acid Yellow 3, and other commercially available dyes.
Examples of quinoline pigments include C.I. I. Pigment Yellow 138 (B.A.
Pariotol Yellow K0961-HD manufactured by S.F.) and the like.

(thiazine dye)
Thiazine dyes include Lauth's Violet obtained by oxidizing P-phenylenediamine in the presence of hydrogen sulfide under FeCl ₂ , methylene blue, methylene green B, C.I. 25, Solvent Blue 8, C.I. Basic Green 5, C.I. Direct Red 70 and the like.

(thiazole dye)
As the thiazole dye, a dye having a thiazole ring is called a thiazole dye.
Specifically, C.I. Basic Yellow 1, C.I. Basic Violet 44, 46, C.I. Basic Blue 116, C.I. Acid Yellow 186, C.I. 17, 18, 22, 28, 29, 30, 54, 59, 165, C.I. Direct Orange 18, C.I. Direct Red 11, and the like.

<chlorination>
The dye (A2) has good spectral characteristics and excellent color development, but has problems with light resistance and heat resistance. Its properties may not be sufficient.
Therefore, in order to improve these drawbacks, in the case of the form of a basic dye, it is preferable to use a salt-forming compound (Z1) which is salt-formed using an organic acid or perchloric acid. As the organic acid, it is preferable to use an organic sulfonic acid or an organic carboxylic acid. Among them, it is preferable to use naphthalenesulfonic acid such as Tobias acid and perchloric acid in terms of resistance.
In addition, in the case of the form of anionic dyes represented by acid dyes,
a salt-forming compound (Z2) produced using a cationic compound represented 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) obtained by sulfonamidation to obtain a sulfonic acid amide compound,
It is preferable to use as in terms of resistance.

Among these, (Z2) and (Z3) are particularly preferred because of their excellent durability and compatibility with pigments, and (Z2) is more preferred.
In (Z2), cationic compounds typified by quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, and primary amine compounds include:
A resin component having a cationic group represented by a quaternary ammonium base, a tertiary amino group, a secondary amino group, or a primary amino group can be preferably used.

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

(anionic dye)
Next, the anionic dye for obtaining the salt-forming compound of the present invention will be explained. As the anionic dye, any coloring compound having an anionic group that ionically bonds with the above-described cationic group may be used. Such coloring compounds are not particularly limited as long as they have a carboxylic acid group, a sulfonic acid group, a phenolic hydroxyl group, a phosphoric acid group, or metal salts thereof in the molecule. It can be appropriately selected in consideration of all required properties such as solubility in liquid, salt-forming property, absorbance, interaction with other components in the present composition, light resistance, and heat resistance.

Examples of anionic dyes include anthraquinone anionic dyes, monoazo anionic dyes, disazo anionic dyes, oxazine anionic dyes, aminoketone anionic dyes, xanthene anionic dyes, quinoline anionic dyes, Examples include triphenylmethane-based anionic dyes. Specific examples of anionic dyes that can be used in synthesizing 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.

Also, 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, 12
2:1, 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, 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, etc. can also be used.

As a yellow dye, 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, 192, 199 and the like.

Also, 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, etc. can also be used.

As an orange dye, 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.
Also, 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, etc. 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, 262, 264, 266, 269, 271, 272, 273, 274, 277, 278, 280 and the like.

Also, C.I. I. Direct Blue 1,2,3,4,6,7,8,8:1,9,10,1
2, 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, also used can.

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. is mentioned.

Also, 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, etc. 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, 37, 38, 40, 41, 42, 44, 54, 55, 59, 66, 69, 70, 71, 81, 84, 94, 95 and the like.
Also, C.I. I. Direct green 11, 13, 14, 24, 30, 34, 38, 42, 49, 55, 56, 57, 60, 78, 79, 80, etc. can also be used.

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

[Salt-Forming Compound of Anionic Dye and/or Sulfonic Acid Amide Compound of Anionic Dye]
Acid dyes preferably used as anionic dyes are salted using quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, primary amine compounds, etc., and resin components having these functional groups, and acid dyes or by sulfonamidation to form a salt-forming compound of a sulfonic acid amide compound, 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 decylamine (myristylamine), pentadecylamine, cetylamine, stearylamine, oleylamine, cocoalkylamine, beef tallow alkylamine, hardened beef tallow alkylamine, aliphatic unsaturated primary amines such as allylamine, aniline, benzylamine, and the like. .

Secondary amine compounds include aliphatic unsaturated secondary amines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine and diallylamine, methylaniline, ethylaniline, dibenzylamine, diphenylamine, dicocoalkyl Amines, di-cured beef tallow alkylamines, distearylamines, etc.

Tertiary amine compounds include trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, dimethylaniline, diethylaniline, tribenzylamine and the like.

Among the dyes (A2) used in the present invention, it is particularly preferable to use an anionic dye by salification using a cationic compound or by sulfonamidating an anionic dye, and these two forms are described below. I will elaborate.

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

(Cationic compound)
The cationic compound is not particularly limited as long as it has at least one onium base. Preferred onium salt structures include ammonium salts, iodonium salts, sulfonium salts, diazonium salts, and the like from the viewpoint of availability. Salts and phosphonium salts are preferred, and ammonium salts, iodonium salts and sulfonium salts are more preferred in consideration of storage stability (thermal stability). Quaternary ammonium salt compounds are more preferred.
As the quaternary ammonium salt compound, a resin component having a quaternary ammonium base can be preferably used.

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

Specific examples of ethylenically unsaturated monomers having a quaternary ammonium salt group, ethylenically unsaturated monomers having an amino group, onium chloride agents, and other ethylenically unsaturated monomers are shown below. In this specification, "(meth)acryl" may be used to refer to either or both of "acryl and methacryl". Similarly, when indicating either or both of "acryloyl and methacryloyl", it may be described as "(meth)acryloyl".

Ethylenically unsaturated monomers having a quaternary ammonium base include, for example, (meth)acryloyloxyethyltrimethylammonium chloride, (meth)acryloyloxyethyltriethylammonium chloride, (meth)acryloyloxyethyldimethylbenzylammonium chloride, (meth) ) Alkyl (meth)acrylate quaternary ammonium salts such as acryloyloxyethylmethylmorpholino ammonium chloride, (meth)acryloylaminopropyltrimethylammonium chloride, (meth)acryloylaminoethyltriethylammonium chloride, (meth)acryloylaminoethyldimethylbenzyl Alkyl(meth)acryloylamide-based quaternary ammonium salts such as ammonium chloride, dimethyldiallylammonium methylsulfate, trimethylvinylphenylammonium chloride and the like are included.

Ethylenically unsaturated monomers having an amino group include, for example, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dipropylaminoethyl (meth)acrylate, diisopropylaminoethyl (meth)acrylate, dibutylamino Ethyl (meth)acrylate, diisobutylaminoethyl (meth)acrylate, di-t-butylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylamide, diethylaminopropyl (meth)acrylamide, dipropylaminopropyl (meth)acrylamide, diisopropyl (Meth)acrylic acid esters or (meth)acrylamides having a dialkylamino group such as aminopropyl (meth)acrylamide, dibutylaminopropyl (meth)acrylamide, diisobutylaminopropyl (meth)acrylamide, di-t-butylaminopropyl (meth)acrylamide styrenes having a dialkylamino group such as dimethylaminostyrene and dimethylaminomethylstyrene; diallylamine compounds such as diallylmethylamine and diallylamine; amino compounds such as N-vinylpyrrolidine, N-vinylpyrrolidone and N-vinylcarbazole A group-containing aromatic vinyl-based monomer can be mentioned.

Examples of onium chloride agents include alkyl sulfates such as dimethyl sulfate, diethyl sulfate, and dipropyl sulfate; sulfonate esters such as methyl p-toluenesulfonate and methyl benzenesulfonate; methyl chloride, ethyl chloride, propyl chloride; Examples include alkyl chlorides such as octyl chloride, alkyl bromides such as methyl bromide, ethyl bromide, propyl bromide and octyl bromide, benzyl chloride and benzyl bromide.

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

Alternatively, alkoxycarbonylalkyl halides can be used as onium chloride agents. Alkoxycarbonylalkyl halide is represented by the following general formula (102).

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

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

Other ethylenically unsaturated monomers are particularly limited as long as they are 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 depending on the application.
From the viewpoint of heat resistance and developability, other ethylenically unsaturated monomers 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 preferred to have hydroxyl groups and/or carboxyl groups in particular.

Examples of ethylenically unsaturated monomers having a hydroxyl group include, but are not limited to, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, Glycerol mono(meth)acrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl acrylate or caprolactone adducts of these monomers (addition mole number is preferably 1 to 5).

Examples of ethylenically unsaturated monomers having a carboxyl group include, for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid, and ethylenic monomers having a carboxylic anhydride group. Examples of unsaturated monomers include maleic anhydride and itaconic anhydride.

Ethylenically unsaturated monomers having an oxetanyl group include 3-(acryloyloxymethyl)3-methyloxetane, 3-(methacryloyloxymethyl)3-methyloxetane, 3-(acryloyloxymethyl)3-ethyloxetane, 3-(methacryloyloxymethyl) 3-ethyloxetane, 3-(acryloyloxymethyl) 3-butyloxetane, 3-(methacryloyloxymethyl) 3-butyloxetane, 3-(acryloyloxymethyl) 3-hexyloxetane and 3- (Methacryloyloxymethyl)3-hexyloxetane and the like.

Ethylenically unsaturated monomers having a t-butyl group include t-butyl acrylate and t-butyl methacrylate.

Ethylenically unsaturated monomers having an isocyanate group include, for example, 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 4-isocyanatobutyl methacrylate and 4-isocyanatobutyl acrylate.

The isocyanate group in the present invention includes a blocked isocyanate group, which can be preferably used. A blocked isocyanate group means that under normal conditions, the isocyanate group is protected with another functional group to suppress the reactivity of the isocyanate group, while the isocyanate group can be deprotected by heating to regenerate the active isocyanate group. Indicates an isocyanate-blocked product.

Commercially available ethylenically unsaturated monomers having such blocked isocyanate groups include, for example, 2-[(3,5-dimethylpyrazolyl)carboxyamino]ethyl methacrylate (Karenzu MOI-BP, manufactured by Showa Denko); 2-(0-[1'methylpropylideneamino]carboxyamino)ethyl methacrylate (Karenzu MOI-BM, manufactured by Showa Denko) and the like.

Moreover, as an ethylenically unsaturated monomer having a blocked isocyanate group, a commercially available product can be used, or it can be prepared by a known method and used. 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 performed. It can be obtained by separating using

The amount of the quaternary ammonium base present in the resin having a quaternary ammonium base is not particularly limited, but the ammonium salt value of the resin is preferably 10 to 200 mgKOH/g, preferably 20 to 130 mgKOH/g. is more preferable.
In order for the ammonium salt value of the resin to satisfy the above range, the preferred content of the structural unit having a quaternary ammonium base is 4 to 74% by weight in the total 100% by weight of the structural units constituting the resin, A more preferred 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 weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) is 1,000 to 500,000. is preferable, and 3,000 to 15,000 is more preferable.

Quaternary ammonium salt compound other than resin having quaternary ammonium salt A preferred form of the quaternary ammonium salt compound other than resin having quaternary ammonium salt 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 must not interfere with the color development of the dye component and cause no color change.

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

general formula (11)

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

By setting the number of C atoms in the side chains of at least two or more of R ¹⁰¹ to R ¹⁰⁴ to 5 to 20, the solubility in solvents is improved. If three or more alkyl groups having less than 5 carbon atoms among R ¹⁰¹ to R ¹⁰⁴ are used, the solubility in solvents will deteriorate, and foreign substances in the coating film will tend to occur. In addition, if an alkyl group having more than 20 carbon atoms is present in the side chain, the salt-forming compound may be impaired in its coloring property.

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, preferably halogen, usually chlorine.

Specific examples of such quaternary ammonium salt compounds include tetramethylammonium chloride (the cation moiety has a molecular weight of 74), tetraethylammonium chloride (the cation moiety has a molecular weight of 122), and monostearyltrimethylammonium chloride (the cation moiety has a molecular weight of 312), distearyldimethylammonium chloride (molecular weight of cationic moiety is 550), tristearylmonomethylammonium chloride (molecular weight of cationic moiety is 788), cetyltrimethylammonium chloride (molecular weight of cationic moiety is 284), trioctylmethylammonium chloride ( dioctyldimethylammonium chloride (molecular weight of cationic moiety is 270), monolauryltrimethylammonium chloride (molecular weight of cationic moiety is 228), dilauryldimethylammonium chloride (molecular weight of cationic moiety is 382), Laurylmethylammonium chloride (molecular weight of cationic moiety is 536), triamylbenzylammonium chloride (molecular weight of cationic moiety is 318), trihexylbenzylammonium chloride (molecular weight of cationic moiety is 360), trioctylbenzylammonium chloride (molecular weight of cationic moiety is 444), trilaurylbenzylammonium chloride (cationic moiety has a molecular weight of 612), benzyldimethylstearylammonium chloride (cationic moiety has a molecular weight of 388), and benzyldimethyloctylammonium chloride (cationic moiety has a molecular weight of 248), or dialkyl (Alkyl is C ₁₄ -C ₁₈ ) dimethylammonium chloride (hardened beef tallow) (molecular weight of cationic moiety is 438-550) and the like are preferably used.

Products include Cortamine 24P, Cortamine 86P Conc, Cortamine 60W, Cortamine 86W, Cortamine D86P, Sanizol C, Sanizol B-50 manufactured by Kao Corporation, Arcade 210-80E, 2C-75, 2HT-75 manufactured by Lion Corporation. 2HT flake, 2O-75I, 2HP-75, or 2HP flake, among others, Cortamine D86P (distearyldimethylammonium chloride), or Arcade 2HT-75 (dialkyl (alkyl is C ₁₄ -C ₁₈ ) dimethylammonium chloride). etc. are preferable.

The molecular weight of the cationic portion of the quaternary ammonium salt compound other than the resin having a quaternary ammonium salt is preferably in the range of 190-900. The cationic portion corresponds to the (NR ¹⁰¹ R ¹⁰² R ¹⁰³ R ¹⁰⁴ ) ⁺ portion in general formula (11). If the molecular weight is less than 190, the light resistance and heat resistance may be lowered, and the solubility in solvents may be lowered. Further, if the molecular weight is more than 900, the ratio of the coloring component in the molecule is lowered, so that the coloring property may be lowered and the brightness may be lowered. More preferably, the molecular weight of the cationic moiety is in the range of 240-850, and particularly preferably in the range of 350-800.
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.

(Method for producing salt-forming compound)
A salt forming compound of an anionic dye and a cationic compound can be produced by a conventionally known method. A specific method is disclosed in Japanese Patent Application Laid-Open No. 11-72969.
For example, after dissolving an anionic dye in water, a cationic compound may be added and chlorinated while stirring. Here, the sulfonic acid group (--SO ₃ H) in the anionic dye
, a salt-forming compound is obtained in which the sodium sulfonate group (--SO ₃ Na) portion and the ammonium group (NH ₄ ⁺ ) portion of the cationic compound are combined. In place of water, methanol and ethanol are also usable solvents for chlorination.

The ratio of the cationic compound to the anionic dye is the composition of the present invention as long as the molar ratio of all cationic units of the cationic compound to all anionic groups of the anionic dye is in the range of 10/1 to 1/4. The salt compound can be suitably adjusted, and more preferably in the range of 2/1 to 1/2.

As the salt-forming compound, 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, excellent solvent solubility can be obtained. When used in combination with the pigment described later, the heat resistance, light resistance, and solvent resistance are further improved. It is presumed that the reason why the salt-forming compound is used in combination with the pigment is that the salt-forming compound is adsorbed to 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, which will be described later, is 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 preferred.

[Sulfonic acid amide compound of acid dye]
Sulfonic acid amide compounds of acid dyes that can be preferably used for the dye (C) are obtained by chlorinating acid dyes having --SO ₃ H and --SO ₃ Na in a conventional manner to convert --SO ₃ H to --SO ₂ Cl.
and this compound can be prepared by reaction with an amine having a --NH ₂ group.
Amine compounds that can be preferably used in sulfonamidation include, specifically, 2-ethylhexylamine, dodecylamine, 3-decyloxypropylamine, 3-(2-ethylhexyloxy)propylamine, and 3-ethoxypropyl. Amines, cyclohexylamines and the like are preferably used.
For example, C.I. I. When obtaining a sulfonic acid amide compound obtained by modifying Acid Red 289 with 3-(2-ethylhexyloxy)propylamine, C.I. I. Acid Red 289 was sulfonyl chlorided and then reacted with the theoretical equivalent of 3-(2-ethylhexyloxy)propylamine in dioxane to give C.I. I. A sulfonic acid amide compound of Acid Red 289 may be obtained.
Also, C.I. I. Acid Red 52 is also modified with 3-(2-ethylhexyloxy)propylamine to obtain a sulfonic acid amide compound. I. Acid Red 52 is sulfonyl chlorided and then reacted with the theoretical equivalent of 3-(2-ethylhexyloxy)propylamine in dioxane to give C.I. I. A sulfonic acid amide compound of Acid Red 52 may be obtained.

[Salt-Forming Compound Consisting of Basic Dyes and Organic Acid and Inorganic Acid Compounds]
Basic dyes are even poorer in light resistance and heat resistance, and their properties are not sufficient for use in image display devices using color filters that require high reliability. Therefore, in order to improve the drawbacks of these dyes, it is preferable to chlorinate the basic dye using an organic acid or an inorganic acid. As the organic acid, organic sulfonic acid and organic carboxylic acid are preferably used, and naphthalenesulfonic acid is particularly preferably used. Tobias acid is particularly preferred. Moreover, 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 coloring agent (A) in an amount of 15% by mass to 100% by mass in order to obtain good color characteristics. From the viewpoint of solvent resistance and coloring power, it is more preferable to contain 20% by mass to 60% by mass.
In the photosensitive coloring composition of the present invention, the total content of the blue pigment (A1) having a phthalocyanine skeleton and the dye (A2) is 65% by mass to 100% by mass in the coloring agent (A). It is preferable because good coloring power can be obtained. More preferably, it is 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 with color index numbers.

Red photosensitive compositions for forming red filter segments include, for example, C.I. I. Pigment 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, 168, 176, 177, 178, 179, 180, 184, 185, 187, 192, 200, 202, 207, 208, 209, 210, 215, 216, 217, 220, 221, 223, 224, 226, 227, Red pigments such as 228, 240, 242, 246, 254, 255, 264, 269, 272, 279 can be used. A yellow pigment and an orange pigment can be used together in the red photosensitive composition.
Furthermore, as the azo pigment, a naphthol azo pigment represented by the following general formula (2) is preferable.

general formula (2)

[In 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 each independently represent 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 , represents -NHCOR ¹² or -SO ₂ NHR ¹³ ; R ⁷ to R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
with the proviso that 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. ]

Among the naphthol azo pigments represented by the general formula (2), preferably an azo pigment in which at least one of R ² to R ⁶ is a trifluoromethyl group, or an azo pigment in which at least one of R ² to R ⁶ is —NHCOR An azo pigment having a number of ¹² is preferable because it is easy to make the pigment particles finer and has an excellent contrast ratio.

As the naphthol azo pigment represented by the general formula (2), C.I. I. Pigment Red 31, 32, 146, 147, 150, 184, 187, 188, 210, 238, 245, 247, 266, 268, 269, C.I. I. Violet 25, 50 and the like. Among these, C.I. I. Pigment Red 150, 170, 187, 266, 268, 269 are preferred.

In general formula (2), the "substituent" of the optionally substituted phenyl group in A includes a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a cyano trifluoromethyl group, nitro group, hydroxyl group, carbamoyl group, N-substituted carbamoyl group, sulfamoyl group, N-substituted sulfamoyl group, carboxyl group, sulfo group, carboxyl group or sulfo group. trivalent metal salts (eg, sodium salts, potassium salts, aluminum salts, etc.) and the like. Accordingly, specific examples of the phenyl group which may have a substituent include a phenyl group, p-methylphenyl group, 4-tert-butylphenyl group, p-nitrophenyl group, p-methoxyphenyl group, o-triphenyl 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-carboxyphenyl group, 2-methyl-4-sulfophenyl group and the like. However, it is not limited to these.

In A, the "substituent" of the optionally substituted heterocyclic group 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, trifluoro monovalent to trivalent metal of acidic group selected from methyl group, nitro group, hydroxyl group, carbamoyl group, N-substituted carbamoyl group, sulfamoyl group, N-substituted sulfamoyl group, carboxyl group, sulfo group, carboxyl group or sulfo group Salts (eg, sodium salts, potassium salts, aluminum salts, etc.) and the like are included. Further, the term "heterocyclic ring" means one 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. Furthermore, it may be a monocyclic ring or a condensed ring. Therefore, the heterocyclic ring includes pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, isoxazole ring and isothiazole ring. , triazole ring, thiadiazole ring, oxadiazole ring, quinoline ring, benzofuran ring, indole ring, morpholine ring, pyrrolidine ring, piperidine ring, tetrahydrofuran ring and the like. Therefore, the heterocyclic group means a monovalent free radical derived from these heterocyclic rings by removing a hydrogen atom. pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrrolyl group, 3-pyrrolyl 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-indolyl group, 2-indolyl group, 2-benzofuryl group, 2-benzothienyl group, 2-quinolino group, Examples include an N-carbazolyl group.

Halogen atoms for R ² to R ⁶ and R ¹⁴ include fluorine, chlorine, bromine and iodine.

Further, the alkyl group having 1 to 4 carbon atoms in R ¹ to R ¹⁴ may be linear or branched, and specific examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group and isobutyl group. , sec-butyl group and tert-butyl group.

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

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

Naphthol azo pigments are water-insoluble pigments that have excellent fastness to solvents and light. By using these pigments, coloring compositions for color filters that are excellent in both brightness and contrast ratio can be obtained. can be obtained.
Naphthol azo pigments may be used alone or in combination of two or more.

Examples of yellow pigments 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, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, etc. can be used.
Among the above, isoindoline-based pigments and quinophthalone-based pigments are preferable. Among these, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 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 brightness and coloring power.
The quinophthalone compound represented by general formula (3) will be described.

General formula (3)

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

Here, halogen atoms include fluorine, chlorine, bromine and iodine.

In the optionally substituted alkyl group, the number of carbon atoms in the alkyl group (not including the number of carbon atoms in the substituent) is preferably 1-10. Examples of substituents include halogen atoms, alkoxy groups having 1 to 10 carbon atoms, nitro groups, and aryl groups having 6 to 18 carbon atoms, and may have two or more substituents. Alkyl groups which may have a substituent include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, neopentyl group, n-hexyl group, 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, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxypen Alkyl groups having substituents such as a diyl group, a 4-nitrobenzyl group and a 2,4-dichlorobenzyl group are included.

In the alkoxyl group which may have a substituent, the number of carbon atoms in the alkoxyl group (not including the number of carbon atoms in the substituent) is preferably 1-10. Examples of substituents include halogen atoms, alkoxy groups having 1 to 10 carbon atoms, nitro groups, and aryl groups having 6 to 18 carbon atoms, and may have two or more kinds of substituents. Alkoxy groups which may have a substituent include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isoptyloxy, tert-butyloxy, neopentyloxy, 2,3- Linear or branched alkoxyl groups such as dimethyl-3-pentoxy, n-hexyloxy, n-octyloxy, stearyloxy and 2-ethylhexyloxy, trichloromethoxy, trifluoromethoxy, 2, 2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropyloxy group, 2,2-ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group , an alkoxyl group having a substituent such as a benzyloxy group.

In the aryl group which may have a substituent, the number of carbon atoms in the aryl group (not including the number of carbon atoms in the substituent) is preferably 6-18. Examples of the substituent include 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, an amino group, and the like. good too. Examples of the aryl group which may have a substituent include aryl groups such as a phenyl group, a naphthyl group and an anthranyl group, as well as p-methylphenyl group, p-bromophenyl group, p-nitrophenyl group and p-methoxyphenyl group. 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, anthraquinonyl group, 2-aminoanthraquinonyl group, and other substituted aryl groups.

Examples of acidic groups include —SO ₃ H and —COOH. Examples of monovalent to trivalent metal salts of these acidic groups include sodium salts, potassium salts, magnesium salts, calcium salts, iron salts, Examples include aluminum salts. Examples of alkylammonium salts of acidic groups include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine and stearylamine; quaternary alkyl salts such as palmityltrimethylammonium, dilauryldimethylammonium and distearyldimethylammonium salts; Ammonium salts are mentioned.

_{The " substituent _ _ _} "" includes the above halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxyl group, an optionally substituted aryl group, and the like.

Adjacent groups of X1 to X4 and/or X10 to X13 in general formula (3) are combined to form at least one aromatic ring which may have a substituent. The aromatic ring referred to herein includes aromatic hydrocarbon rings and heteroaromatic rings. Examples of aromatic hydrocarbon rings include benzene, naphthalene, anthracene, and phenanthrene rings. Examples of heteroaromatic rings include pyridine ring, pyrazine ring, pyrrole ring, quinoline ring, quinoxaline ring, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, oxazole ring, thiazole ring, imidazole ring, pyrazole ring, indole ring, carbazole ring and the like.
Moreover, these yellow pigments can be used individually or in combination of 2 or more types.

Examples of orange pigments include C.I. I. Pigment orange 36, 38, 43, 51, 55, 59, 61, 71, 73, etc. can be used.
Moreover, these orange pigments can be used individually or in combination of 2 or more types.

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

Blue pigments include, for example, C.I. I. Blue pigments such as Pigment Blue 16, 22, 60, 64, 80 can be used.
Purple pigments include 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. Metal lake pigments such as rhodamine dyes such as Pigment Red 81, 81:1, 81:2, 81:3, 81:4 and 81:5 can be used together. Furthermore, the yellow pigment mentioned above can be used together for chromaticity adjustment.

Examples of black pigments include carbon black, aniline black, anthraquinone black pigments, perylene black pigments, and specifically C.I. I. Pigment Black 1, 6, 7, 12, 20, 31, etc. can be used.
A mixture of red, blue and green pigments can also be used in the black photosensitive composition. As the black pigment, carbon black is preferable because of its price and high light-shielding properties, and the carbon black may be surface-treated with a resin or the like. Moreover, 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 (red iron oxide (III)), cadmium red, ultramarine blue, Prussian 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 applicability, sensitivity, developability, and the like while balancing chroma and lightness. Further, for toning, a dye can be contained within a range that does not lower the heat resistance.

Based on the total non-volatile components of the photosensitive composition (100% by mass), the concentration of the coloring agent (A) is preferably 5% by mass or more, more preferably 10% by mass or more, most preferably 10% by mass or more, from the viewpoint of obtaining sufficient color reproducibility. Preferably, it is 15% by mass or more. Further, 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, because the stability of the photosensitive composition is improved.
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 (100% by mass). 35% by mass or more is most preferable in some cases. According to the present 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 color filters is lower than the above, depending on the type of colorant, photoradical polymerization may be inhibited, making it difficult to obtain good chemical resistance. , the present invention has the advantage that good chemical resistance is 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 developing solubility in an alkali developing step, and has an acid group. Moreover, a resin having a radically polymerizable group is used in order to further improve the photosensitivity.

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 the coating film is formed by exposure to the active energy ray. Heat resistance is improved, and fading of the colorant due to heat (degradation of spectral characteristics) can be suppressed. It also has the effect of suppressing aggregation and deposition of pigment components in the development process.

The alkali-soluble resin (B) having an aradical 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 range of 400 to 700 nm in the visible light region. is preferred.

The weight-average molecular weight (Mw) of the alkali-soluble resin (B) having a radically polymerizable group in the present invention is 2,000 or more and 10,000 or less, preferably 3,000 or more and 9,000 or less, and 4,000 or more, in order to impart alkali developing solubility. 8000 or less is more preferable. Also, the value of Mw/Mn is preferably 10 or less. If the weight-average molecular weight (Mw) is less than 2000, the adhesiveness to the substrate is lowered and the exposure pattern is less likely to remain. If it exceeds 10,000, the solubility in alkali development will be lowered, and a residue will be generated to deteriorate the linearity of the pattern. The acid value of the alkali-soluble resin in the present invention is 50 or more and 200 or less (KOHmg/g) for imparting alkali development solubility, preferably 100 or more and 180 or less, more preferably 110 or more and 170 or less. Range. If the acid value is less than 50, the solubility in alkali development is lowered, and residues are generated, which deteriorates the linearity of the pattern. 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 to be 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, it is used in an amount of 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 expressed.

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)) and 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 copolymer (B7) having a hydroxyl group formed by ring-opening a group is obtained, and a resin ( b1) is preferred.
The resin obtained by the reaction is a mixture of various products, not all reactive functional groups in the reaction between epoxy group and acid and between hydroxyl group and acid anhydride. Therefore, since it is impossible or almost impractical to specify and describe the alkali-soluble resin (B) having a radically polymerizable group, the manufacturing method will be described.

<<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. to obtain a copolymer (B6), the obtained copolymer (B6) and a compound (B4) having an unsaturated monobasic acid are reacted to obtain a copolymer (B7), and further obtained It is a resin obtained by reacting a copolymer (B7) and 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 properties.

<Compound (B1) having at least one unsaturated bond>
Compounds (B1) having at least one unsaturated bond include the following (a), (b), (c), and (d), compounds having an epoxy group and an unsaturated bond in one molecule (B2
).

一般式（１２）：

(b) A compound having an aromatic ring group represented by general formula (11) or general formula (12):
General formula (11):

General formula (12):

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

化学式（１５）：

(b) A compound having an alicyclic group represented by chemical formula (14) or chemical formula (15):
Chemical formula (14):

Chemical formula (15):

(C) Other compounds (f2)

Compound (a), compound (b), and compound (c) are described in order below. As used herein, the weight percent content of each compound is the weight percent of the precursor that provides each compound to resin (C1).

[Compound (a)]
The compound (a) has a cyclic structure with an aromatic ring group 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 amount of 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 developing time becomes long, and the productivity deteriorates.

General formula (11):

General formula (12):

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

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

General formula (13):

(In 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 atom optionally having a benzene ring. number 1 to 20
and n is an integer of 1-15. )

Examples of ethylenically unsaturated monomers represented by formula (13) include:
Daiichi Kogyo Seiyaku Co., Ltd. New Frontier CEA [EO-modified cresol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : methyl group, n=1 or 2], NP-2 [n-nonylphenoxypolyethylene 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 to 17], or PHE [phenoxyethyl acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n=1],
Daicel Corporation, IRR169 [ethoxylated phenyl acrylate (EO 1 mol), R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n=1] or Ebecryl 110 [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 (n ≈ 2) acrylate manufactured by Toagosei Co., Ltd. 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 : hydrogen atom, R ₇ : propylene group, R ₈ : n-nonyl group, 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 [phenoxypolyethylene 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],
NOF CORPORATION BLEMMER ANE-300 [nonylphenoxy polyethylene glycol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : -nonyl group, n≈5], ANP-300 [nonylphenoxy polypropylene glycol acrylate, R ₆ : hydrogen atom, R ₇ : propylene 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 a 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 [phenoxypolyethylene 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 [phenoxy polyethylene 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],
NK ESTER AMP-10G [phenoxyethylene glycol acrylate (EO1 mol), R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n=1] manufactured by Shin Nakamura Chemical Co., Ltd., AMP-20G [phenoxyethylene glycol acrylate (EO 2 mol), R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n≈2], AMP-60G [phenoxyethylene glycol acrylate (EO 6 mol), R ₆ : hydrogen atom, R ₇ : 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],
Osaka Organic Chemical Co., Ltd. Viscoat #192 [phenoxyethyl acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n=1], or
Nippon Kayaku 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 : hydrogen atom, R ₇ : ethylene group, R ₈ : n-nonyl group], etc., but two or more types may be used in combination without being limited to these.

In the ethylenically unsaturated monomer represented by formula (13), the alkyl group of R ₈ has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. Alkyl groups include not only linear alkyl groups, but also branched alkyl groups and alkyl groups having a benzene ring as a substituent. When the number of carbon atoms in the alkyl group of R ₈ is 1 to 10, the adhesion to the substrate is enhanced, but when the number of carbon atoms exceeds 10, the long alkyl group tends to hinder the adhesion to the substrate. This tendency becomes more conspicuous as the carbon chain length of the alkyl group of _R8 becomes longer. 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 formula (13), n is preferably an integer of 1-15. If n exceeds 15, the hydrophilicity increases and the solvation effect decreases, the viscosity of the resin (A1) increases, and the viscosity of the photosensitive composition using the resin (A1) also increases, affecting fluidity. may give. From the viewpoint of solvation, n is particularly preferably 1 to 4.

As the precursor of compound (a), from the viewpoint of copolymerization with other precursors and chemical resistance, styrene, α-methylstyrene, benzyl acrylate, benzyl methacrylate, or general formula (7) The indicated ethylenically unsaturated monomers are preferred. These are particularly preferred because they can introduce a benzene ring 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 developability. Furthermore, benzyl acrylate and/or benzyl methacrylate are most preferred from the viewpoint of development residue.

[Compound (b)]
Compound (b) has a cyclic structure with an alicyclic group represented by chemical formulas (14) and (15), imparts hardness, and functions as a hydrophobic site to an alkaline developer. Based on the weight of all constituent compounds of the resin (A), the content of the compound (b) is preferably 2 to 40% by weight from the viewpoint of developability and hardness. If the amount is less than 2% by weight, the developability and hardness may be insufficient, and a problem may arise in that a high-quality touch panel coating film cannot be obtained. In addition, due to insufficient hydrophobicity during development, problems of pattern peeling and chipping occur in the pixel portion. If it exceeds 40% by weight, the dissolution rate in an alkaline developer becomes slow, the development time becomes long, and the productivity of the coating film deteriorates.

Chemical formula (14):

Chemical formula (15):

Precursors of the compound (ii) include ethylenically unsaturated monomers represented by general formula (16) and ethylenically unsaturated monomers represented by general formula (17).
General formula (16):

General formula (17):

[In general formulas (16) and (17), R ₉ is a hydrogen atom or a methyl group, and R _1
0 is an alkylene group having 2 or 3 carbon atoms, and m is an integer of 1-15. ]

Examples of ethylenically unsaturated monomers represented by formula (16) include:
Fancryl FA-513A [dicyclopentanyl acrylate, R ₉ : hydrogen atom, R ₁₀ : none, m=0] manufactured by Hitachi Chemical Co., Ltd., or FA-513M [dicyclopentanyl methacrylate, R ₉ : methyl, R ₁₀ : none, m=0], etc., but two or more types can be used in combination without being limited to these.

Examples of unsaturated ethylene monomers represented by the general formula (17) include:
Hitachi Chemical Funcryl 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], etc., but two or more types can be used in combination without being limited to these.

[Compound (C)]
Compound (c) is an ethylenically unsaturated monomer other than compounds (a) and (b), which is a precursor of compounds (a) and (b), and an ethylenically unsaturated monomer There is no particular limitation as long as it is copolymerizable. Among them, 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.

Ethylenically unsaturated monomers having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol (Meth)acrylates and hydroxyalkyl (meth)acrylates such as cyclohexanedimethanol mono(meth)acrylate can be mentioned, and these may be used alone or in combination of two or more. In addition, polyether mono(meth)acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide, etc. to the above hydroxyalkyl (meth)acrylate, (poly)γ-valerolactone, (poly)ε-caprolactone , and/or (poly)ester mono(meth)acrylates added with (poly)12-hydroxystearic acid and the like can also be used. 2-Hydroxyethyl (meth)acrylate or glycerol (meth)acrylate is preferred from the viewpoint of suppressing coating film foreign substances.

Ethylenically unsaturated monomers having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis[(meth)acryloyloxy]ethyl isocyanate, but are limited to these. Alternatively, two or more types can be used in combination.

The side chain type cyclic ether-containing monomer is, for example, an unsaturated compound containing at least one skeleton selected from the group consisting of a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton, and a lactone skeleton.
The tetrahydrofuran skeleton includes tetrahydrofurfuryl (meth)acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, (meth)acrylic acid tetrahydrofuran-3-yl ester;
As the furan skeleton, 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-hexene-3-one, 6-furan-2-yl-hex-1-ene -3-one, 2-furan-2-yl-1-methyl-ethyl acrylate, 6-(2-furyl)-6-methyl-1-hepten-3-one and the like;
As the tetrahydropyran skeleton, (tetrahydropyran-2-yl)methyl methacrylate, 2,6-dimethyl-8-(tetrahydropyran-2-yloxy)-oct-1-en-3-one, tetrahydropyran 2-methacrylate -2-yl esters, 1-(tetrahydropyran-2-oxy)-butyl-3-en-2-one and the like;
As the pyran skeleton, 4-(1,4-dioxa-5-oxo-6-heptenyl)-6-methyl-2-pyrone, 4-(1,5-dioxa-6-oxo-7-octenyl)-6 -methyl-2-pyrone and the like;
As the lactone skeleton, 2-methyl-tetrahydro-2-oxo-3-furanyl 2-propenoate, 2-methyl-7-oxo-6-oxabicyclo[3.2.1]oct-2-propenoate, 2-methyl-hexahydro-2-oxo-3,5-methano-2H-cyclopenta[b]furan-7-yl ester of 2-propenoic acid, 2-methyl-tetrahydro-2-oxo-2-propenoic acid 2H-pyran-3-yl ester, 2-propenoic acid (tetrahydro-5-oxo-2-furanyl) methyl ester, 2-propenoic acid hexahydro-2-oxo-2,6-methanofuro[3,2-b]- 6-yl ester, 2-methyl-2-propenoic acid 2-(tetrahydro-5-oxo-3-furanyl)ethyl ester, 2-methyl-decahydro-8-oxo-5,9-methano-2H 2-propenoic acid -furo[3,4-g]-1-benzopyran-2-yl ester, 2-methyl-2-[(hexahydro-2-oxo-3,5-methano-2H-cyclopenta[b]furan 2-propenoate -6-yl)oxy]ethyl ester, 2-propenoic acid 3-oxo-3-[(tetrahydro-2-oxo-3-furanyl)oxy]propyl ester, 2-propenoic acid 2-methyl-2-oxy-1 -oxaspiro[4.5]dec-8-yl ester and the like.
Among these, tetrahydrofurfuryl (meth)acrylate is preferred from the viewpoint of coloration 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, and n (meth)acrylate. -butyl, isobutyl (meth)acrylate, t-butyl (meth)acrylate, methyl 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 2- (meth)acrylate (Meth)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 and acrylonitrile; vinyl esters such as vinyl acetate; Among these, methyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, and styrene are preferred because they have good transparency and are less likely to impair heat resistance. These other copolymerizable monomers may be used alone or in combination of two or more.

The polymerization reaction method of the monomer component is not particularly limited, and conventionally known various polymerization methods can be employed, but the solution polymerization method is particularly preferred. The polymerization temperature and 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 Preferably, the polymerization temperature is 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

The alkali-soluble resin (B) having a radically polymerizable group is a compound (B1) having at least one or more unsaturated bonds such as the above compounds (a) to (c), 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 resulting copolymer (B6) and a compound having an unsaturated monobasic acid (B4
) to obtain a copolymer (B7), and further obtained by reacting the obtained copolymer (B7) with a polybasic acid anhydride (B5)

<Compound (B2) having an epoxy group and an unsaturated bond in one molecule>
Examples of the compound (B2) having an epoxy group and an unsaturated bond in one molecule include ethylenically unsaturated monomers having an epoxy group, such as glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 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. I don't mind. Glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with the unsaturated monobasic acid in the next step.

<Compound (B4) having unsaturated monobasic acid>
Examples of unsaturated monobasic acids include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted (meth)acrylic acid. Monocarboxylic acids and the like can be mentioned, and these may be used alone or in combination of two or more.

<Polybasic acid anhydride (B5)>
Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. These may be used alone or in combination of two or more. I don't mind. If necessary, such as increasing the number of carboxyl groups, use a tricarboxylic anhydride such as trimellitic anhydride, or use a tetracarboxylic dianhydride such as pyromellitic dianhydride to remove the remaining anhydride. It is also possible to hydrolyze the group and the like. Moreover, when tetrahydrophthalic anhydride or maleic anhydride having a radically polymerizable double bond is used as the polybasic acid anhydride, the number of radically polymerizable double bonds 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, most preferably 350 g/mol or more and 1000 g/mol or less. If the double bond equivalent weight of the resin (b1) is more than 1300 g/mol, the development rate will be slow, and even if patterning is possible, the coating film will have a large amount of residue. If the double bond equivalent is less than 350 g/mol, the amount of cross-linking components is too large, resulting in poor stability and brittle coating films.

<<Other resins (B6)>>
The photosensitive composition of the present invention may further contain other resins. When the other resin (B6) is a copolymer, it corresponds to a resin containing no radically polymerizable group or a resin containing no alkali-soluble group.
The other resin (B6) is preferably 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. Other resins include thermoplastic resins, thermosetting resins, and photosensitive resins, and these can be used alone or in combination of two or more.

Examples of thermoplastic resins include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl resin, polyvinyl chloride resin, polyvinylidene chloride resin, vinyl chloride-vinyl acetate copolymer, polyvinyl Vinyl acetate, polyurethane resin, polyester resin, acrylic resin, methacrylic resin, alkyd resin, polystyrene resin, silicone resin, fluorine resin, polyamide resin, rubber resin, cyclized rubber resin, chlorinated rubber, oxidized rubber, hydrochloric acid Examples include rubber, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resin, petroleum resin, casein, shellac, nitrocellulose, cellulose acetate butyrate, but are not necessarily limited to these.

Examples of thermosetting resins include epoxy resins, benzoguanamine resins, melamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, rosin-modified maleic acid resins, rosin-modified phenolic resins, urea resins, amino resins, phenolic resins, non- Examples include saturated polyester resins, drying oils, synthetic drying oils, and the like, but are not necessarily limited to these. They can also be used in combination as a thermal cross-linking agent for the thermoplastic resin.

Examples of photosensitive resins include linear polymers having reactive substituents such as hydroxyl groups, carboxyl groups, and amino groups, and (meth)acrylic compounds and cinnamon compounds having reactive substituents such as isocyanate groups, aldehyde groups, and epoxy groups. A resin obtained by reacting an acid to introduce a photocrosslinkable group such as a (meth)acryloyl group or a styryl group into the linear polymer is used. In addition, linear polymers containing acid anhydrides such as styrene-maleic anhydride copolymers and α-olefin-maleic anhydride copolymers are treated with (meth)acrylic compounds having hydroxyl groups such as hydroxyalkyl (meth)acrylates. A half-esterified one is also used. However, it is not necessarily limited to these.

<Polyfunctional (meth)acrylate monomer (C)>
The photosensitive coloring composition in the invention contains a polyfunctional (meth)acrylate monomer (C). Polyfunctional (meth)acrylate monomers (C) include monomers or oligomers that are cured by ultraviolet light, heat, or the like to form transparent resins.
Among the polyfunctional (meth)acrylate monomers (C), trimethylolpropane triacrylate is preferred because of its excellent chemical resistance. Commercially available products include M-309 (manufactured by Toagosei Co., Ltd.), Viscoat #295 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), and A-TMPT (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).

Examples of other polyfunctional (meth)acrylate monomers (C) include trimethylolpropane trimethacrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, and ethylene oxide. Examples include various acrylic acid esters and methacrylic acid esters such as modified trimethylolpropane tri(meth)acrylate and propylene oxide-modified trimethylolpropane tri(meth)acrylate.

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

In addition, it is preferable to contain a polyfunctional monomer having an acidic group, for example, free hydroxyl group-containing poly (meth) acrylates of polyhydric alcohol and (meth) acrylic acid, and esters of dicarboxylic acids; polyvalent carboxylic acid and esters of monohydroxyalkyl (meth)acrylates. Specific examples include monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. and free carboxyl group-containing monoesters with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid and terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic 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, 2-hydroxyethyl acrylate, 2- Monohydroxy monoacrylates such as hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, and free carboxyl group-containing oligoesters with monohydroxy monomethacrylates can be mentioned.

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 [wherein 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, h is an integer of 2 to 18, and i is an integer of 1 to 3. ]

Here, the compound represented by general formula (18) can be easily obtained, for example, by the following method.
(1) A method in which a compound giving an organic group represented by X is esterified with acrylic acid to acrylate, and then a mercapto compound is added to the resulting compound. (2) A compound giving an organic group represented by X. is modified with a polyisocyanate compound, the obtained compound is acrylated with an acrylate compound having a hydroxyl group, and then a mercapto compound is added to the obtained compound. (3) Giving an organic group represented by X A method of esterifying a compound with acrylic acid to acrylate it, modifying it with a polyisocyanate compound, and adding a mercapto compound to the resulting compound.

Examples of compounds that provide an organic group represented by X include pentaerythritol, caprolactone-modified pentaerythritol, polyisocyanate-modified pentaerythritol, dipentaerythritol, caprolactone-modified dipentaerythritol, and polyisocyanate of dipentaerythritol. Modifications can be mentioned.

Mercapto compounds include, for example, mercaptoacetic acid, 2-mercaptopropionic acid,
3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, mercaptosuccinic acid and the like.

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 polyfunctional (meth)acrylate monomer (C) is less than 5% by weight, the effect of increasing the surface hardness and imparting solvent resistance cannot be obtained, and if it is more than 40% by weight, the resolution necessary for patterning cannot be obtained. I can't More preferably, it is 5 to 30% by weight.

<<Photoinitiator (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 within the range of 350 to 400 nm. as an essential ingredient.

<Carbazole-based oxime compound (D1) having a maximum absorption wavelength in the range of 350 to 400 nm>
Component (D1) has a maximum absorption wavelength in the wavelength range of 350 to 400 nm even in the presence of a blue pigment (A1) having a phthalocyanine skeleton or a dye (A2), so it can sufficiently generate radicals. . Thereby, the curing of the coating film can be sufficiently advanced.
Furthermore, it is more preferable that the component (D1) has a nitro group.
Examples of such a (D1) component include NCI-831 (manufactured by ADEKA).
The carbazole-based oxime compound (D1) having a maximum absorption wavelength in the range of 350 to 400 nm in the present invention is used 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 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 necessary for patterning cannot be obtained. More preferably, it is 0.01 to 3% by weight.

In addition, the photosensitive coloring composition of the present invention further contains at least one phenyl-based oxime compound or acetophenone compound (D2) having an absorption maximum wavelength in the range of 300 to 350 nm as a photopolymerization initiator (D). contains
<Phenyl Oxime Compound or Acetophenone Compound (D2) Having Maximum Absorption Wavelength in the Range of 300 to 350 nm>
Component (D2) usually cannot sufficiently cure a coating film in the presence of blue pigment (A1) having a phthalocyanine skeleton or dye (A2), but it can be used in combination with component (D1). Curing progresses to the deep part of the coating film, and the chemical resistance becomes very good. (D1) When used alone, hardening of the film surface proceeds easily, but hardening does not reach deep portions, and erosion from the pattern edge surface is likely to occur due to immersion in chemicals. In the present invention, using either one of (D1) and (D2) alone does not result in good chemical resistance, and synergistic effects are produced by the combined use.
Furthermore, the ratio of (D1) and (D2) used together is (D1) / (D2) = 5/95 to 30/
70 is preferred. More preferably, (D1) / (D2) = 5/95 to 20/
80, most preferably (D1)/(D2)=5/95 to 10/90. Component (D1
) is not contained above a certain level, the curing of the coating film does not proceed sufficiently. On the other hand, if the component (D1) is used excessively, the light absorption performance of the component (D1) itself impairs the color characteristics as a coloring composition. to become
(D2) as the component, for example,
1,2-octadione-1-[4-(phenylthio)-,2-(o-benzoyloxime)], phenyl oxime compounds such as ethanone, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, Diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) -butan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl] -1-[4-(4-morpholinyl)phenyl]-1-butanone and other acetophenone compounds.
The phenyl-based oxime compound or acetophenone compound (D2) having an absorption maximum wavelength within the range of 300 to 350 nm in the present invention is 0.1 to 10% by weight in 100% by weight of the total solid content of the photosensitive resin composition. is preferably used in an 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 Photoinitiators (D3)>
Other photopolymerization initiators can also be used in combination with the photosensitive coloring composition of the present invention. Specifically, benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, and acrylated benzophenone. , 4-benzoyl-4′-methyldiphenyl sulfide, 3,3′,4,4′-tetra(t-butylperoxycarbonyl)benzophenone compounds such as benzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, Thioxanthone compounds such as isopropylthioxanthone, 2,4-diisopropylthioxanthone, 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-(naphth-1-yl)-4,6-bis(trichloro methyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, 2,4-trichloromethyl(4′-methoxystyryl)-6-triazine, triazine compounds such as compounds described in JP-B-59-1281, JP-B-61-9621, and JP-A-60-60104, 1,2- Octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], JP-A-2001-264530, JP-A-2001-261761, JP-A-2000-80068, JP-A-2001-233842, Special table 2004-534797, JP 2006-342166, JP 2008-094770, JP 2009-40762, JP 2010-15025, JP 2010-189279, JP 2010-189280, special table 2010-526846, special table 2010- 527338, JP 2010-527339, USP3558309 (1971), USP4202697 (1980), JP-A 61-24558, JP2012-519191, JP2012-526185, JP2013-543875, oxime ester compounds such as compounds described in JP-A-2011-209710, bis(2,4,6-trimethylbenzoyl)phenyl Phosphine oxide, phosphine compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2 '-biimidazole, 2,2'-bis(o-methoxyphenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-chlorophenyl)-4,4', 5,5′-tetra(p-methylphenyl)biimidazole, imidazole compounds such as compounds described in JP-A-55-127550 and JP-A-60-202437, 9,10-phenanthrenequinone, camphorquinone, quinone compounds such as ethyl anthraquinone, borate compounds such as compounds described in JP-A-2-157760, carbazole compounds, titanocene compounds such as compounds described in JP-A-61-151197, JP-A-59-1504, Organic peroxides such as compounds described in JP-A 61-243807, JP-B 43-23684, JP-B 44-6413, JP-B 47-1604, diazonium compounds such as compounds described in USP No. 3567453, USP No. 2848328 specification, USP No. 2852379 specification, organic azide compounds such as compounds described in USP No. 2940853 specification, JP-B-36-22062, JP-B-37-13109, JP-B-38-18015, JP-B-45 -ortho-quinone diazides, such as the compounds described in 9610, described in JP-B-55-39162, JP-A-59-140203, "MACROMOLECULES", Vol. 10, p. 1307 (1977) Various onium compounds including iodonium compounds, azo compounds such as 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 allene complexes such as the compounds described in “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 organic halogen compounds such as the compounds of , sulfonium complexes and oxosulfonium complexes described in JP-A-5-255347, and the like.

These photopolymerization initiators (D) can be used singly or as a mixture of two or more at any ratio as required. The photopolymerization initiator (D) is preferably 0.01 to 60 parts by mass, more preferably 0.01 to 10 parts by mass, still more preferably 0.01 to 60 parts by mass in 100 parts by mass of the solid content in the photosensitive coloring composition. 03 to 7 parts by mass. It is preferably 0.01 parts by mass or more from the viewpoint of photopolymerization, that is, the progress of the polymerization reaction, and suppresses deterioration of transparency due to the effect of yellowing of the initiator and pattern resolution due to excessive photopolymerization during exposure. It is preferably 10 parts by mass or less from the viewpoint of suppressing a decrease in the

Furthermore, the photosensitive coloring composition of the present invention can contain a sensitizer. Examples of sensitizers include 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 derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indolines derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyr Radin derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, Michler ketone derivatives, biimidazole derivatives, etc. is mentioned.

Further specific examples include Shin Okawara et al., "Dye Handbook" (1986, Kodansha), Shin Okawara et al., "Chemistry of Functional Dyes" (1981, CMC), Chuzaburo Ikemori et al., "Special Functional Materials" (1986, CMC), but are not limited to these. In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region can also be included. The sensitizer may contain two or more sensitizers in any ratio.

The sensitizer is preferably used in an amount of 0.1 to 150 parts by weight with respect to 100 parts by weight of the photopolymerization initiator (D) in the photosensitive coloring composition, and is used in an amount of 1 to 100 parts by weight. is more preferable.

<<Other Materials>>
The photosensitive coloring composition of the present invention can further contain the following materials as long as they do not impair the object of the invention.

<Organic solvent>
An organic solvent may be used in order to improve handling when applying the photosensitive coloring composition. 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, ethylbenzene , xylene, cyclohexane, hexane, octane, cyclomethane, chloroform, dimethylformamide, dimethylacetamide, acetonitrile, dimethylsulfoxide, and the like. These can be used singly or in combination of two or more.
Among them, it is preferable to use a ketone-based, ester-based, or ether-based solvent because the solubility of other constituents is good.

The amount of the organic solvent used is preferably such that the solid 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 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 coating the photosensitive composition, smoothness of the obtained film or fine pattern, and transparency. is 5% by mass or more, it is easy to obtain a film and a pattern with a predetermined thickness.

When a colorant is added to the photosensitive coloring composition of the present invention to form a photosensitive coloring composition for a color filter, which will be described later, and a color filter segment or black matrix is produced, it is dried on a transparent substrate such as a glass substrate or a film substrate. It is applied so that the film thickness is 0.2 to 10 μm. Organic solvents are used to facilitate this, such as 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,3-butylene glycol diacetate, 4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate , 3-methyl-1,3-butanediol, 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 diethyl Butyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary 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, cyclo Hexanol 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 , methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid esters and the like are preferably used. These can be used singly 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, screen printing method, offset printing method, gravure printing method, etc. 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 (bp 168.1°C), ethylene glycol monobutyl ether (bp 171.2°C), ethylene glycol monohexyl ether (bp 208.1°C), ethylene glycol monobutyl ether acetate (bp 191.5°C), ethylene glycol dibutyl ether (bp 203. 3°C), diethylene glycol monomethyl ether (bp 194.0°C), diethylene glycol monoethyl ether (bp 202.0°C), diethylene glycol diethyl ether (bp 188.4°C), diethylene glycol monoisopropyl ether (bp 207.3°C), propylene glycol monobutyl ether (bp 170.2°C), propylene glycol diacetate (bp 190.0°C), dipropylene glycol monomethyl ether (bp 187.2°C), dipropylene glycol monoethyl ether (bp 197.8°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 (bp 172.5° C.) ), 3-methoxy-3-methylbutyl acetate (bp 188°C), γ-butyrolactone (bp 204°C), N,N-dimethylacetamide (bp 166.1°C), N-methylpyrrolidone (bp 202°C), p-chlorotoluene (bp162.0°C), o-diethylbenzene (bp183.4°C), m-diethylbenzene (bp181.1°C), p-diethylbenzene (bp183.8°C), o-dichlorobenzene (bp180.5°C), m- Dichlorobenzene (bp 173.0°C), n-butylbenzene (bp 183.3°C), sec-butylbenzene (bp 178.3°C), tert-butylbenzene (bp 169.1°C), cyclohexanol (b 161.1° C.), cyclohexyl acetate (bp 173° C.), methylcyclohexanol (bp 174° C.), etc., 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 10,000 parts by weight, preferably 500 to 5,000 parts by weight, per 100 parts by weight of the coloring agent in the photosensitive coloring composition for color filters.

<Polyfunctional thiol>
The photosensitive coloring composition of the present invention can contain a polyfunctional thiol. Polyfunctional thiols are compounds having two or more thiol (SH) groups.
By using the polyfunctional thiol together with the photopolymerization initiator (D) described above, in the radical polymerization process after light irradiation, it acts as a chain transfer agent and generates thiyl radicals that are less susceptible to polymerization inhibition by oxygen. The sensitive coloring composition becomes highly sensitive.
Polyfunctional aliphatic thiols in which SH groups are bonded to aliphatic groups such as methylene and ethylene groups are particularly preferred.
For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tris. thioglycolate, trimethylolpropane tristhiopropionate, trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptopropionate), Pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), trimercaptopropionate tris(2-hydroxy ethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine and the like. .
These polyfunctional thiols can be used singly or in combination 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, per 100 parts by mass of the colorant. Better development resistance can be obtained by using 0.05 parts by mass or more of the polyfunctional thiol. By using a thiol having multiple thiol (SH) groups, development resistance can be improved.

<Ultraviolet 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.
UV absorbers include, for example, 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-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, etc. hydroxyphenyltriazine series, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, Benzotriazoles such as 2-(3-tbutyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2' , 4,4′-tetrahydroxybenzophenone and other benzophenones, phenyl salicylate, p-tert-butylphenyl salicylate and other salicylates, ethyl-2-cyano-3,3′-diphenyl acrylate and other cyanoacrylates system, 2,2,6,6-tetramethylpiperidine-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 the like, and these are used singly or in combination.
Examples of polymerization inhibitors include hydroquinones such as methylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 4-benzoquinone, 4-methoxyphenol, 4-methoxy-1-naphthol and t-butylcatechol. Derivatives and phenolic compounds, amine compounds such as phenothiazine, bis-(1-dimethylbenzyl)phenothiazine, 3,7-dioctylphenothiazine, copper such as copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, manganese diphenyldithiocarbamate and manganese salt compounds, nitroso compounds such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, N-nitrosophenylhydroxylamine, and their ammonium salts or aluminum salts, which may be used singly or in combination. and use it.

The ultraviolet absorber and polymerization inhibitor are preferably 0.01 to 20 parts by weight, more preferably 0.05 to 10 parts by weight, per 100 parts by weight of the coloring agent in the photosensitive coloring composition.
Better resolution can be obtained by using 0.01 parts 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. Storage stabilizers include, for example, 2,6-bis(1,1-dimethylethyl)-4-methylphenol, pentaerythyryl-tetrakis[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 phosphines such as phenylphosphine and tetraphenylphosphine; phosphites such as zinc dimethyldithiophosphate, zinc dipropyldithiophosphate and molybdenum dibutyldithiophosphate; sulfur compounds such as dodecyl sulfide and benzothiophene; Examples include quaternary ammonium chlorides such as diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, methyl ethers thereof, and the like, which are used alone or in combination.

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

<Adhesion improver>
The photosensitive coloring composition of the present invention preferably contains an adhesion improver such as a silane coupling agent in order to improve adhesion to a transparent substrate. Adhesion improvers include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxysilane. 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 -chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatopropyltriethoxysilane and the like.
Among them, silane-based additives are preferable because they improve the adhesion to glass substrates, etc., and 3-methacryloxypropyltrimethoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltri Methoxysilane is particularly preferred.

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

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

A particularly preferable leveling agent is a type 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 when added to the photosensitive pigment composition. , It is characterized by its low surface tension lowering ability, and it is useful to have good wettability to a glass plate despite its low surface tension lowering ability, and an addition that does not cause defects in the coating film due to bubbling. Any amount that can sufficiently suppress electrification can be preferably used.
A dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used as a leveling agent having such preferred properties. Polyalkylene oxide units include polyethylene oxide units and polypropylene oxide units, and dimethylpolysiloxane may have both polyethylene oxide units and polypropylene oxide units.

In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane is a pendant type in which the polyalkylene oxide unit is bonded to the repeating unit of dimethylpolysiloxane, a terminal modified type in which the terminal is bonded to the terminal of dimethylpolysiloxane, and a dimethylpolysiloxane. It may be of any linear block copolymer type with alternating repeating bonds. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Dow Corning Toray Co., Ltd., such as FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ -2207, but not limited to.

Anionic, cationic, nonionic, or amphoteric surfactants can be added to the leveling agent as auxiliaries. Two or more kinds of surfactants may be mixed and used.
Examples of anionic surfactants added to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, and alkyldiphenyl ether disulfonic acid. Sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate and esters.

Cationic surfactants added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate. , polyethylene glycol monolaurate; alkylbetaines such as alkyldimethylaminoacetic acid betaine; amphoteric surfactants such as alkylimidazoline; and fluorine-based and silicone-based surfactants.

<Amine compound>
The photosensitive composition for color filters preferably contains an amine-based compound capable of reducing dissolved oxygen. Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylamino benzoate. ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl p-toluidine and the like.

<Others>
If necessary, additives such as a curing agent, a light stabilizer, an antioxidant, an inorganic filler, an adhesion imparting agent, and a surfactant may be added to the thermosetting resin. These additives can be added in any amount as long as the purpose of the resin composition is not impaired.

<<Method for producing a photosensitive coloring composition>>
The photosensitive coloring composition of the present invention comprises a coloring agent (A), an alkali-soluble resin (B) having a radically polymerizable group, a polyfunctional (meth)acrylate monomer (C), and a photopolymerization initiator (D).
, can be prepared by mixing and stirring other components as necessary.

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

<Method for producing photosensitive coloring composition for color filter>
One aspect of the present invention relates to a photosensitive coloring composition for color filters. Since the photosensitive coloring composition for a color filter contains a coloring agent, photocuring is difficult to progress, and the problem that chemical resistance and photolithography are in a trade-off relationship is particularly conspicuous. 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 color filters of the present embodiment, it is possible to achieve both chemical resistance and photolithography even under low-temperature curing conditions.
When a coloring agent 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-developing or alkali-developing colored resist material. The photosensitive coloring composition contains an alkali-soluble resin (B) having a radically polymerizable group
, a polyfunctional (meth)acrylate monomer (C), and a photopolymerization initiator (D), and a colorant dispersed therein. The photosensitive coloring composition for color filters is prepared by dispersing coloring agents such as pigments and dyes in pigment carriers such as resins and/or solvents using various dispersing means such as three-roll mill, two-roll mill, sand mill, kneader, and attritor. to produce a pigment dispersion by finely dispersing it, 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 optionally, a silane compound, a sensitizer, a polyfunctional thiol, an ultraviolet absorber, a polymerization inhibitor, a storage stabilizer, and other components are mixed and stirred. In addition, a photosensitive coloring composition containing two or more pigments is prepared by mixing each pigment dispersion separately and finely dispersed in a pigment carrier and / or solvent, and an alkali-soluble resin having a radically polymerizable group. (B), a polyfunctional (meth)acrylate monomer (C), a photopolymerization initiator (D), an organic solvent, etc. can be mixed and stirred for production.
The alkali-soluble resin (B) having a radically polymerizable group and the polyfunctional (meth)acrylate monomer (C) may be used as a pigment carrier when producing a pigment dispersion.

When dispersing the pigment in a pigment carrier such as a resin and/or a solvent, a dispersing aid such as a resin-type pigment dispersant, a surfactant, or a pigment derivative can be added as appropriate. Dispersing aids are excellent in dispersing pigments and have a great effect of preventing reaggregation of pigments after dispersion. When a coloring composition is used, a color filter with excellent transparency can be obtained.
The dispersing aid is preferably used in an amount of 0.1 to 40 parts by weight, more preferably 0.1 to 30 parts by weight, per 100 parts by weight of the pigment.

The resin-type pigment dispersant has a pigment affinity site that has the property of adsorbing to the pigment and a site that is compatible with the dye carrier, and acts to adsorb to the pigment and stabilize the dispersion of the pigment to the dye carrier. It is intended to Specific examples of resin-type pigment dispersants include polyurethanes, polycarboxylic acid esters such as polyacrylates, 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 thereof, amides formed by the reaction of poly(lower alkyleneimine) with polyesters having free carboxyl groups, and their Oil-based dispersants such as salts, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone, etc. soluble resins, water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide/propylene oxide adducts, phosphoric acid esters, etc., and these can be used alone or in combination of two or more.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by BYK-Chemie Japan. , 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 2410000, 2410000, 2410000, 2410000, 241000, 241000, 241000, 241000, 2000 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., EFKA-486, 47 manufactured by Chiba Japan Co., Ltd. , 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453 , 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. Ajinomoto Fine-Techno Co., Ltd. Ajisper PA111, PB711, PB821, PB822, PB824 etc. are mentioned.

Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, 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; cationic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethyl Alkylbetaines such as betaine aminoacetate and amphoteric surfactants such as alkylimidazolines can be mentioned, and these can be used alone or in combination of two or more.

A pigment derivative is a compound obtained by introducing a substituent into an organic pigment. Organic pigments include naphthalene-based, anthraquinone-based, and other pale yellow aromatic polycyclic compounds that are not generally called pigments. Pigment derivatives are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, etc. These can be used alone or in combination of two or more.

<Step of obtaining a coating film by applying a photosensitive composition onto a substrate>
The method of applying the photosensitive composition of the present invention to a glass substrate, ITO, metal film, organic film, etc. is not particularly limited, and examples thereof include dipping, spraying, roll coating, die coating, and spin coating. etc., and other printing methods such as screen printing, offset printing, and gravure printing can also be used for coating. It is also possible to form patterns by photolithography. Substrates include, for example, glass, ceramics, polycarbonate, polyester, urethane, acrylic, polyacetate cellulose, polyamide, polyimide, polystyrene, epoxy resin, polyolefin, polycycloolefin, polyvinyl alcohol, various metals such as stainless steel, and the like.
The thickness for manufacturing these display members is preferably 0.005 to 30 μm in a dry state, more preferably 0.01 to 20 μm, particularly 0.1 to 10 μm. preferable. By setting the thickness in such a range, suitable mechanical strength and heat resistance can be obtained, and there is little possibility of impairing the light transmittance.

The drying method after applying the photosensitive composition of the present invention to a substrate is not particularly limited, and can be changed depending on the type of each constituent component used in the photosensitive composition, the amount added (mixture amount), and the like. can. For example, a vacuum dryer, an oven, an infrared heater, etc. can be used. For negative photolithography, it is preferable to use a vacuum dryer that does not heat during drying so as not to deteriorate the developability of the unexposed areas. When heating using an oven, an infrared heater, etc., 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 through a mask>
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 is preferably used for irradiation with ultraviolet rays.
The photo-curing method is also not particularly limited. 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 varied depending on the type of each component used in the photosensitive composition, the amount added (mixed amount), etc., but usually the irradiation dose of ultraviolet rays is 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)>
Development can be carried out by immersing in a solvent or alkaline developer, or by spraying the developer with a spray or the like to remove uncured portions to 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. Moreover, an antifoaming agent or a surfactant can be added to the developer.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a puddle (liquid puddle) development method, or the like can be applied.

<Step of post-baking the pattern at 80° C. to 150° C. after step (iii)>
Regarding the thermosetting temperature after photocuring, it is necessary to change it depending on the heat resistance of the base material and other optical materials used, but as much as possible photopolymerization in the alkali-soluble resin (A) and the photopolymerizable compound (B) Among the functional groups, it is preferable to raise the temperature to a temperature at which those remaining unreacted in the photocuring step undergo a cross-linking reaction. More preferably, it is heat-cured at a temperature of 80° C. to 100° C. for 0.1 to 10 hours.

<Manufacturing method of color filter>
A method for producing a color filter using the photosensitive coloring composition for color filters of the present invention will be described.
The color filter is provided with a filter segment or a black matrix formed from a photosensitive coloring composition for a color filter on a transparent substrate. and at least one blue filter segment, or at least one magenta filter segment, at least one cyan filter segment, and at least one yellow filter segment.

According to the photolithographic method, the filter segments and black matrix can be formed with higher precision than printing methods such as screen printing, offset printing, and gravure printing. The formation of each color filter segment and black matrix by photolithography is performed by the following method. That is, a photosensitive colored composition for color filters prepared as a solvent-developable or alkali-developable colored resist material is coated on a transparent substrate by a coating method such as spray coating, spin coating, slit coating, roll coating, etc. to form a dry film thickness. is applied so that the thickness is 0.2 to 10 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact or non-contact with this film.
After that, it is immersed in a solvent or alkaline developer, or the developer is sprayed by spraying or the like to remove the uncured portion, and a desired pattern is formed to form a filter segment and a black matrix.
Further, heat curing is performed to impart chemical resistance to the filter segments and black matrix formed by development.

As the transparent substrate, glass plates such as soda lime glass, low-alkali borosilicate glass, alkali-free aluminoborosilicate glass, etc., and resin plates such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, etc. are used. A transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate for driving the liquid crystal after panelization.

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

A vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used to dry the coating film. The drying conditions can be changed depending on the type of each component used in the photosensitive composition for color filters, the amount added (mixed amount), etc. However, in order to carry out negative photolithography, it is necessary to develop the unexposed portion. In order not to deteriorate the properties, it is preferable to use a vacuum dryer which is not heated during drying. When heating using an oven, an infrared heater, etc., it is preferable to dry at a temperature of 40 to 80° C. for 1 minute to 1 hour. The heating temperature is preferably 60° C. or lower, more preferably 50° C. or lower, from the viewpoint of suppressing the generation of development residues due to crosslinking of the photosensitive composition.

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

In order to increase the UV exposure sensitivity, after applying and drying the photosensitive coloring composition for color filters, 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 due to oxygen. It is also possible to perform ultraviolet exposure after forming a film that does.

<Organic EL display device>
The organic EL display device in the present invention is a display device having a color filter formed from 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 nm.
have peak wavelengths (λ ₁ ) and (λ ₂ ) at which the emission intensity is maximum in the range of m and the wavelength range of 560 nm to 620 nm, and the emission intensity I _{1 at the wavelength λ 1 and} the emission intensity I ₂ at the wavelength λ ₂ (I ₂ /I ₁ ) preferably has an emission spectrum of 0.4 or more and 0.9 or less, more preferably 0.5 or more and 0.8 or less. Especially preferably, it is 0.5 or more and 0.7 or less.
When the emission spectrum has an emission spectrum in which the ratio (I ₂ /I ₁ ) of emission intensity I ₂ is 0.4 or more and 0.9 or less, high brightness and wide color reproducibility can be obtained, which is preferable.

Further, it preferably has a maximum emission intensity or a shoulder in the wavelength range of 530 nm to 650 nm.
A wavelength range of 430 nm to 485 nm is preferable when a color display device having the color filter displays blue with good color reproducibility. More preferably, it is in the range of 430 nm to 475 nm.
By using the organic EL element and the color filter that satisfy these configurations, it is possible to obtain a color display device having a wide color reproduction range and high brightness.

An organic EL element is composed of an element in which one or more organic layers are formed between an anode and a cathode. Here, the single-layer organic EL element refers to an element consisting only of a light-emitting layer between an anode and a cathode, while the multilayer-type organic EL element refers to a light-emitting layer in addition to holes and holes to the light-emitting layer. For the purpose of facilitating injection of electrons and smooth recombination of holes and electrons in the light-emitting layer, a hole-injection layer, a hole-transport layer, a hole-blocking layer, and an electron-injection layer are used. Refers to a stack of layers. Therefore, a typical element structure of a multilayer organic EL element is (1) anode/hole injection layer/light-emitting layer/cathode, (2) anode/hole-injection layer/hole transport layer/light-emitting layer/cathode. , (3) anode/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-transporting layer/light-emitting layer/hole-blocking layer/electron-injection layer/cathode, (7) Examples thereof include an element configuration in which a multilayer configuration such as anode/light emitting layer/hole blocking layer/electron injection layer/cathode and (8) anode/light emitting layer/electron injection layer/cathode are laminated. However, the organic EL element used in the present invention is not limited to these.

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

First, specific examples of materials that can be used for these layers are given. However, 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. There are also materials that are chemically doped conductive polymer compounds, such as polyethylenedioxythiophene (abbreviation: PEDOT) doped with polystyrene sulfonic acid (abbreviation: PSS) and polyaniline (abbreviation: PANI). can also In addition, inorganic semiconductor thin films such as molybdenum oxide (abbreviation: MoO _x ), vanadium oxide (abbreviation: VO _x ), and nickel oxide (abbreviation: NiO _x ), and inorganic insulating materials such as aluminum oxide (abbreviation: Al ₂ O ₃ ) Ultra-thin films of the body are also effective. Also, 4,4′,4″-tris(N,N-diphenyl-amino)-triphenylamine (abbreviation: TDATA), 4,4′,4″-tris[N-(3-methylphenyl) -N-phenyl-amino]-triphenylamine (abbreviation: MTDATA), 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-(4-( Aromatic amine compounds such as N,N-di-m-tolyl)amino)phenyl-N-phenylamino]biphenyl (abbreviation: DNTPD) can also be used. Further, a substance exhibiting acceptor properties for these aromatic amine compounds may be added to the aromatic amine compounds. Specifically, 2,3,5,6-tetrafluoro-7 , _7,8,8 -tetracyanoquinodimethane (abbreviation: F4-TCNQ) or α-NPD to which MoOx as an acceptor is added may be used.

Aromatic amine-based compounds are preferable as the material that can be used for the hole transport layer, and TDATA, MTDATA, TPD, α-NPD, DNTPD, etc. described in the hole injection material can be used.

Examples of electron-transporting materials that can be used in the electron-transporting layer include 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)benzoxazola and bis[2-(2-hydroxyphenyl)benzothiazolato]zinc (abbreviation: Zn(BTZ)2). Furthermore, in addition to metal complexes, 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (abbreviation: PBD), 1,3-bis[5- Oxadiazole derivatives such as (p-tert-butylphenyl)-1,3,4-oxadiazol-2-yl]benzene (abbreviation: OXD-7), 3-(4-tert-butylphenyl)-4 -Phenyl-5-(4-biphenylyl)-1,2,4-triazole (abbreviation: TAZ), 3-(4-tert-butylphenyl)-4-(4-ethylphenyl)-5-(4-biphenylyl) )-1,2,4-triazole (abbreviation: p-EtTA Z) and other triazole derivatives, 2,2′,2″-(1,3,5-benzenetriyl)tris[1-phenyl-1H-benz imidazole] (abbreviation: TPBI) and phenanthroline derivatives such as bathophenanthroline (abbreviation: BPhen) and bathocuproine (abbreviation: BCP) can be used.

Materials that can be used for the electron injection layer include the previously described Alq3, Almq3, BeBq2, BAlq, Zn(BOX) ₂ , Zn(BTZ) ₂ , PBD, OXD-7, TAZ, p-EtTAZ, TPBI, Electron transport materials such as BPhen, BCP can be used. In addition, ultra-thin insulating films such as alkali metal halides such as LiF and CsF, alkaline earth halides such as _CaF2 , and alkali metal oxides such as Li2O _are often used. Alkali metal complexes such as lithium acetylacetonate (abbreviation: Li(acac)) and 8-quinolinolato-lithium (abbreviation: Liq) are also effective. Further, a substance that exhibits a donor property to these electron injection materials may be added to the electron injection material, and alkali metals, alkaline earth metals, rare earth metals, or the like can be used as the donor. Specifically _, BCP to which lithium as a donor is added and Alq3 to which lithium as a donor is added can be used.

Further, for the hole blocking layer, a hole blocking material is used which can prevent holes passing through the light emitting layer from reaching the electron injection layer and can form a layer excellent in thin film formability. Examples of such hole-blocking materials include aluminum complex compounds such as bis(8-hydroxyquinolinate)(4-phenylphenolate)aluminum and bis(2-methyl-8-hydroxyquinolinate). Gallium complex compounds such as (4-phenylphenolato)gallium, nitrogen-containing condensed aromatic compounds such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (abbreviation: BCP) mentioned.

The light-emitting layer for obtaining white light is not particularly limited, but for example, the following can be used. That is, the energy level of each layer of an organic EL laminated structure is defined and light is emitted using tunnel injection (European Patent No. 0390551). What is described (JP-A-3-230584), what describes a two-layer structure light-emitting layer (JP-A-2-220390 and JP-A-2-216790), a plurality of light-emitting layers (JP-A-4-51491), which is divided and composed of materials with different emission wavelengths, and a blue light emitter (fluorescence peak of 380 to 480 nm) and a green light emitter (480 to 580 nm) are laminated, Furthermore, a structure containing a red phosphor (Japanese Patent Laid-Open No. 6-207170), a blue emitting layer containing a blue fluorescent dye, a green emitting layer having a region containing a red fluorescent dye, and further green fluorescent Examples include those having a structure containing a body (Japanese Patent Laid-Open No. 7-142169).

Further, as the light-emitting material used in the present invention, conventionally known light-emitting materials may be used. Compounds suitable for blue, green, orange to red emission are exemplified below. However, the light-emitting material is not limited to those specifically exemplified below.

Blue light emission can be obtained by using, for example, perylene, 2,5,8,11-tetra-t-butylperylene (abbreviation: TBP), 9,10-diphenylanthracene derivative, or the like as a guest material. In addition, styrylarylene derivatives such as 4,4'-bis(2,2-diphenylvinyl)biphenyl (abbreviation: DPVBi), 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). Polymers such as poly(9,9-dioctylfluorene) may also be used.

More preferred specific examples are shown in Table 1.

Green light emission is produced by coumarin pigments such as coumarin 30 and coumarin 6, bis[2-(2,4-difluorophenyl)pyridinato]picolinatoiridium (abbreviation: FIrpic), bis(2-phenylpyridinato)acetyl Acetonatoiridium (abbreviation: Ir (ppy) (a
cac)) or the like as a guest material. In addition, metal complexes such as tris(8-hydroxyquinoline) aluminum (abbreviation: Alq ₃ ), BAlq, Zn(BTZ), bis(2-methyl-8-quinolinolato)chlorogallium (abbreviation: Ga(mq) ₂ Cl) can also be obtained from Polymers such as poly(p-phenylene vinylene) may also be used.

More preferred specific examples are shown in Table 2.

Orange to red emission is from rubrene, 4-(dicyanomethylene)-2-[p-(dimethylamino)styryl]-6-methyl-4H-pyran (abbreviation: DCM1), 4-(dicyanomethylene)-2- Methyl-6-(9-julolidyl)ethynyl-4H-pyran (abbreviation: DCM2), 4-(dicyanomethylene)-2,6-bis[p-(dimethylamino)styryl]-4H-pyran (abbreviation: BisDCM) , bis[2-(2-thienyl)pyridinato]acetylacetonatoiridium (abbreviation: Ir(thp)2(acac)), bis(2-phenylquinolinato)acetylacetonatoiridium (abbreviation: Ir(pq)(acac )) as a guest material. It can also be obtained from metal complexes such as bis(8-quinokilinolato)zinc (abbreviation: Znq2) and bis[2-cinnamoyl-8-quinolinolato]zinc (abbreviation: Znsq2). Polymers such as poly(2,5-dialkoxy-1,4-phenylene vinylene) may also be used.

More preferred specific examples are shown in Table 3.

Furthermore, the material used for the anode of the organic EL element used in the present invention is preferably a material having a large work function (4 eV or more), an alloy, an electrically conductive compound, or a mixture thereof as an electrode material. Specific examples of such electrode materials include metals such as Au, and conductive materials such as CuI, ITO, SNO ₂ and ZNO. To form this anode,
A thin film can be formed from these electrode materials by a method such as a vapor deposition method or a sputtering method. It is desirable that the anode has such a characteristic that the transmittance of the light emitted from the anode is greater than 10% when the light emitted from the light-emitting layer is extracted from the anode. Also, the sheet resistance of the anode is preferably several hundred Ω/cm ² or less. Furthermore, the film thickness of the anode is usually selected in the range of 10 nm to 1 μm, preferably 10 to 200 nm, depending on the material.

In addition, the material used for the cathode of the organic EL element used in the present invention is an electrode material having a small work function (4 eV or less), an alloy, an electrically conductive compound, or a mixture thereof. Specific examples of such electrode materials include sodium, sodium-potassium alloys, magnesium, lithium, magnesium-silver alloys, aluminum/aluminum oxide, aluminum-lithium alloys, indium, and rare earth metals. 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 light emitted from the light-emitting layer is extracted from the cathode, it is preferable that the transmittance of the light emitted from the cathode is greater 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 of producing the organic EL device used in the present invention, the anode, the light-emitting layer, the hole injection layer if necessary, and the electron injection layer if necessary are formed by the materials and methods described above, and finally the cathode is formed. should be formed. Alternatively, the organic EL element can be fabricated in the reverse order from the cathode to the anode.

This organic EL element is produced on a translucent substrate. This light-transmitting substrate is a substrate for supporting the organic EL element, and the light-transmitting property thereof should preferably have a transmittance of 50% or more, preferably 90% or more, of light in the visible region of 400 to 700 nm. Furthermore, it is preferable to use a smooth substrate.

These substrates are not particularly limited as long as they have mechanical and thermal strength and are transparent. For example, glass plates and synthetic plates are preferably used. As a glass plate, especially saw
Plates molded from da-lime glass, barium-strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz, and the like can be mentioned. Examples of synthetic resin plates include plates of polycarbonate resin, acrylic resin, polyethylene terephthalate resin, polyether sulfide resin, polysulfone resin, and the like.

Methods for forming each layer of the organic EL element used in the present invention include dry film formation methods such as vacuum deposition, electron beam irradiation, sputtering, plasma, and ion plating, or spin coating, dipping, flow coating, and inkjet. Wet film forming methods such as methods, methods of vapor-depositing a luminescent material on a donor film, and methods disclosed in JP-T-2002-534782 and S.P. T. Lee, et al. , Proceedings of SID'02, p. 784 (2002), a LITI (Laser Induced Thermal Imaging) method, printing (offset printing, flexo printing, gravure printing, screen printing), ink jet, and the like can also be applied.

The organic layer is particularly preferably a molecular deposition film. Here, the term "molecule deposition film" refers to a thin film formed by deposition from a material compound in a gaseous state, or a film formed by solidifying a material compound in a solution or liquid phase. can be distinguished from the thin film (molecule-accumulated film) formed by the LB method based on differences in aggregation structure and higher-order structure, and functional differences resulting therefrom. Further, as disclosed in Japanese Patent Application Laid-Open No. 57-51781, a binder such as a resin and a material compound are dissolved in a solvent to form a solution, and then the solution is formed into a thin film by spin coating or the like. can also form an organic layer. The thickness of each layer is not particularly limited, but if the thickness is too thick, a large applied voltage is required to obtain a constant light output, resulting in poor efficiency. etc. occur, making it difficult to obtain sufficient luminance even when an electric field is applied. Therefore, the film thickness of each layer is suitably in the range of 1 nm to 1 μm, more preferably in the range of 10 nm to 0.2 μm.

In order to improve the stability of the organic EL element against temperature, humidity, atmosphere, etc., a protective layer may be provided on the surface of the element, or the entire element may be covered or sealed with resin or the like. In particular, when covering 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 device, but considering the power consumption and life of the device, it is desirable to emit light efficiently with as little electrical 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. In addition, as a method of extracting light from the organic EL element of this embodiment, not only a method called bottom emission, in which light is extracted from the anode side, but also a method called top emission, in which light is extracted from the cathode side, can be applied. These methods and techniques are described in Junji Kido, "All About Organic EL", Nihon Jitsugyo Publishing Co., Ltd. (published in 2003).

The main system of the full-color organic EL element used in the present invention is the color filter system. In the color filter method, an organic EL element that emits white light is used to extract light of three primary colors through a color filter. , the luminous efficiency of the entire device can be increased.

Furthermore, the organic EL device used in the present invention may employ 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, and emitted light causes multiple interference between the anode and the cathode. By appropriately selecting the optical characteristics such as the index and the film thickness of the organic layer sandwiched between them, it is a technology that actively utilizes the multiple interference effect and controls the emission wavelength extracted from the device. . This also makes it possible to improve the emission chromaticity. The mechanism of this multiple interference effect is described in J. Am. Yamada et al., AM-LCD Digest of Technical Papers, OD-2, p. 77-80 (2002).

As described above, RGB color filter layers are produced by arranging them side by side on a glass substrate or the like, and a light emitting layer (backlight) produced using the ITO electrode layer and the above organic EL element is placed on the color filter layer. Thus, color display becomes possible, and a color display device is obtained. In this case, a color display device with a high contrast ratio can be realized by controlling the current flow during light emission by the TFT.

<<Other uses>>
The application of the photosensitive composition of the present invention is not particularly limited, and it is used to manufacture color filters for organic EL display devices, color filters for quantum dot display devices, color filters for C-MOS, black matrices, various coatings, and the like. can be used to

EXAMPLES The embodiments of the present invention will be described in more detail below with reference to examples, but the following examples are not intended to limit the scope of rights of the present invention. In addition, "part" in an Example represents "mass part", and "%" represents "mass %."
In the following examples, the molecular weight of the resin is the polystyrene-equivalent weight-average molecular weight measured by GPC (gel permeation chromatography). was measured using three TSKgelSuperHM-M (manufactured by Tosoh Corporation) at a flow rate of 0.6 ml/min, an injection volume of 10 µl, and a column temperature of 40°C.

IR measurement was performed using Spectrum One manufactured by PerkinElmer. The acid value was measured as follows. About 1 g of a compound solution whose acid value is to be measured 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 subjected to potentiometric titration with a 0.1 N potassium hydroxide ethanol solution. A blank test was also conducted in the same manner. The non-volatile content of the target product was measured by heating at 200 ° C. for 10 minutes, and the obtained titration value and non-volatile content were calculated. The number of mg of was calculated|required.
In the present specification, the non-volatile content means a value calculated from the weight of the sample after heating/the weight of the sample before heating when 1 g of the sample is heated at 200° C. for 10 minutes. However, in the case of commercial products, a value calculated based on the method specified by the manufacturer may be adopted. As used herein, solid content and non-volatile content are synonymous.

Subsequently, the organic EL element, the alkali-soluble resin solution, the salt-forming dye resin, 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 are described. do.

<Production example of organic EL element>
An example of manufacturing an organic EL element used as a white light source will be specifically shown below. In the production examples of the organic EL device, all mixing ratios are weight ratios unless otherwise specified. Deposition (vacuum deposition) was performed in a vacuum of 10 ^-6 Torr without temperature control such as substrate heating and cooling. In addition, in evaluating the light emission characteristics of the device, the characteristics of an organic EL device having an electrode area of 2 mm×2 mm were measured.

(Manufacture of organic EL element 1 (EL-1))
After treating the cleaned glass plate with ITO electrodes with oxygen plasma for about 1 minute, 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (α-NPD) was vacuum-deposited, A hole injection layer with a film thickness of 150 nm was obtained. On this hole injection layer, the compound (R-2) and the compound (R-3) shown in Table 3 were co-deposited at a composition ratio of 100:2 to form a first light-emitting layer having a thickness of 10 nm. did. Further, the compound (B-1) and the compound (B-4) shown in Table 1 were co-deposited at a composition ratio of 100:3 to form a second light-emitting layer having a thickness of 20 nm. On this light-emitting layer, 5 nm of α-NPD and 20 nm of the compound (G-3) shown in Table 2 were vapor-deposited to form a third light-emitting layer. Further, a tris(8-hydroxyquinoline)aluminum complex was vacuum-deposited to form an electron injection layer having a thickness of 35 nm, and lithium fluoride was first deposited thereon to a thickness of 1 nm and then aluminum was deposited to a thickness of 200 nm to form an electrode. , an organic EL device 1 was obtained.

Furthermore, in order to protect this organic EL device from the surrounding environment, it was hermetically sealed in a dry glow box filled with pure nitrogen. At a DC voltage of 5 V, this device provided white light with a luminance of 950 (cd/m ² ), a maximum luminance of 55000 (cd/m ² ), and a luminous efficiency of 3.9 (lm/W). FIG. 1 shows the emission spectrum of the obtained organic EL element EL-1.

<Production of alkali-soluble resin (B) having radically polymerizable group>
[Production Example 1]
90.0 parts of propylene glycol monomethyl ether acetate was placed in a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, and gas introduction pipe, and heated to 60°C while injecting nitrogen gas into the vessel. 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 dropwise addition, the mixture was further reacted at 60° C. for 1 hour, and then 0.5 parts of 2,2′-azobisisobutyronitrile dissolved in 10.0 parts of propylene glycol monomethyl ether acetate was added. Stirring was continued at the same temperature for 3 hours to obtain a copolymer. Subsequently, dry air was introduced 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 methoquinone were added and heated to 100°C. Then, stirring was continued for 20 hours, and 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 added to the reaction vessel and stirred at 60°C for 3 hours. 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 non-volatile content of 40% and radically polymerizable groups. The weight average molecular weight was 8,000.

[Production Examples 2-3]
Alkali-soluble resins B-2 to B-3 having a non-volatile content of 40% were obtained by synthesizing in the same manner as in Production Example 1 except that the raw materials and charging amounts shown in Table 4 were used.

Abbreviations in Table 4 are shown below. The amount of 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: Rikacid TH (manufactured by Shin Nippon Rika Co., Ltd.)

<Production of dispersant (X)>
[Production Example 4]
(first process)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer, 44.0 parts of PGMEA (propylene glycol monomethyl ether acetate), 5.0 parts of methacrylic acid (MAA), 10.0 parts of benzyl methacrylate (BzMA), 10.0 parts of tert-butyl methacrylate (t-BA) and 70.0 parts of methyl methacrylate (MMA) were charged and purged with nitrogen gas. The inside of the reaction vessel was 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 were added. , reacted for 12 hours. Solid content measurement confirmed that 95% had reacted.
(Second step)
Next, 6.46 parts of pyromellitic anhydride (PMA) and 0.46 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene (DBU) as a catalyst are added to the solution obtained in the first step. Two parts were charged and reacted at 120° C. for 7 hours. The reaction was continued until 98% or more of the acid anhydride was half-esterified as measured by the acid value.
The reaction solution was cooled and the solid content was adjusted with PGMEA to prepare a solution with a non-volatile content of 50%, thereby obtaining a dispersant X-1 solution having a weight average molecular weight of 8100 and an acid value of 60 mgKOH/g.

<<Photosensitive composition>>
<Method for producing colorant (A)>
<Method for producing pigment>
(Blue pigment (PB-1))
C. I. Pigment Blue 15:6 (PB15:6) ("Lionol Blue ES" manufactured by Toyocolor Co., Ltd.) 100 parts, pulverized salt 800 parts, and diethylene glycol 100 parts were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), and 70 C. for 12 hours. This mixture was poured into 3,000 parts of hot water and stirred for 1 hour while heating to 70°C to form a slurry, which was repeatedly filtered and washed with water to remove salt and solvent. A coloring agent (PB-1) was obtained. The average primary particle size was 28.3 nm.

(Purple pigment (PV-1))
C. I. Pigment Violet 23 (PV23) ("Fast V
iolet RL"), 1,600 parts of pulverized salt, and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 90° C. for 18 hours. This mixture was poured into 5000 parts of hot water and stirred for 1 hour while heating to 70°C to form a slurry, which was repeatedly filtered and washed with water to remove salt and solvent, then dried at 80°C for a day and night to give 118 parts of purple color. A coloring agent (PV-1) was obtained. The average primary particle size was 26.4 nm.

<Method for producing dye>
(Purple dye (PV-2))
The C.I. I. A purple dye (PV-2) was prepared from Acid Red 289 and the following resin Y-1 having a cationic group in the side chain.
To 2000 parts of water, 51 parts of the following resin B-1 having a cationic group on the side chain is added, thoroughly stirred and mixed, and then heated to 60°C. On the other hand, 10 parts of C.I. I. Prepare an aqueous solution in which Acid Red 289 is dissolved, and drop it little by little into the previous resin solution. After dropping, the mixture is stirred at 60° C. for 120 minutes to sufficiently react. To confirm the end point of the reaction, the reaction solution was added dropwise to a filter paper, and the point at which no bleeding occurred was regarded as the end point, and it was determined that a salt-forming compound was obtained. After allowing to cool to room temperature while 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 moisture with a dryer, followed by drying with 32 parts of C.I. I. A purple dye (PV-2) was obtained by combining Acid Red 289 with 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)
A four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser was charged with 75.1 parts of isopropyl alcohol and heated 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 methacrylate salt, and separately 7.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in 23.4 parts of methyl ethyl ketone was homogenized, charged into a dropping funnel, attached to a four-necked separable flask, and allowed to stand for 2 hours. dripped over. After 2 hours from the completion of 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. Thereafter, 14.3 parts of methanol was added to obtain a resin Y-1 having a cationic group in the side chain and containing 40% by weight of the resin component. The ammonium salt value of the obtained resin was 32 mgKOH/g.

<Method for Producing Colorant Dispersion>
[Preparation of Blue Colorant Dispersion DB-1]
After uniformly stirring and mixing a mixture having the following composition, using zirconia beads with a diameter of 1 mm, the mixture was dispersed for 5 hours with an Eiger mill (manufactured by Eiger Japan Co., Ltd. "Mini Model M-250 MKII"), 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.

<Production of photosensitive coloring composition for color filter>
[Example 1]
A mixture having the following composition was uniformly stirred and mixed, and 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 B-1 having a radically polymerizable group: 16.9 parts Polyfunctional acrylate monomer: 1.5 parts ("Aronix M402" manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator 1: 0.37 parts ("NCI-831" manufactured by ADEKA (absorption maximum wavelength 370 nm, manufactured by ADEKA, nitro group-containing carbazole structure oxime initiator))
Photopolymerization initiator 2: 0.37 parts (BASF "IRGACURE 379" absorption maximum wavelength 320 nm, BASF, acetophenone-based initiator))
Leveling agent: 1.0 parts (2% PGMEA solution of "BYK-330" manufactured by BYK-Chemie)
Solvent: 49.9 parts (propylene glycol monomethyl ether acetate (PGMEA))

[Examples 2 to 29, Comparative Examples 1 to 8]
Each material was mixed and stirred with the composition and blending amount shown in Table 5, and filtered through a 1 μm filter to obtain each photosensitive coloring composition PB-2 to PB-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: Adekacruz 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 initiator)
Irg.369: IRGACURE 369 (absorption maximum wavelength 320 nm, manufactured by BASF,
acetophenone initiator)
Irg.379: IRGACURE 379 (absorption maximum wavelength 320 nm, manufactured by BASF,
acetophenone initiator)
OXE-01: IRGACURE OXE01 (absorption maximum wavelength 330 nm, manufactured by BASF, phenyl structure-containing oxime 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 resulting photosensitive composition, chemical resistance, brightness and developed line width were evaluated by the following methods. Table 6 shows the results.

[Evaluation of chemical resistance]
A coated film prepared in the same procedure as for 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 resulting film was measured, and the film was immersed in propylene glycol monomethyl ether acetate for 5 minutes at room temperature, washed with deionized water, and air-dried. After that, the film was visually observed and measured for chromaticity, and the color difference ΔE was calculated. The chromaticity was measured with a microscopic spectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.) using a C light source. The rank of evaluation is as follows.
○: No change in appearance, ΔE ≤ 2.0: Good level △: No change in appearance, ΔE ≤ 2.0 to 5.0: Practical level ×: Change in appearance, and / or 5.0 < ΔE: Level unsuitable for practical use

[Color characteristic evaluation]
The color characteristics of the coating film prepared for chemical resistance were measured using a microscopic spectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). Table 6 lists the brightness Y when y=0.06 using the organic EL white light source shown in FIG. The rank of evaluation is as follows.
◎: Brightness Y 3.5 or more Very good level ○: Brightness Y 3.2 or more and less than 3.5 Good level .8 or more and less than 3.0 Practical level x: Brightness Y Less than 2.8 Level not suitable for practical use

[Evaluation of development line width]
Examples 2 to 29, the photosensitive coloring composition of Comparative Examples 1 to 8, 100 mm × 100 mm, 250 μm thick polyethylene naphthalate film fixed with an adhesive on a glass substrate, after drying under reduced pressure using a spin coater It was applied so that the finished film thickness would be 2.0 μm, and dried under reduced pressure. After cooling this film to room temperature, an ultra-high pressure mercury lamp was used to
00 μm) UV rays were irradiated through a striped pattern photomask at an illuminance of 20 mW/cm ² and an exposure amount of 50 mJ/cm ² . Thereafter, this film was developed by spraying with an aqueous solution of sodium carbonate at 23° C., washed with deionized water, air-dried, and heated at 100° C. for 20 minutes in a clean oven. After allowing to cool, the film was peeled off from the glass substrate to obtain a film for evaluation. The spray development was carried out for the film using each photosensitive coloring composition at a time extended by 10 seconds from the development time at which no residue was developed. The resulting patterned 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 better the photosensitive composition that can be made with higher definition. The rank of evaluation is as follows.
◎: 50 μm or more to less than 53 μm ○: 53 μm or more to less than 56 μm △: 56 μm or more to less than 65 μm ×: 65 μm or more In addition, ◎ and ○ are practically preferable levels, △ is practical levels, and × is not suitable for practical use. level.

As shown in Table 6, all of the photosensitive coloring compositions of Examples 1 to 29 exhibit excellent chemical resistance even under low-temperature curing conditions. Specifically, in Examples 6 to 14, the ratio of components (D1) and (D2) is set between 5/95 and 30/70 to provide high brightness and resolution in addition to chemical resistance. I know there is. Furthermore, in Examples 15 to 20, the blue pigment (A1) is 65% by weight or more based on the total colorant (A), so that even higher brightness can be achieved. As can be seen by comparing Comparative Examples 4 and 5, when the amount of the blue pigment (A1) increases, the photocuring does not proceed sufficiently and the chemical resistance decreases, but in Examples 15 to 20, the amount of the blue pigment (A1) increased, the chemical resistance did not decrease. 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 the dye (A2) in an amount of 15% by weight or more, it was possible to achieve even higher lightness.
Comparative Example 1 is a case where only the initiator (D1) is used, but only the surface effect is advanced, chemical resistance is deteriorated, and brightness is greatly reduced. Comparative Examples 2 to 4 are cases where only the initiator (D2) is used, but also have low chemical resistance. Comparative Example 5 uses an initiator that has an acetophenone structure but does not have a maximum absorption wavelength within the range of 300 to 350 nm, so that good effects cannot be obtained even when used in combination with the initiator (D1). Comparative Example 6 has a small amount of the blue pigment (A1) and thus has slightly good chemical resistance, but the chemical resistance when cured at 100° C. is not practical.
Comparative Examples 7 and 8 are cases in which a sensitizer is used in combination, but the chemical resistance in low temperature curing is not good.
As described above, it has chemical resistance at low temperatures, high transmittance (brightness), and good resolution. It was possible to use it suitably even when it was used for

The photosensitive coloring composition of the present invention can be used for color liquid crystal display devices, color organic EL display devices, solid-state imaging devices, color filters used in quantum dots, black matrices, and the like.

Claims (7)

A photosensitive coloring composition containing a coloring agent (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) comprises a carbazole-based oxime compound (D1) having a maximum absorption wavelength in the range of 350 to 400 nm, and a phenyl-based oxime compound (D2) having a maximum absorption wavelength in the range of 300 to 350 nm. ),
A photosensitive coloring composition for a color filter, wherein the coloring agent (A) contains at least one selected from a blue pigment (A1) having a phthalocyanine skeleton and a dye (A2). 2. The photosensitive coloring composition for color filters according to claim 1, wherein the ratio of compounds (D1) and (D2) is (D1)/(D2)=5/95 to 30/70. 3. The photosensitive coloring composition for a color filter according to claim 1, wherein the carbazole-based oxime compound (D1) is a compound having a nitro group. 3. Any one of claims 1 to 3 , wherein the coloring agent (A) contains a dye (A2), and the content of the dye (A2) is 15% by weight or more in the coloring agent (A). 4. The photosensitive coloring composition for color filters according to . A color filter for an organic EL display device, comprising a cured product formed from the photosensitive coloring composition for a color filter according to any one of claims 1 to 4 on a substrate. An organic EL display device comprising the color filter according to claim 5 . A method for producing a color filter for an organic EL display device comprising the following steps (i), (ii), (iii) and (iv), wherein the following photosensitive composition comprises a coloring agent (A), a radically polymerizable group A photosensitive coloring composition containing an alkali-soluble resin (B) having a polyfunctional (meth)acrylate monomer (C) and a photopolymerization initiator (D), wherein the photopolymerization initiator (D) is 350 A coloring agent (A) containing a carbazole-based oxime compound (D1) having a maximum absorption wavelength in the range of up to 400 nm and a phenyl-based oxime compound (D2) having a maximum absorption wavelength in the range of 300 to 350 nm. is a photosensitive composition containing at least one selected from a blue pigment (A1) having a phthalocyanine skeleton and a dye (A2).

<Process>
(i): Step (ii) of obtaining a coating film by applying a photosensitive composition onto a substrate: Step (iii) of exposing the coating film with ultraviolet rays through a mask after step (i): Step ( After ii), the exposed coating film is developed with an alkaline developer to obtain a pattern (iv): After step (iii), the pattern is post-baked at 80° C. to 150° C.

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