WO2023238762A1

WO2023238762A1 - Method for producing blue cured film, blue photosensitive composition, color filter and method for producing same, and display device

Info

Publication number: WO2023238762A1
Application number: PCT/JP2023/020425
Authority: WO
Inventors: 充史小野; 亮林
Original assignee: 株式会社Ｄｎｐファインケミカル
Priority date: 2022-06-10
Filing date: 2023-06-01
Publication date: 2023-12-14
Also published as: TW202409219A

Abstract

This method for producing a blue cured film includes: a step for forming, on a substrate, a coating film of a blue photosensitive composition that contains a colorant, an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator that contains an oxime-based photoinitiator and a sensitizer which is different from the oxime-based photoinitiator and which has a sensitizing effect at wavelengths of 400 nm to 420 nm; and a step for curing the coating film by exposing the coating film to light using an LED light source have emission peak wavelengths at 360 nm to 380 nm and 400 nm to 420 nm.

Description

Method for producing a blue cured film, blue photosensitive composition, color filter and method for producing the same, and display device

The present invention relates to a method for producing a blue cured film, a blue photosensitive composition, a color filter and a method for producing the same, and a display device.

In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays has increased. The penetration rate of mobile displays (mobile phones, smartphones, tablet PCs) is also increasing, and the market for liquid crystal displays is expanding. Organic light emitting display devices such as organic EL displays, which have high visibility due to their self-emission, are also attracting attention as next-generation image display devices.
Color filters are used in these liquid crystal display devices and organic light emitting display devices. For example, when forming a color image on a liquid crystal display device, light that has passed through a color filter is colored as it is in the color of each pixel that makes up the color filter, and the lights of these colors are combined to form a color image. In addition to conventional cold cathode tubes, organic light-emitting elements that emit white light or inorganic light-emitting elements that emit white light may be used as light sources in this case. Organic light emitting display devices use color filters for color adjustment and the like.

Here, the color filter generally includes a substrate, a colored layer formed on the substrate and consisting of colored patterns of the three primary colors of red, green, and blue, and formed on the substrate so as to partition each colored pattern. It has a light shielding part.
As a method for forming a colored layer in a color filter, for example, a colored resin composition is formed by adding a binder resin, a photopolymerizable compound, and a photoinitiator to a coloring material dispersion obtained by dispersing a coloring material with a dispersant or the like. After coating on a glass substrate and drying, a colored pattern is formed by exposing using a photomask and developing, and the pattern is fixed by heating to form a colored layer. These steps are repeated for each color to form a color filter.

Conventionally, a high-pressure mercury lamp has been used in the exposure step. High-pressure mercury lamps have problems such as the risk of bursting, high power consumption, and easy deterioration.
On the other hand, LEDs are increasingly being used as light sources for exposure from the viewpoint of energy saving and environmental load reduction.
For example, Patent Document 1 describes (1) forming a coating film of a colored radiation-sensitive composition containing at least one selected from the group consisting of dyes and lake pigments on a substrate; and (2) the coating film. A method for forming a pixel pattern including a step of exposing at least a portion of the image using an ultraviolet LED is described, and an ultraviolet LED having a peak wavelength of 365 nm is used.
Further, Patent Document 2 describes (A) a photopolymerizable compound, (B) a photopolymerization initiator which is an oxime ester compound having a specific structure having a 9,9-disubstituted fluorenyl group, and (C) a sensitizer. It is described that a photosensitive composition containing the above cures well even when exposed to light using an LED, and a commercially available LED light is used.

Japanese Patent Application Publication No. 2012-189994 JP 2017-125972 Publication

The LED lamp exposure machine has a single wavelength, and mainly uses an LED lamp having an emission peak wavelength of i-line at 365 nm. However, when an LED lamp having an emission peak wavelength of i-line at 365 nm is used, there is a problem in that the blue resist (blue photosensitive composition) in particular is difficult to cure.
Since the i-line of 365 nm is a wavelength range that is easily absorbed by blue resist and difficult to transmit, it was considered that the photoinitiator was difficult to react with and hard to cure. In recent years, blue resists with higher coloring material concentrations have been particularly difficult to cure. Insufficient curing causes problems such as a decrease in the residual film rate after development, a line width that becomes too thin, poor adhesion to the substrate during pattern formation, and the inability to form a good pattern.
On the other hand, when using an LED lamp that has a peak emission wavelength in the H-line 405 nm, which is a longer wavelength than the I-line 365 nm, the light spreads and the line width tends to increase because the blue resist easily passes through the wavelength range, but the energy is Since the h-line is weaker than the i-line, it is difficult to ensure the remaining film rate after development, and it is difficult to maintain a balance between the remaining film rate and the line width.

The present invention has been made in view of the above circumstances, and provides a method for producing a blue cured film that can form a good pattern even by LED exposure, and a method for producing a color filter using the method for producing the blue cured film. The purpose is to provide Another object of the present invention is to provide a blue photosensitive composition suitably used in the method for producing the blue cured film, and a color filter and display device formed using the blue photosensitive composition.

That is, the present invention relates to the following [1] to [7].
[1] A photoinitiator containing a coloring material, an alkali-soluble resin, a photopolymerizable compound, an oxime-based photoinitiator, and a sensitizer having a sensitizing effect at 400 nm to 420 nm different from the oxime-based photoinitiator. a step of forming a coating film of a blue photosensitive composition containing on a substrate, and
a step of exposing and curing the coating film using an LED light source having an emission peak wavelength of 360 nm to 380 nm and 400 nm to 420 nm;
A method for producing a blue cured film comprising:
[2] In the LED light source, the intensity ratio (A/B) between the intensity of the emission peak wavelength of 360 nm to 380 nm (A) and the intensity of the emission peak wavelength of 400 nm to 420 nm (B) is 10/90 to 90/10. The method for producing a blue cured film according to [1] above.
[3] The oxime photoinitiator is selected from the group consisting of an oxime photoinitiator having a diphenyl sulfide skeleton, an oxime photoinitiator having an indole skeleton, and an oxime photoinitiator having a carbazole skeleton. At least one method for producing a blue cured film according to [1] or [2].
[4] A coloring material, an alkali-soluble resin, a photopolymerizable compound, an oxime-based photoinitiator represented by the following general formula (A), and a sensitizing effect at 400 nm to 420 nm different from the oxime-based photoinitiator. A blue photosensitive composition for curing by exposure using an LED light source having an emission peak wavelength of 360 nm to 380 nm and 400 nm to 420 nm.

(In general formula (A), Z ¹ , Z ³ , Z ⁴ and Z ⁵ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a C 3 to 20 represents a cycloalkyl group or a phenyl group, and each of the alkyl group, cycloalkyl group, and phenyl group is substituted with a substituent selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and a phenyl group. ( ^Z2 represents an alkyl group having 1 to 20 carbon atoms substituted with a cycloalkyl group.)

[5] A method for producing a color filter comprising at least a substrate and a colored layer including a blue cured film provided on the substrate,
A method for producing a color filter, comprising the step of producing the cured blue film by the method for producing a cured blue film according to any one of [1] to [3] above.
[6] A color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is a cured product of the blue photosensitive composition according to [4] above. color filter.
[7] A display device comprising the color filter according to [6] above.

According to the present invention, it is possible to provide a method for manufacturing a blue cured film that can form a good pattern even by LED exposure, and a method for manufacturing a color filter using the method for manufacturing the blue cured film. Further, the present invention can provide a blue photosensitive composition suitably used in the method for producing the blue cured film, and a color filter and display device formed using the blue photosensitive composition.

FIG. 1 is a schematic diagram showing an example of a color filter of the present invention. FIG. 2 is a schematic diagram showing an example of a liquid crystal display device of the present invention. FIG. 3 is a schematic diagram showing an example of an organic light emitting display device of the present invention.

Hereinafter, a method for producing a blue cured film, a blue photosensitive composition, a color filter and a method for producing the same, and a display device according to the present invention will be explained in detail in order.
Note that in the present invention, light includes electromagnetic waves with wavelengths in visible and non-visible regions, as well as radiation, and radiation includes, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves with a wavelength of 5 μm or less and electron beams.
In the present invention, (meth)acryloyl represents each of acryloyl and methacryloyl, (meth)acrylic represents each of acrylic and methacryl, and (meth)acrylate represents each of acrylate and methacrylate.
Furthermore, in this specification, "~" indicating a numerical range is used to include the numerical values written before and after it as a lower limit value and an upper limit value.

I. Method for producing a blue cured film The method for producing a blue cured film according to the present invention includes a coloring material, an alkali-soluble resin, a photopolymerizable compound, an oxime-based photoinitiator, and a oxime-based photoinitiator having a wavelength of 400 nm to 420 nm different from the oxime-based photoinitiator. a step of forming on a substrate a coating film of a blue photosensitive composition containing a photoinitiator containing a sensitizer having a sensitizing effect;
The method includes a step of exposing and curing the coating film using an LED light source having an emission peak wavelength of 360 nm to 380 nm and 400 nm to 420 nm.

The method for producing a blue cured film according to the present invention includes a coloring material, an alkali-soluble resin, a photopolymerizable compound, an oxime-based photoinitiator, and an oxime-based photoinitiator that has a sensitizing effect at a wavelength of 400 nm to 420 nm different from the oxime-based photoinitiator. A coating film of a blue photosensitive composition containing a photoinitiator containing a sensitizer is exposed and cured using an LED light source having emission peak wavelengths of 360 nm to 380 nm and 400 nm to 420 nm. It is possible to improve the residual film rate after development while suppressing line width shift, it is possible to form a good pattern with suppressed undercuts after development, and the adhesion of the formed blue cured film pattern to the substrate is also improved. . A blue photosensitive composition that can effectively use light having an emission peak wavelength of 400 nm to 420 nm by combining an oxime photoinitiator and a sensitizer different from the oxime photoinitiator and having a sensitizing effect in the 400 nm to 420 nm range. In addition, since we use LED light sources with emission peak wavelengths in both 360 nm to 380 nm and 400 nm to 420 nm, they complement each other's disadvantages of insufficient curing and line width shift, and suppress line width shift. Since it can be cured well to the deep part, it is thought that a good pattern can be formed while suppressing line width shift, and the adhesion to the substrate is also improved.

(1) Coating film forming process First, a coloring material, an alkali-soluble resin, a photopolymerizable compound, an oxime-based photoinitiator, and a sensitizer having a sensitizing effect at 400 nm to 420 nm different from the oxime-based photoinitiator. The method includes forming a coating film of a blue photosensitive composition containing a photoinitiator on a substrate. Here, the blue-sensitive composition used in the present invention will be described later.

As the substrate, a transparent substrate, a silicon substrate, or a substrate in which a thin film of aluminum, silver, silver/copper/palladium alloy, etc. is formed on a transparent substrate or a silicon substrate is used. Other color filter layers, resin layers, transistors such as TFTs, circuits, etc. may be formed on these substrates.
The transparent substrate in the present invention is not particularly limited as long as it is a base material that is transparent to visible light, and for example, a transparent substrate used in general color filters can be used. Specifically, non-flexible transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible materials that have flexibility such as transparent resin films, optical resin plates, and flexible glass. Examples include wood.
The thickness of the transparent substrate is not particularly limited, but may be, for example, about 100 μm to 1 mm depending on the use of the blue cured film produced by the present invention.

A blue photosensitive composition to be described later is applied onto the substrate using a coating method such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, or a die coating method to form a wet coating film. Form. Among these, spin coating and die coating are preferably used.

Next, the wet coating film is dried (prebaked) using a hot plate, an oven, or the like to form a coating film.
Prebaking is usually performed by combining reduced pressure drying and heat drying. Drying under reduced pressure is usually carried out until a pressure of 50 Pa to 200 Pa is reached. The heating drying conditions are usually about 1 minute to 10 minutes at a temperature of 70° C. to 110° C. using a hot plate. Further, the thickness of the applied coating film may be adjusted appropriately depending on the use of the blue cured film, and the thickness of the coating film after drying is, for example, 0.5 μm to 5.0 μm, preferably 1 μm. Examples include .0 μm to 3.0 μm.

(2) Exposure step In the present invention, the exposure step is a step of exposing and curing the coating film using an LED light source having an emission peak wavelength of 360 nm to 380 nm and 400 nm to 420 nm.
Here, the "emission peak wavelength" refers to the wavelength at which the emission intensity is maximum in the LED emission spectrum, and is measured using a spectral irradiance meter (for example, USR-45DA-14 (manufactured by Ushio Inc.)). be able to.
As the LED light source having emission peak wavelengths of 360 nm to 380 nm and 400 nm to 420 nm used in the present invention, there are cases in which light having the above two types of emission peak wavelengths is irradiated from one LED irradiation device, and two cases. Both cases of irradiation from the above LED irradiation device are included.
Furthermore, an LED light source having emission peak wavelengths between 360nm and 380nm and between 400nm and 420nm may have two or more emission peak wavelengths between 360nm and 380nm, and two or more emission peak wavelengths between 400nm and 420nm. May have.
Furthermore, the LED light sources having emission peak wavelengths in 360 nm to 380 nm and 400 nm to 420 nm may or may not have emission peak wavelengths in other wavelength ranges.

In the LED light source used in the present invention, the intensity ratio (A/B) between the intensity of the emission peak wavelength of 360 nm to 380 nm (A) and the intensity of the emission peak wavelength of 400 nm to 420 nm (B) is It may be appropriately selected depending on the use of the cured film and is not particularly limited. The intensity ratio (A/B) may be, for example, 1/99 to 99/1, 5/95 to 95/5, and preferably 10/90 to 90/10, More preferably, the ratio is 10/90 to 80/20. The intensity ratio (A/B) may be from 20/80 to 80/20, and even more from 40/60 to 60/40, depending on the use of the blue photosensitive composition and its cured film.
The intensity ratio (A/B) can be confirmed using a spectral irradiance meter (for example, USR-45DA-14 (manufactured by Ushio Inc.)).
For example, when there are two or more emission peak wavelengths in the range of 360 nm to 380 nm, the sum of the intensities of the two emission peak wavelengths is defined as the intensity (A) of the emission peak wavelengths in the range of 360 nm to 380 nm.

The LED light source used in the present invention having an emission peak wavelength of 360nm to 380nm and 400nm to 420nm includes an LED chip having an emission peak wavelength of 360nm to 380nm, and an LED chip having an emission peak wavelength of 400nm to 420nm. They may be used in combination. In this case, the intensity ratio (A/B) and the curing of the blue photosensitive composition are determined depending on the number and ratio of LED chips having an emission peak wavelength of 360 nm to 380 nm and LED chips having an emission peak wavelength of 400 nm to 420 nm. This is preferable because it is easy to adjust the properties appropriately.
The LED chip used in the LED light source may be equipped with a condenser lens for the purpose of further increasing the illuminance.
As the LED chip having an emission peak wavelength of 360 nm to 380 nm or 400 nm to 420 nm, commercially available LEDs can be appropriately selected and used. As a commercially available LED, for example, a UV-LED manufactured by Nichia Chemical Industries, Ltd. can be used, and specifically, NVSU233B (365 nm), NWSU333B (365 nm), NWSU333B-D4 (367 nm), NCSU276C (365 nm). , NVSU119C (375 nm), NVSU119C (405 nm), etc., but are not limited to these.

When using a combination of an LED chip having an emission peak wavelength of 360 nm to 380 nm and an LED chip having an emission peak wavelength of 400 nm to 420 nm as an LED light source used in the present invention, the arrangement of each LED chip is particularly limited. It is not something that will be done. The number ratio of each LED chip can be adjusted according to the intensity ratio (A/B), and the LED chips can be arranged, for example, with or without regularity.

Alternatively, as the LED light source used in the present invention, an LED irradiation device having an emission peak wavelength of 360 nm to 380 nm and an LED irradiation device having an emission peak wavelength of 400 nm to 420 nm may be used simultaneously or sequentially for exposure. good. Further, the order of exposure of each LED irradiation device is not limited either.

The illumination intensity of the LED light source used in the present invention may be adjusted as appropriate, but is usually 5 mW/cm ² or more, preferably 15 mW/cm ² to 60 mW/cm ² , and 60 mW/cm 2 or more. It may be ² or more.

In the exposure process, the cumulative amount of ultraviolet light from the LED light source may be adjusted appropriately depending on the thickness of the coating film, etc., but is usually 5 mJ/cm ² to 200 mJ/cm ² , and 200 mJ/cm ² to 1000 mJ/cm ² . There may be.

In the method for producing a blue cured film according to the present invention, after the exposure step, if necessary, (3) developing the exposed coating film (development step); and/or (4) developing the coating film. A post-baking process (heating process) may be performed.

(3) Development process After the exposure process, a cured coating film is formed in a desired pattern by performing a development process using a developer and dissolving and removing unexposed areas.
The developer is preferably an alkaline developer, such as sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, An aqueous solution of 1,5-diazabicyclo-[4.3.0]-5-nonene or the like is used. For example, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, or a surfactant may be added to the alkaline developer. Note that after the alkaline development treatment, washing with water is usually performed.

As the development method, for example, a shower development method, a spray development method, a dip development method, a paddle development method, etc. can be applied. Development conditions can be, for example, at room temperature for 5 seconds to 300 seconds.

(4) Heating process After exposure and before the development process, the cured coating film may be subjected to heat treatment in order to accelerate the polymerization reaction. The heating conditions are appropriately selected depending on the heating means used, the blending ratio of each component in the blue-sensitive composition, the thickness of the cured coating film, etc.

After the development process, the developer is usually washed and the cured coating film of the blue photosensitive composition is dried to form a blue cured film. Note that, after the development step, heat treatment may be performed in order to sufficiently harden the cured coating film. The heating conditions are not particularly limited and are appropriately selected depending on the heating means used, the blending ratio of each component in the blue-sensitive composition, the thickness of the cured coating film, etc. When a hot air heating furnace is used, the heating time can be, for example, at 150° C. to 250° C. for about 20 minutes to 40 minutes.

The thickness of the patterned blue cured film thus formed after drying is, for example, 0.5 μm to 5.0 μm, preferably 1.0 μm to 3.0 μm.

The blue cured film thus formed has chromaticity coordinates in the JIS Z8701 XYZ color system measured using a C light source: x=0.110 or more and 0.150 or less, y=0.035 The cured film may be in the range of 0.190 or more, and in particular, from the viewpoint of improving color reproducibility, x = 0.120 or more and 0.147 or less, y = 0.038 or more and 0.180 or less. The cured film may be in the range of x = 0.122 or more and 0.147 or less, y = 0.038 or more and 0.150 or less, and x = 0.125 or more and 0.147. Hereinafter, the cured film may be in the range of y=0.038 or more and 0.120 or less.

According to the method for producing a blue cured film of the present invention, it is possible to improve the residual film rate after development while suppressing line width shift, and it is possible to form a good pattern with suppressed undercuts after development. Since the adhesion of the blue cured film pattern to the substrate is also improved, the method for producing the blue cured film is suitably used in the method for producing color filters.

II. blue photosensitive composition
The blue photosensitive composition used in the method for producing a blue cured film of the present invention includes a coloring material, an alkali-soluble resin, a photopolymerizable compound, an oxime-based photoinitiator, and a 400 nm wavelength different from the oxime-based photoinitiator. Contains a photoinitiator containing a sensitizer that has a sensitizing effect at ~420 nm.

Among them, the blue photosensitive composition of the present invention suitably used in the method for producing a blue cured film of the present invention comprises a coloring material, an alkali-soluble resin, a photopolymerizable compound, and a composition represented by the following general formula (A). and a photoinitiator containing a sensitizer that has a sensitizing effect at 400 nm to 420 nm, which is different from the oxime photo initiator. This is a blue photosensitive composition to be cured by exposure using an LED lamp having a wavelength.

The blue photosensitive composition used in the method for producing a blue cured film of the present invention is such that the blue cured film formed by the method for producing a blue cured film of the present invention has a JIS color measured using, for example, a C light source. Select each component so that the cured film has chromaticity coordinates in the XYZ color system of Z8701 in the range of x = 0.110 or more and 0.150 or less and y = 0.035 or more and 0.190 or less. I can do it.
Hereinafter, each component contained in the blue photosensitive composition used in the method for producing a blue cured film of the present invention will be explained in order.

<Color material>
The coloring material is not particularly limited as long as it is such that the color of the photosensitive composition is in the blue region, and is mixed so as to satisfy the above-mentioned range of chromaticity coordinates, for example.
The coloring material includes a blue coloring material, may further contain a purple coloring material, and may further contain other coloring materials.

The blue coloring material used in the present invention has a 440 nm transmittance of 60% or more and a 520 nm transmittance when a 2.5 μm coating film is formed at P/V = 0.2 and the spectral transmittance spectrum is measured. A coloring material having a transmittance of 10% or more and less than 10% at 580 nm is used.
Note that to measure the color of a single blue coloring material as a coating, it is possible to prepare a coating solution by blending the blue coloring material with an appropriate dispersant, binder component, and solvent, and then apply it on a transparent substrate. It may be dried and hardened if necessary. As the binder component, a non-curing thermoplastic resin composition may be used as long as it can form a transparent coating film that allows color measurement, or a photocurable (photosensitive) or thermosetting resin composition may be used. You may also use Specifically, for example, the solid content other than the coloring material used in the photosensitive composition of Example 1 described below can be used as a dispersant and a binder component.
As a transparent coating film containing a dispersant and a binder component and capable of color measurement, for example, a film thickness of 2.0 μm and a spectral transmittance of 95% or more in the range from 380 nm to 780 nm are recommended. It can be done.
Note that the spectral transmittance spectrum can be measured using a spectrometer (for example, Olympus Microspectrophotometer OSP-SP200).

The blue coloring material used in the present invention is not particularly limited, and known blue organic pigments, blue dyes, blue lake coloring materials that are salt-forming compounds of blue dyes, etc. can be used. Here, the blue organic pigment has excellent resistance such as heat resistance and light resistance compared to dyes and lake coloring materials, and the blue dye has higher transparency than the organic pigment because it is soluble. Furthermore, since lake coloring materials are derived from dyes, they have higher transmittance than ordinary pigments and can meet the demands for high brightness.

Examples of the blue organic pigment include C.I. I. Pigment Blue 15, C. I. Pigment Blue 15:3, C. I. Pigment Blue 15:4, C. I. Pigment Blue 15:6, C. I. Pigment Blue 16, C. I. Pigment Blue 60 and the like. Among these, copper phthalocyanine-based blue pigments are preferred because they have relatively excellent brightness.

Examples of the blue dye include methine dyes, anthraquinone dyes, azo dyes, triarylmethane dyes, and phthalocyanine dyes.

In the blue lake coloring material, which is a salt-forming compound of the blue dye, the counter ion differs depending on the type of dye, and the counter ion of the acidic dye is a cation, and the counter ion of the basic dye is an anion.
Counter cations for acidic dyes include ammonium cations, metal cations, inorganic polymers, and the like.
Preferred examples of the lake forming agent that generates ammonium ions include primary amine compounds, secondary amine compounds, and tertiary amine compounds. It is preferable to use an amine compound or a tertiary amine compound.
Further, the lake forming agent that generates metal cations may be appropriately selected from metal salts having desired metal ions.
The counter cations of acidic dyes can be used alone or in combination of two or more.

On the other hand, the counter anion of the basic dye may be an organic anion or an inorganic anion. Examples of the organic anion include organic compounds having an anionic group as a substituent.
Furthermore, a known acidic dye may be used as the organic anion. In this case, in the lake coloring material, an acidic dye and a basic dye exist as an ion pair. Examples of the lake forming agent that generates these organic anions include alkali metal salts and alkaline earth metal salts of the above-mentioned organic anions.
On the other hand, examples of inorganic anions include oxoacid anions (phosphate ion, sulfate ion, chromate ion, tungstate ion (WO ₄ ^2- ), molybdate ion (MoO ₄ ^2- ), etc.), and Examples include inorganic anions such as polyacid anions condensed with oxo acids, and mixtures thereof.
The polyacid may be an isopolyate anion (M _m O _n ) ^c- or a heteropolyacid anion (X _l M _m O _n ) ^c- . In the above ionic formula, M represents a poly atom, X represents a hetero atom, m represents a composition ratio of poly atoms, and n represents a composition ratio of oxygen atoms. Examples of the poly atom M include Mo, W, V, Ti, and Nb. Examples of the heteroatom X include Si, P, As, S, Fe, and Co. c is a valence number and may be an integer of 2 or more.
Among these, from the viewpoint of heat resistance, a polyacid anion containing at least one of molybdenum (Mo) and tungsten (W) is preferable, and a c-valent polyacid anion containing at least tungsten is more preferable.
Examples of the lake forming agent that generates inorganic anions include alkali salts and alkali metal salts of the above-mentioned inorganic anions.
The counter anions of the basic dyes in the lake coloring material can be used alone or in combination of two or more.

As the blue lake coloring material, for example, C.I. I. Pigment Blue 1, C. I. Pigment Blue 1:2, C. I. Pigment Blue 2, C. I. Pigment Blue 3, C. I. Pigment Blue 8, C. I. Pigment Blue 9, C. I. Pigment Blue 10, C. I. Pigment Blue 12, C. I. Pigment Blue 14, C. I. Pigment Blue 17:1, C. I. Pigment Blue 18, C. I. Pigment Blue 19, C. I. Pigment Blue 24, C. I. Pigment Blue 24:1, C. I. Pigment Blue 53, C. I. Pigment Blue 56, C. I. Pigment Blue 56:1, C. I. Pigment Blue 61, C. I. Pigment Blue 61:1, C. I. Pigment Blue 62, C. I. Pigment Blue 63, C. I. Pigment Blue 78 and the like.
In addition, from the viewpoint of reliability such as heat resistance and weather resistance, the blue lake coloring material may be a triarylmethane-based lake coloring material, and may be a coloring material represented by the following general formula (1) or a coloring material represented by the following general formula. It may be at least one type of lake coloring material selected from the group consisting of coloring materials represented by (2).

(In general formula (1), A is an a-valent organic group in which the carbon atom directly bonded to N does not have a π bond, and the organic group has at least a saturated aliphatic carbon at the end directly bonded to N. It represents an aliphatic hydrocarbon group having a hydrogen group or an aromatic group having the aliphatic hydrocarbon group, and a hetero atom may be included in the carbon chain.B ^c- represents a c-valent polyacid anion. R ⁱ to R ^v each independently represent a hydrogen atom, an alkyl group that may have a substituent, or an aryl group that may have a substituent, and R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v may be combined to form a ring structure. R ^vi and R ^vii each independently represent an alkyl group that may have a substituent, an alkoxy group that may have a substituent, a halogen atom, or a cyano atom. represents a group. Ar ¹ represents a divalent aromatic group which may have a substituent. A plurality of R ⁱ to R ^vii and Ar ¹ may be the same or different.
a and c represent integers of 2 or more, and b and d represent integers of 1 or more. f and g represent integers from 0 to 4. A plurality of f and g may be the same or different. )

(In general formula (2), R ^I to R ^VI each independently represent a hydrogen atom, an alkyl group that may have a substituent, or an aryl group that may have a substituent, and R ^I and R ^II , R ^III and R ^IV , and R ^V and R ^VI may combine to form a ring structure. R ^VII and R ^VIII each independently represent an alkyl group that may have a substituent, or a substituent. represents an alkoxy group, a halogen atom, or a cyano group that may have a substituent.Ar ² represents a divalent aromatic heterocyclic group that may have a substituent, and the plurality of R ^I to R ^VIII and Ar ² are Each may be the same or different. E ^m- represents an m-valent polyacid anion.
m represents an integer of 2 or more. j is 0 or 1; when j is 0, there is no bond. k and l represent integers from 0 to 4, and k+j and l+j are from 0 to 4. A plurality of j, k, and l may be the same or different. )

The explanation of each symbol of at least one lake coloring material selected from the group consisting of the coloring material represented by the general formula (1) and the coloring material represented by the general formula (2) is given in International Publication No. 2020 Paragraphs 0031 to 0061 of Publication No./071041 can be referred to.

The blue coloring material may be appropriately selected depending on the use of the blue cured film, but in the case of color filter use, C. I. Pigment Blue 15:6, C. I. Pigment Blue 15:3, C. I. Pigment Blue 15:4, and one or more selected from the group consisting of triarylmethane lake coloring materials are preferred from the viewpoint of hue.

As a purple coloring material, when a 2.5 μm coating film is formed at P/V = 0.2 and the spectral transmittance spectrum is measured, the 440 nm transmittance is 40% or more, the 520 nm transmittance is less than 10%, and the 680 nm transmittance is 40% or more. A coloring material with a transmittance of 40% or more is used.
The purple coloring material used in the present invention includes a reddish-purple coloring material that is called a red dye.
Note that color measurement by forming a single coating film on the purple coloring material can be performed in the same manner as in the case of the blue coloring material described above.

The purple coloring material used in the present invention is not particularly limited, and known purple organic pigments, purple dyes, purple lake coloring materials, and the like can be used.

Examples of the purple organic pigment include C.I. I. Pigment Violet 1, 14, 15, 19, 23, 29, 32, 33, 36, 37, 38 and the like. Among them, Pigment Violet 23 is preferred because it has relatively excellent coloring power.

Examples of the purple dye include C.I. I. Anthraquinone acid dyes such as Acid Violet 29, 31, 33, 34, 36, 36:1, 39, 41, 42, 43, 47, 51, 63, 76, 103, 118, 126, C.I. I. Cyanine acid dyes such as Basic Red 12, triarylmethane acid dyes such as Acid Violet 15, 16, 17, 19, 21, 23, 24, 25, 38, 49, 72, C.I. I. Acid Red 289, C. I. Acid Violet 9, C. I. Rhodamine acid dyes such as Acid Violet 30; also C.I. I. Triarylmethane basic dyes such as

Basic Violet

1, 3, 14, C.I. I. Examples include xanthene basic dyes such as Basic Violet 11.

Examples of the purple lake coloring material include those obtained by turning the above-mentioned purple dye into a lake using a lake forming agent.
In the lake coloring material, the counter ions differ depending on the type of dye, and the counter ions for acidic dyes are cations, and the counter ions for basic dyes are anions. As the counter cation of the acidic dye and the counter anion of the basic dye, the same ones as mentioned above for the blue dye can be used.

The purple lake coloring material is preferably one or more selected from the group consisting of anthraquinone coloring materials, cyanine coloring materials, and xanthene coloring materials from the viewpoint of hue.

Further, as the purple dye and the purple lake coloring material, a xanthene coloring material containing xanthene as a basic skeleton and including a rhodamine coloring material is preferable from the viewpoint of improving the brightness and contrast of the colored layer.
The xanthene acid dye in the lake coloring material preferably contains a compound represented by the following general formula (3), that is, a rhodamine acid dye.

(In general formula (3), R ^a to R ^d each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and R ^a and R ^b , and R ^c and R ^d bond A ring structure may be formed.R ^e represents an acidic group, X represents a halogen atom, m represents an integer of 0 to 5. General formula (3) has one or more acidic groups; , n is an integer greater than or equal to 0.)

For the explanation of each symbol of the compound represented by the general formula (3), reference can be made to paragraphs 0057 to 0059 of International Publication No. 2018/135370.

A metal lake coloring material is preferably used as the lake coloring material of the xanthene acid dye. The metal lake coloring material includes a metal atom as a lake agent. By using a lake forming agent containing metal atoms, the heat resistance of the coloring material increases. As such a lake forming agent, a lake forming agent containing a metal atom that becomes a divalent or higher metal cation is preferable.

As other coloring materials used in the present invention, for example, red coloring materials, orange coloring materials, green coloring materials, etc. are suitably used, and among them, from the viewpoint of hue, red coloring materials, green coloring materials, etc. It may be a coloring material.
Examples of other coloring materials include, but are not limited to, the following.
As a red colorant, C. I. Pigment Red 177, 168, 254, etc.
As a green coloring material, C. I. Pigment Green 7, 36, 58, 59, etc.

In the blue photosensitive composition used in the present invention, the content ratio of the blue coloring material to the entire coloring material may be appropriately adjusted according to the desired chromaticity, and is not particularly limited.
From the viewpoint of desired chromaticity for various light sources, it is preferable to contain a blue coloring material at 50% by mass or more and 100% by mass or less with respect to the total amount of coloring materials, and contain a blue coloring material at 60% by mass or more and 90% by mass or less. It is more preferable to do so, and the content may be 70% by mass or more and 80% by mass or less.

In the blue photosensitive composition used in the present invention, the content ratio of the purple coloring material to the blue coloring material is not particularly limited as long as it is appropriately adjusted according to the desired chromaticity.
In terms of desired chromaticity for various light sources, it is possible to include 3 parts by mass or more and 100 parts by mass or less of a violet coloring material per 100 parts by mass of a blue coloring material, and 5 parts by mass or more and 80 parts by mass or less. May be contained.
In addition, the purple coloring material may be contained in 1% by mass or more and 50% by mass or less, 3% by mass or more and 40% by mass or less, and 5% by mass or more and 30% by mass or less, based on the total amount of the coloring material. You may.

In the blue photosensitive composition used in the present invention, the coloring material may further contain other coloring materials, but the total content of the blue coloring material and the purple coloring material is based on the total amount of the coloring material. It is more preferably 70% by mass or more and 100% by mass or less, even more preferably 80% by mass or more and 100% by mass or less.

In the blue photosensitive composition according to the present invention, the content of the coloring material is not particularly limited. From the viewpoint of dispersibility and dispersion stability, the content of the coloring material is usually within the range of 3% by mass to 65% by mass, preferably 4% by mass to 60% by mass, based on the total solid content of the blue photosensitive composition. %, more preferably 15% to 60% by weight. If it is at least the above lower limit, the colored layer will have sufficient color density when the blue photosensitive composition is applied to a predetermined thickness (usually 1.0 μm to 5.0 μm). Moreover, if it is below the said upper limit, a colored layer which is excellent in storage stability, and has sufficient hardness and adhesiveness with the substrate can be obtained. In particular, when forming a colored layer with a high colorant concentration, the total content of colorants is preferably 20% by mass to 65% by mass, more preferably 30% by mass, based on the total solid content of the blue-sensitive composition. It is within the range of 60% by mass.

<Alkali-soluble resin>
The alkali-soluble resin in the present invention has an acidic group, and can be appropriately selected and used from those that act as a binder resin and are soluble in the alkaline developer used in pattern formation.
In the present invention, the alkali-soluble resin can be defined as having an acid value of 40 mgKOH/g or more.
Preferred alkali-soluble resins in the present invention are resins having an acidic group, usually a carboxyl group, and specifically, for example, a (meth)acrylic copolymer having a carboxyl group and a styrene-(meth) copolymer having a carboxyl group. Examples include (meth)acrylic resins such as acrylic copolymers, and epoxy (meth)acrylate resins having a carboxyl group.

Among these, particularly preferred are those having a carboxy group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain. When containing a photopolymerizable functional group, in the exposure step, the alkali-soluble resins may form crosslinks with each other, or the alkali-soluble resin and a photopolymerizable compound such as a polyfunctional monomer may form a crosslink. When a photopolymerizable functional group is contained, the film strength is improved, so that pigments are less likely to aggregate even during post-baking, and the retardation can be maintained at a low level. Furthermore, the film strength of the cured film is improved, development resistance is improved, and thermal shrinkage of the cured film is suppressed, resulting in excellent adhesion to the substrate.
The method for introducing ethylenically unsaturated bonds into the alkali-soluble resin may be appropriately selected from conventionally known methods. For example, a method of adding a compound having both an epoxy group and an ethylenically unsaturated bond in the molecule, such as glycidyl (meth)acrylate, to the carboxyl group of an alkali-soluble resin to introduce an ethylenically unsaturated bond into the side chain. Or, a method in which a structural unit having a hydroxyl group is introduced into a copolymer, and a compound having an isocyanate group and an ethylenically unsaturated bond is added to the molecule to introduce an ethylenically unsaturated bond into the side chain. Examples include.

Moreover, it is preferable that the alkali-soluble resin further has a hydrocarbon ring from the viewpoint of excellent adhesion of the colored layer. By having a hydrocarbon ring, which is a bulky group, in the alkali-soluble resin, shrinkage during curing is suppressed, peeling from the substrate is alleviated, and adhesion to the substrate is improved.
Examples of such hydrocarbon rings include aliphatic hydrocarbon rings that may have a substituent, aromatic hydrocarbon rings that may have a substituent, and combinations thereof. may have a substituent such as an alkyl group, a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group, a hydroxyl group, a nitro group, an amino group, or a halogen atom.
The hydrocarbon ring may be included as a monovalent group, or may be included as a divalent or higher group.

Specific examples of hydrocarbon rings include aliphatic rings such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, isobornane, tricyclo[5.2.1.0(2,6)]decane (dicyclopentane), and adamantane. Hydrocarbon rings: Aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, and fluorene; chain polycyclic rings such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, and stilbene; ); Examples include groups in which a part of these groups is substituted with a substituent.
Examples of the substituent include an alkyl group, a cycloalkyl group, an alkylcycloalkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, a halogen atom, and the like.

When the hydrocarbon ring includes an aliphatic hydrocarbon ring, it is preferable because the heat resistance and adhesion of the colored layer are improved and the brightness of the obtained colored layer is improved.
Further, when the cardo structure is included, it is particularly preferable because the curability of the colored layer is improved, fading of the coloring material is suppressed, and solvent resistance (NMP swelling suppression) is improved.

(Meth)acrylic resins such as (meth)acrylic copolymers having structural units having a carboxyl group and styrene-(meth)acrylic copolymers having a carboxyl group are, for example, ethylenic polymers having a carboxyl group. It is a (co)polymer obtained by (co)polymerizing a saturated monomer and, if necessary, other copolymerizable monomers by a known method.
Examples of the carboxyl group-containing ethylenically unsaturated monomer include (meth)acrylic acid, vinylbenzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. It will be done. In addition, addition reaction products of monomers having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and cyclic anhydrides such as maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono(meth)acrylates can also be used. Furthermore, anhydride-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride may be used as a precursor of the carboxy group. Among these, (meth)acrylic acid is particularly preferred in terms of copolymerizability, cost, solubility, glass transition temperature, and the like.

The alkali-soluble resin in the present invention is a carboxyl group-containing resin such as a (meth)acrylic copolymer having a structural unit having a carboxyl group and a structural unit having a hydrocarbon ring, or a styrene-(meth)acrylic copolymer. A (meth)acrylic copolymer and a styrene-( More preferably, it is a carboxyl group-containing copolymer such as a meth)acrylic copolymer.

Examples of ethylenically unsaturated monomers having a hydrocarbon ring include cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, and phenoxyethyl. Examples include (meth)acrylate, styrene, etc.; cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl ( It is preferable to use at least one selected from meth)acrylate, benzyl(meth)acrylate, and styrene.

The carboxy group-containing copolymer may further contain other structural units such as ester group-containing structural units such as methyl (meth)acrylate and ethyl (meth)acrylate. The structural unit having an ester group not only functions as a component that suppresses the alkali solubility of the photosensitive composition, but also functions as a component that improves the solubility in a solvent and further the resolubility in a solvent.

The carboxyl group-containing copolymer can be made into an alkali-soluble resin having desired performance by appropriately adjusting the amount of each constituent unit added.
The amount of the carboxyl group-containing ethylenically unsaturated monomer charged is preferably 5% by mass or more, more preferably 10% by mass or more based on the total amount of monomers, from the viewpoint of obtaining a good pattern. On the other hand, from the viewpoint of suppressing film roughness on the pattern surface after development, the amount of the carboxyl group-containing ethylenically unsaturated monomer added is preferably 50% by mass or less, and 40% by mass or less based on the total amount of monomers. It is more preferable that there be.

In addition, carboxy group-containing copolymers such as (meth)acrylic copolymers and styrene-(meth)acrylic copolymers having structural units having ethylenically unsaturated bonds are more preferably used as alkali-soluble resins. The compound having both an epoxy group and an ethylenically unsaturated bond is preferably 10% by mass or more and 95% by mass or less, and 15% by mass or more and 90% by mass based on the charged amount of the carboxyl group-containing ethylenically unsaturated monomer. % or less is more preferable.

The preferred weight average molecular weight (Mw) of the carboxyl group-containing copolymer is preferably in the range of 1,000 to 50,000, more preferably 3,000 to 20,000. When it is 1,000 or more, the binder function after curing is improved, and when it is 50,000 or less, pattern formation becomes good during development with an alkaline developer.
The weight average molecular weight (Mw) of the alkali-soluble resin can be measured using Shodex GPC System-21H using polystyrene as a standard substance and THF as an eluent.

The epoxy (meth) acrylate resin having a carboxyl group is not particularly limited, but includes epoxy (meth) acrylate obtained by reacting a reaction product of an epoxy compound and an unsaturated group-containing monocarboxylic acid with an acid anhydride. Acrylate compounds are suitable.
The epoxy compound, unsaturated group-containing monocarboxylic acid, and acid anhydride can be appropriately selected from known ones and used.
The epoxy (meth)acrylate resin having a carboxyl group preferably has the hydrocarbon ring in the molecule, and among them, those containing a cardo structure improve the curability of the colored layer and prevent discoloration of the coloring material. This is preferable from the viewpoint of suppressing the amount of color and increasing the residual film rate of the colored layer.
The epoxy (meth)acrylate resins having a carboxyl group may be used alone or in combination of two or more.

It is preferable to select and use an alkali-soluble resin having an acid value of 40 mgKOH/g or more from the viewpoint of developability (solubility) in an alkaline aqueous solution used as a developer. The alkali-soluble resin preferably has an acid value of 40 mgKOH/g or more and 300 mgKOH/g or less, from the viewpoint of developability (solubility) in an alkaline aqueous solution used in the developer and adhesion to the substrate. It is preferably 50 mgKOH/g or more and 280 mgKOH/g or less.

When the alkali-soluble resin has an ethylenically unsaturated group in its side chain, the ethylenically unsaturated bond equivalent improves the film strength of the cured film, makes it easier to maintain a low retardation, improves development resistance, and improves bonding with the substrate. In order to obtain the effect of excellent adhesion, the number is preferably in the range of 100 to 2,000, more preferably in the range of 140 to 1,500, and may be in the range of 140 to 1,000. If the ethylenically unsaturated bond equivalent is below the upper limit, it is easy to maintain a low retardation, and the development resistance and adhesion are excellent. In addition, if it is above the lower limit, it is possible to relatively increase the proportion of other structural units such as the structural unit having a carboxy group or a structural unit having a hydrocarbon ring, resulting in excellent developability and heat resistance. ing.
Here, the ethylenically unsaturated bond equivalent refers to the mass average molecular weight per mole of ethylenically unsaturated bonds in the alkali-soluble resin, and is expressed by the following formula (1).

Formula (1)
Ethylenically unsaturated bond equivalent (g/mol) = W (g)/M (mol)
(In formula (1), W represents the mass (g) of the alkali-soluble resin, and M represents the number of moles (mol) of ethylenically unsaturated bonds contained in the alkali-soluble resin W (g).)

The ethylenically unsaturated bond equivalent can be determined, for example, by measuring the number of ethylenically unsaturated bonds contained per gram of alkali-soluble resin in accordance with the iodine value test method described in JIS K 0070:1992. It may be calculated.

The alkali-soluble resins used in the blue photosensitive composition may be used alone or in combination of two or more. The content of the alkali-soluble resin is not particularly limited, but is preferably in the range of 5% to 60% by mass, more preferably 10% to 40% by mass, based on the total solid content of the blue photosensitive composition. It is within. When the content of the alkali-soluble resin is at least the above lower limit, sufficient alkali developability can be obtained, and when the content of the alkali-soluble resin is at or below the above upper limit, film roughness and pattern chipping may occur during development. It can be suppressed.

<Photopolymerizable compound>
The photopolymerizable compound used in the blue-sensitive composition of the present invention is not particularly limited as long as it can be polymerized by a photoinitiator, and compounds having two or more ethylenically unsaturated bonds are usually preferred. It is preferably a polyfunctional (meth)acrylate that is used for, and has two or more acryloyl groups or methacryloyl groups.
Such polyfunctional (meth)acrylates may be appropriately selected from conventionally known ones. Specific examples include those described in JP-A No. 2013-029832.

One type of these polyfunctional (meth)acrylates may be used alone, or two or more types may be used in combination. In addition, in the blue-sensitive composition of the present invention, since excellent photocurability is required, the polyfunctional (meth)acrylate is preferably a compound having three or more ethylenically unsaturated bonds (trifunctional). , more preferably a compound containing 3 to 15 ethylenically unsaturated bond groups, and even more preferably a compound containing 3 to 6 ethylenically unsaturated bond groups. Further, the polymerizable compound is preferably a 3- to 15-functional (meth)acrylate compound, more preferably a 3- to 6-functional (meth)acrylate compound.
As the compound having three or more ethylenically unsaturated bonds (trifunctional), for example, poly(meth)acrylates of trihydric or higher polyhydric alcohols and dicarboxylic acid modified products thereof are preferable. Methylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, succinic acid modified product of pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta Preferred are (meth)acrylate, a succinic acid-modified product of dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like.

The photopolymerizable compound used in the blue photosensitive composition of the present invention may contain a photopolymerizable compound having an acidic group from the viewpoint of developability. Examples of the acidic group include a carboxyl group, a sulfo group, a phosphoric acid group, and a carboxyl group is preferred. Commercially available photopolymerizable compounds having acidic groups include Aronix M-510, M-520, Aronix TO-2349 (manufactured by Toagosei Co., Ltd.), and the like.
In the photopolymerizable compound used in the blue photosensitive composition of the present invention, the content of the photopolymerizable compound having an acidic group is 20% by mass or less based on the total amount of the photopolymerizable compound from the viewpoint of developability. The content may be 10% by mass or less, 5% by mass or less, and 0% by mass from the viewpoint of the acid value of the alkali-soluble resin to be combined.

The photopolymerizable compound used in the blue photosensitive composition of the present invention is a photopolymerizable compound having a caprolactone structure because it is good in terms of adjusting curability, is easy to form a fine pattern, and is easy to suppress chipping. may contain. The photopolymerizable compound having a caprolactone structure may contain a ring-opened structure of ε-caprolactone, and may contain a ring-opened structure of ε-caprolactone as a repeating unit.
A photopolymerizable compound having a caprolactone structure can be obtained, for example, by esterifying an alcohol, (meth)acrylic acid, and ε-caprolactone, and among them, a polyhydric alcohol, (meth)acrylic acid, and ε-caprolactone. A compound obtained by esterifying caprolactone is preferably used.
As the photopolymerizable compound having a caprolactone structure, commercially available products may be used as appropriate. As a commercial product, for example, it is commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series.
In the photopolymerizable compound used in the blue photosensitive composition of the present invention, the content of the photopolymerizable compound having a caprolactone structure is 0% by mass based on the total amount of the photopolymerizable compound from the viewpoint of adjusting curability. It may be between 70% and 10% and 50% by weight.

In addition, the photopolymerizable compound used in the blue photosensitive composition of the present invention is a photopolymerizable compound having an alkyleneoxy group because it is good in terms of adjusting curability, easily forms fine patterns, and easily suppresses chipping. It may contain a polymerizable compound. The photopolymerizable compound having an alkyleneoxy group is preferably a photopolymerizable compound having an ethyleneoxy group and/or a propyleneoxy group, more preferably a photopolymerizable compound having an ethyleneoxy group, and has 4 to 20 ethyleneoxy groups. More preferred are tri- to hexa-functional (meth)acrylate compounds having the following. Commercially available photopolymerizable compounds having an alkyleneoxy group include, for example, ethoxylated (4) pentaerythritol tetraacrylate (manufactured by Sartomer Co., Ltd., trade name SR-494), trimethylolpropane tripropoxy triacrylate (Nippon Kayaku Co., Ltd.) Co., Ltd., product name KAYARAD TPA-330), ethylene oxide 12 mole modified dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd., product name KAYARAD DPEA-12), Daiichi Kogyo Seiyaku Co., Ltd. product name New Frontier MF -001 etc.
In the photopolymerizable compound used in the blue photosensitive composition of the present invention, the content of the photopolymerizable compound having an alkyleneoxy group is set to 0 mass with respect to the total amount of the photopolymerizable compound from the viewpoint of adjusting curability. % to 50% by weight, and 5% to 40% by weight.

As the mass average molecular weight per mole of photopolymerizable groups of the entire photopolymerizable compound used in the blue photosensitive composition of the present invention, for example, the unsaturated bond equivalent is preferably 300 or less from the viewpoint of curability, It is more preferably 250 or less, still more preferably 200 or less. The unsaturated bond equivalent may be 97 or less from the viewpoint of curability. Although the unsaturated bond equivalent is preferably small, the lower limit may be about 50.
The unsaturated bond equivalent herein refers to the mass average molecular weight per mole of unsaturated bonds of the photopolymerizable compound, and is expressed by the following formula (2).
Formula (2)
Unsaturated bond equivalent (g/mol) = W2 (g)/M2 (mol)
(In formula (1), W2 represents the mass (g) of the photopolymerizable compound, and M2 represents the number of moles (mol) of unsaturated bonds contained in the photopolymerizable compound W2 (g).)

The content of the photopolymerizable compound used in the blue-sensitive composition is not particularly limited, but is preferably 5% by mass to 60% by mass, more preferably 5% by mass, based on the total solid content of the blue-sensitive composition. is within the range of 10% by mass to 40% by mass. If the content of the photopolymerizable compound is at least the above lower limit, photocuring will proceed sufficiently, and elution of the exposed area during development can be suppressed, and if the content of the photopolymerizable compound is below the above upper limit, Alkaline developability is sufficient.

<Photoinitiator>
The photoinitiators in the blue photosensitive composition used in the method for producing a blue cured film of the present invention include an oxime photoinitiator and a sensitizer having a sensitizing effect in the range of 400 nm to 420 nm, which is different from the oxime photoinitiator. including.
Among them, the blue photosensitive composition of the present invention suitably used in the method for producing a blue cured film of the present invention is an oxime-based photoinitiator represented by the following general formula (A), which is different from the oxime-based photoinitiator. Contains a sensitizer that has a sensitizing effect at 400 nm to 420 nm.

(oxime photoinitiator)
In the present invention, the oxime-based photoinitiator refers to a photoinitiator having an oxime ester skeleton.
Examples of oxime photoinitiators include 1,2-octadione-1-[4-(phenylthio)phenyl]-,2-(o-benzoyloxime), ethanone, 1-[9-ethyl-6-(2 -Methylbenzoyl)-9H-carbazol-3-yl]-,1-(o-acetyloxime), JP 2000-80068, JP 2001-233842, JP 2010-527339, JP 2010-527339, JP Oxime-based photoinitiators described in JP 2010-527338, JP 2013-041153, WO 2015/152153, WO 2018/062105, etc. can be appropriately selected and used.
Among the oxime-based photoinitiators used in the present invention, when a blue coloring material and an LED light source having the above-mentioned two specific emission peak wavelengths are combined, sensitivity and undercut width that occurs after development can be improved. In order to improve suppression, at least one member selected from the group consisting of an oxime photoinitiator having a diphenyl sulfide skeleton, an oxime photoinitiator having an indole skeleton, and an oxime photoinitiator having a carbazole skeleton. It is preferable that there be.

As an oxime photoinitiator having a diphenyl sulfide skeleton, among others, a compound represented by the following general formula (A) is used in combination with a blue coloring material and an LED light source having the above-mentioned two specific emission peak wavelengths. It is preferably used because it improves sensitivity, suppresses undercut width that occurs after development, and improves water resistance after development.

In the general formula (A), the linear or branched alkyl group having 1 to 12 carbon atoms in Z ¹ , Z ³ , Z ⁴ and Z ⁵ includes, for example, a methyl group, an ethyl group, and an n-propyl group. , i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group , n-decyl group, n-undecyl group, n-dodecyl group, etc.
Examples of the cycloalkyl group having 3 to 20 carbon atoms in Z ¹ , Z ³ , Z ⁴ and Z ⁵ include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclooctadecyl group. Examples include groups.
The cycloalkyl group in Z ² may be the same as the cycloalkyl group having 3 to 20 carbon atoms, and cyclopentyl group and cyclohexyl group are preferable.
Examples of the alkyl group having 1 to 20 carbon atoms in Z ² include n-tetradecyl, n-hexadecyl, n-octadecyl groups, etc. in addition to the linear or branched alkyl group having 1 to 12 carbon atoms. It will be done.

Further, in Z ¹ , Z ³ , Z ⁴ and Z ⁵ , examples of the halogen atom which may be substituted in the alkyl group, cycloalkyl group, and phenyl group include a fluorine atom, a chlorine atom, a bromine atom, etc. .
In Z ¹ , Z ³ , Z ⁴ and Z ⁵ , the alkyl group, cycloalkyl group, and alkoxy group having 1 to 6 carbon atoms which may be substituted with a phenyl group include, for example, a methoxy group, an ethoxy group , n-propoxy group, i-propoxy group, n-butoxy group, t-butoxy group, etc.

In general formula (A), from the viewpoint of improving sensitivity, Z ¹ is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group, more preferably a methyl group, an ethyl group, or a phenyl group, and more preferably a methyl group. More preferred.
In general formula (A), Z ³ , Z ⁴ and Z ⁵ are preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an i-propyl group from the viewpoint of brightness.

In general formula (A), from the viewpoint of solvent solubility and compatibility, Z ² is preferably an alkyl group having 1 to 14 carbon atoms substituted with a cycloalkyl group having 5 to 6 carbon atoms; An alkyl group having 1 to 10 carbon atoms substituted with 6 cycloalkyl groups is more preferred, a cyclohexylmethyl group or a cyclopentylmethyl group is even more preferred, and a cyclohexylmethyl group is particularly preferred.

As the photoinitiator represented by the general formula (A), an oxime ester compound represented by the following chemical formula (A-1) is particularly preferable, since sublimates are unlikely to be generated. Commercially available products include TR-PBG-3057 (manufactured by Changzhou Strong Electronics New Materials Co., Ltd.).

For the photoinitiator represented by the general formula (A), for example, refer to Japanese Patent Application Publication No. 2012-526185, diphenyl sulfide or a derivative thereof is used, and depending on the material used, the solvent, reaction temperature, reaction time, It can be synthesized by appropriately selecting a purification method and the like. Alternatively, commercially available products may be appropriately obtained and used.

Examples of oxime photoinitiators having a diphenyl sulfide skeleton include 1,2-octadione, 1-[4-(phenylthio)phenyl]-,2-(o-benzoyloxime) (for example, Irgacure OXE01, manufactured by BASF), 1,2-propanedione, 3-cyclopentyl-1-[4-(phenylthio)phenyl]-,2-(o-benzoyloxime) (e.g., TR-PBG-305, manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), 1 , 2-propanedione, 3-cyclopentyl-1-[4-[(2-hydroxyethoxy)phenylthio]phenyl]-, 2-(o-acetyloxime), 1-pentanone, 1-[4-[4-( 2-Benzofuranylcarbonyl)phenylthio]phenyl]-4-methyl,1-(o-acetyloxime), commercially available products such as Adeka Arcles NCI-930 (manufactured by ADEKA) and Irgacure OXE04 (manufactured by BASF) were used. It's okay.

Examples of the oxime photoinitiator having an indole skeleton include a compound represented by the following general formula (B).

(wherein R ¹ and R ² each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN,
R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an arylalkyl group having 2 to 20 carbon atoms. represents a heterocyclic group,
The hydrogen atoms of the groups represented by R ¹¹ , R ¹² and R ¹³ are further represented by R ²¹ , OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , -NR ²² -OR ²³ , -NCOR ²² - OCOR ²³ , NR ²² COR ²¹ , OCOR ²¹ , COOR ²¹ , SCOR ²¹ , OCSR ²¹ , COSR ²¹ , ^{CSOR 21} , optionally substituted with a hydroxyl group, a nitro group, CN, or a halogen atom,
R ²¹ , R ²² and R ²³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an arylalkyl group having 2 to 20 carbon atoms. represents a heterocyclic group,
The hydrogen atoms of the groups represented by R ²¹ , R ²² and R ²³ may be further substituted with a hydroxyl group, a nitro group, CN, a halogen atom, or a carboxy group,
The alkylene moiety of the group represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ is -O-, -S-, -COO-, -OCO-, -NR ²⁴ -, -NR ²⁴ CO-, -NR ²⁴ COO-, -OCONR ²⁴ -, -SCO-, -COS-, -OCS- or -CSO- may contain 1 to 5 of them, provided that oxygen atoms are not adjacent to each other,
^R24 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms;
The alkyl portion of the group represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ²⁴ may have a branched side chain or may be a cyclic alkyl,
R ³ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or ^a heterocyclic group having 2 to 20 carbon atoms; The alkyl portion of the group represented may have a branched side chain or may be a cyclic alkyl, and R ³ and R ⁷ and R ³ and R ⁸ may each be taken together to form a ring. You can also
The hydrogen atom of the group represented by R ³ is further R ²¹ , OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , -NR ²² -OR ²³ , -NCOR ²² -OCOR ²³ , NR ²² COR ²¹ , OCOR ²¹ , COOR ²¹ , SCOR ²¹ , OCSR ²¹ , COSR ²¹ , CSOR ²¹ , which may be substituted with a hydroxyl group, a nitro group, CN, or a halogen atom,
R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹⁴ , CONR ¹⁵ R ¹⁶ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹⁴ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹⁴ , CSOR ¹¹ represent a hydroxyl group, CN or a halogen atom, and R ⁴ and R ⁵ , R ⁵ and R ⁶ , and R ⁶ and R ⁷ may each be taken together to form a ring,
R ¹⁴ , R ¹⁵ and R ¹⁶ represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the alkyl portion of the group represented by R ¹⁴ , R ¹⁵ and R ¹⁶ may have a branched side chain. , cyclic alkyl, ^R8 may be ^R11 , ^OR11 , ^SR11 , ^COR11 , ^CONR12R13 , ^NR12COR11 , ^OCOR11 ^, ^COOR11 , ^SCOR11 ^, ^OCSR11 , ^COSR11 , CSOR ¹¹ represents a hydroxyl group, CN or a halogen atom,
k represents 0 or 1. )

The oxime ester compound represented by the general formula (B) has geometric isomers due to the double bond of the oxime, but these are not distinguished. That is, in this specification, the compound represented by the above general formula (B), the compound represented by the following general formula (B') which is a preferred form of the compound described below, and its exemplary compounds are a mixture of both or either It represents either one of the isomers, and is not limited to the structure showing the isomer.

1 to 20 carbon atoms represented by R ³ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²¹ , R ²² , R ²³ and R ²⁴ in the above general formula (B) Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t- Octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl and the like.

The aryl group having 6 to 30 carbon atoms represented by R ³ , R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ²⁴ in the above general formula (B) includes, for example, phenyl , tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, phenyl substituted with one or more of the above alkyl groups, biphenylyl, naphthyl, anthryl, and the like.

The arylalkyl group having 7 to 30 carbon atoms represented by R ³ , R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ²⁴ in the above general formula (B) is, for example, Examples include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, and phenylethyl.

The heterocyclic group having 2 to 20 carbon atoms represented by R ³ , R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ²⁴ in the above general formula (B) includes, for example , pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl, isoxazolidyl, piperidyl, piperazyl, morpholinyl, etc. ~7-membered heterocycles.
In the above general formula (B), the ring that can be formed by combining R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ³ and R ⁷ , and R ³ and R ⁸ is: For example, 5- to 7-membered rings such as a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a benzene ring, a piperidine ring, a morpholine ring, a lactone ring, and a lactam ring are preferably mentioned.

Further, halogen atoms represented by R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ in the above general formula (B), and R ³ , R ¹¹ , R ¹² in the above general formula (B) , R ¹³ , R ²¹ , R ²² and R ²³ include fluorine, chlorine, bromine, and iodine.

In the above general formula (B), the alkylene moiety of the group represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ is -O-, -S-, -COO-, -OCO -, -NR ²⁴ -, -NR ²⁴ CO-, -NR ²⁴ COO-, -OCONR ²⁴ -, -SCO-, -COS-, -OCS- or -CSO- from 1 to 1 under the condition that oxygen atoms are not adjacent to each other. It may contain 5 divalent groups, and in this case, the divalent groups contained may be one type or two or more types of groups, and in the case of groups that can be contained consecutively, two or more groups may be contained consecutively. .

In addition, the alkyl (alkylene) moiety of the group represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ²⁴ in the above general formula (B) has a branched side chain. It may also be a cyclic alkyl.
Among the compounds represented by the above general formula (B), those in which R ³ is an optionally fused aromatic ring or the compounds represented by the following general formula (B') have high sensitivity and are easy to manufacture. This is preferable because it is easy.

(In the formula, R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and k are the same as in the above general formula (B), and R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are each independently R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹¹ , CONR ¹⁵ R ¹⁶ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹⁴ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹⁴ , CSOR ¹¹ , hydroxyl group , represents a nitro group, CN, or a halogen atom, and R ³¹ and R ³² , R ³² and R ³³ , R ³³ and R ³⁴ , and R ³⁴ and R ³⁵ may each be taken together to form a ring.)

Examples of rings formed by R ³¹ and R ³² , R ³² and R ³³ , R ³³ and R ³⁴ and R ³⁴ and R ³⁵ are R ⁴ and R ⁵ , R ⁵ and R ⁶ and R ⁶ Examples of rings that can be formed by combining and R ⁷ , R ³ and R ⁷ , and R ³ and R ⁸ include the same rings as those listed above.

In the above general formulas (B) and (B'), R ¹ is an alkyl group having 1 to 12 carbon atoms or an arylalkyl group having 7 to 15 carbon atoms, R ¹¹ is an aryl group having 6 to 12 carbon atoms, and R 11 is an aryl group having 6 to 12 carbon atoms; ~8 alkyl groups are preferred because they have high solvent solubility; ^R2 are preferably methyl, ethyl, or phenyl groups because they have high reactivity; ^R4 ~ ^R7 are hydrogen atoms or cyano A group, especially a hydrogen atom, is preferred because it is easy to synthesize, a hydrogen atom as R ⁸ is preferred because it is easy to synthesize, and a group where k is 1 is preferred because it has high sensitivity. ), at least one of R ³¹ to R ³⁵ is a nitro group, CN, a halogen atom, or COR ¹¹ , and R ¹¹ is an aryl group having 6 to 12 carbon atoms or an alkyl group having 1 to 8 carbon atoms; It is preferable because the sensitivity is high, and it is more preferable that at least one of R ³¹ to R ³⁵ is a nitro group, CN, a halogen atom, or COPh (here, Ph is a phenyl group), and R ³³ is a nitro group, CN, a halogen atom, or a COPh group. Particularly preferred are atoms or COPh.

Preferable specific examples of the compound represented by the above general formula (B) include the following compounds. In addition, compound No. 1, which is described in International Publication No. 2015/152153, 1~No. 212 is mentioned.

The compound represented by the above general formula (B) can be prepared by, for example, referring to International Publication No. 2015/152153, and selecting the solvent, reaction temperature, reaction time, purification method, etc. appropriately according to the materials used. Can be synthesized. Alternatively, commercially available products may be appropriately obtained and used.

Examples of oxime photoinitiators having a carbazole skeleton include ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) (for example, Irgacure OXE02, manufactured by BASF), methanone, [8-[[(acetyloxy)imino][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methyl]-11-(2- ethylhexyl)-11H-benzo[a]carbazol-5-yl]-, (2,4,6-trimethylphenyl) (e.g. Irgacure OXE-03, manufactured by BASF), ethanone, 1-[9-ethyl-6- (1,3-dioxolane, 4-(2-methoxyphenoxy)-9H-carbazol-3-yl]-, 1-(o-acetyloxime), methanone, (9-ethyl-6-nitro-9H-carbazol- 3-yl)[4-(2-methoxy-1-methylethoxy-2-methylphenyl]-,o-acetyloxime, 1-propanone,3-cyclopentyl-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazol-3-yl]-,1-(o-acetyloxime) (for example, TR-PBG-304, manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), 1-propanone, 3-cyclopentyl-1-[ 2-(2-pyrimidinylthio)-9H-carbazol-3-yl]-, 1-(o-acetyloxime), ethanone, 2-cyclohexyl-1-[2-(2-pyrimidinyloxy)-9H-carbazole- 3-yl]-,1-(o-acetyloxime), ethanone, 2-cyclohexyl-1-[2-(2-pyrimidinylthio)-9H-carbazol-3-yl]-,1-(o-acetyloxime) ), 1-octanone, 1-[4-[3-[1-[(acetyloxy)imino]ethyl]-6-[4-[(4,6-dimethyl-2-pyrimidinyl)thio]-2-methyl Benzoyl]-9H-carbazol-9-yl]phenyl]-,1-(o-acetyloxime) (for example, EXTA-9, manufactured by Union Chemical), commercially available products include ADEKA OPT-N-1919 (manufactured by ADEKA) , ADEKA Arkles NCI-831 (manufactured by ADEKA), and the like.
As the oxime photoinitiator having a carbazole skeleton, a compound represented by the following general formula (C) is particularly preferred.

(In formula (C), X ¹ , X ³ and X ⁶ each independently represent R ⁴¹ , OR ⁴¹ , COR ⁴¹ , SR ⁴¹ , CONR ⁴² R ⁴³ or CN, and X ² has a carbon number of 1 to 20 alkyl group, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, and X ⁴ and X ⁵ are each independently R ⁴¹ , OR ⁴¹ , SR ⁴¹ , COR ⁴¹ , CONR ⁴² R ⁴³ , NR ⁴² COR ⁴¹ , OCOR ⁴¹ , COOR ⁴¹ , SCOR ⁴¹ , OCSR ⁴¹ , COSR ⁴¹ , CSOR ⁴¹ , CN, represents a halogen atom or a hydroxyl group.
R ⁴¹ , R ⁴² and R ⁴³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an arylalkyl group having 2 to 20 carbon atoms. represents a heterocyclic group,
R ⁴¹ ^, R ⁴² ^and ^R ⁴³ ^, and ^the hydrogen atom ^of ^the ^group ^represented ^by ⁵³ , -NCOR ⁵² -OCOR ⁵³ , NR ⁵² COR ⁵¹ , OCOR ⁵¹ , COOR ⁵¹ , SCOR ⁵¹ , OCSR ⁵¹ , COSR ⁵¹ , CSOR ⁵¹ , optionally substituted with a hydroxyl group, a nitro group, CN, or a halogen atom,
R ⁵¹ , R ⁵² and R ⁵³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an arylalkyl group having 2 to 20 carbon atoms. represents a heterocyclic group,
The hydrogen atoms of the groups represented by R ⁵¹ , R ⁵² and R ⁵³ may be further substituted with a hydroxyl group, a nitro group, CN, a halogen atom, or a carboxy group,
The alkylene moiety of the group represented by R ⁴¹ , R ⁴² , R ⁴³ , X ² , R ⁵¹ , R ⁵² and R ⁵³ is -O-, -S-, -COO-, -OCO-, -NR ⁵⁴ - , -NR ⁵⁴ CO-, -NR ⁵⁴ COO-, -OCONR ⁵⁴ -, -SCO-, -COS-, -OCS- or -CSO-, even if it contains 1 to 5 oxygen atoms adjacent to each other. often,
R ⁵⁴ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms;
The alkyl portion of the group represented by R ⁴¹ , R ⁴² , R ⁴³ , R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ may have a branched side chain or may be a cyclic alkyl.
a and b are each independently an integer of 0 to 3. )

The oxime ester compound represented by the general formula (C) also has geometric isomers due to the double bond of the oxime, but these are not distinguished. That is, in this specification, the compound represented by the general formula (C) and its exemplified compounds represent a mixture of both or either one, and are not limited to structures showing isomers.

In the above general formula (C ⁾ ^, ^the alkyl ^group ^having 1 ^to ²⁰ carbon atoms ^represented by Examples include the same alkyl groups having 1 to 20 carbon atoms in (B).
The aryl group having 6 to 30 carbon atoms represented by X ² , R ⁴¹ , R ⁴² , R ⁴³ , R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ in the general formula (C) is Examples include those similar to the aryl group having 6 to 30 carbon atoms in (B).
In the above general ^formula ⁽ C ⁾ , ^the arylalkyl ^group having ⁷ ^to ³⁰ carbon atoms represented by Examples include those similar to the arylalkyl group having 7 to 30 carbon atoms in formula (B).
The heterocyclic group having 2 to 20 carbon atoms represented by X ² , R ⁴¹ , R ⁴² , R ⁴³ , R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ in the above general formula (C) is Examples include those similar to the heterocyclic group having 2 to 20 carbon atoms in formula (B).
Furthermore, examples of the halogen atom in the above general formula (C) include the same halogen atoms as in the above general formula (B).

In the above general formula (C), the alkylene moiety of the group represented by R ⁴¹ , R ⁴² , R ⁴³ , X ² , R ⁵¹ , R ⁵² and R ⁵³ is -O-, -S-, -COO- , -OCO-, -NR ⁵⁴ -, -NR ⁵⁴ CO-, -NR ⁵⁴ COO-, -OCONR ⁵⁴ -, -SCO-, -COS-, -OCS- or -CSO- under conditions where oxygen atoms are not adjacent to each other. It may contain 1 to 5 divalent groups, and the divalent groups contained in this case may be one type or two or more types of groups, and in the case of groups that can be contained consecutively, two or more groups may be contained consecutively. It's okay.

In the above general formula (C), X ¹ is more preferably a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, from the viewpoint of sensitivity, solubility, and compatibility. Alkyl groups having 1 to 10 carbon atoms such as t-butyl group, n-amyl group, isoamyl group, t-amyl group, n-hexyl group and 2-ethylhexyl group; 5 carbon atoms such as cyclopentyl group and cyclohexyl group; A cyclic alkyl group which may have ~10 side chains, or a methoxymethyl group, an ethoxymethyl group, an ethoxyethyl group, a 2-(1-methoxypropyl) group, a 2-(1-ethoxypropyl) group, etc. An alkyl group having one ether bond in a methylene chain having 2 to 10 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms such as a methyl group, ethyl group, or 2-ethylhexyl group.

In the general formula (C), X ² , X ³ and X ⁶ are each independently particularly preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group alkyl groups having 1 to 6 carbon atoms such as n-butyl, isobutyl, t-butyl, n-amyl, isoamyl, t-amyl and n-hexyl groups, cyclopentyl and cyclohexyl groups, etc. A cyclic alkyl group having 5 to 6 carbon atoms, or a cyclic alkyl group having a carbon number of 5 to 6, such as a methoxymethyl group, an ethoxymethyl group, an ethoxyethyl group, a 2-(1-methoxypropyl) group, and a 2-(1-ethoxypropyl) group. An alkyl group having 2 to 6 carbon atoms and one ether bond in the methylene chain, more preferably an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 2 to 6 carbon atoms and one ether bond in the methylene chain. is an alkyl group having
From the viewpoint of sensitivity, solubility, and compatibility, X ³ and X ⁶ are each independently an alkyl group having 1 to 6 carbon atoms.
From the viewpoints of sensitivity, solubility and compatibility, X ² is more preferably an alkyl group having 2 to 6 carbon atoms and having one ether bond in the methylene chain.

In the general formula (C), X ⁴ and X ⁵ are each independently particularly preferably hydrogen, methyl group, ethyl group, n-propyl group, Alkyl groups having 1 to 6 carbon atoms such as isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-amyl group, isoamyl group, t-amyl group and n-hexyl group.

Preferred specific examples of the compound represented by the above general formula (C) include the following compounds.

The compound represented by the above general formula (C) can be prepared by, for example, referring to JP-A No. 2010-256891 and selecting the solvent, reaction temperature, reaction time, purification method, etc. as appropriate depending on the materials used. Can be synthesized. Alternatively, commercially available products may be appropriately obtained and used.

In the blue photosensitive composition used in the present invention, the oxime photoinitiator can be used alone or in a mixture of two or more.

(Sensitizer that has a sensitizing effect at 400 nm to 420 nm)
In the blue photosensitive composition used in the present invention, since an LED lamp having an emission peak wavelength of 400 nm to 420 nm is used, in addition to the oxime photoinitiator, an LED lamp having an emission peak wavelength of 400 nm to 420 nm, which is different from the oxime photoinitiator, is used. A sensitizer having a sensitizing effect at 420 nm is contained.
The sensitizer having a sensitizing effect in the wavelength range of 400 nm to 420 nm, which is different from the oxime photoinitiator, can be used without particular limitation as long as it has absorption in the wavelength range of 400 nm to 420 nm. Whether or not the sensitizer used in the present invention has a sensitizing effect in the wavelength range of 400 nm to 420 nm can be determined by observing the absorption spectrum of a solution prepared by dissolving the sensitizer in a solvent such as acetonitrile at a concentration of 0.01 mg/ml under ultraviolet light. It can be measured with a visible spectrophotometer and can be determined to have absorption in the range of 400 nm to 420 nm. The sensitizer used in the present invention has an absorbance of 0.1 or more when the absorption spectrum of a solution dissolved in a solvent such as acetonitrile at a concentration of 0.01 mg/ml is measured using an ultraviolet-visible spectrophotometer. It is preferable.

The sensitizers having a sensitizing effect in the wavelength range of 400 nm to 420 nm used in the present invention include, for example, thioxanthone sensitizers, aromatic ketone sensitizers, anthracene sensitizers, and naphthalene sensitizers. At least one selected from the group can be appropriately selected and used.
Examples of thioxanthone-based sensitizers include 2,4-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, and 2,4-dichlorothioxanthone.
Examples of the aromatic ketone sensitizer include benzophenone sensitizers, such as benzophenone, 4,4'-bisdiethylaminobenzophenone, and 4-methoxy-4'-dimethylaminobenzophenone.
Examples of anthracene-based sensitizers include anthracene compounds substituted with alkoxy or acyloxy groups, such as 9,10-bis(acetyloxy)anthracene, 9,10-bis(propionyloxy)anthracene, and 9,10-bis(propionyloxy)anthracene. Bis(n-propylcarbonyloxy)anthracene, 9,10-bis(isopropylcarbonyloxy)anthracene, 9,10-bis(n-butylcarbonyloxy)anthracene, 9,10-bis(isobutylcarbonyloxy)anthracene, 9, 10-bis(n-hexanoyloxy)anthracene, 9,10-bis(n-heptanoyloxy)anthracene, 9,10-bis(n-octanoyloxy)anthracene, 9,10-bis(2-ethylhexane) Examples include 9,10-bis(n-nonanoyloxy)anthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-dibutoxyanthracene.
Examples of naphthalene-based sensitizers include naphthalene compounds substituted with alkoxy or acyloxy groups, such as 1,4-diethoxynaphthalene.

The sensitizers having a sensitizing effect in the wavelength range of 400 nm to 420 nm used in the blue-sensitive composition of the present invention can be used alone or in combination of two or more.

(Other photoinitiators)
The blue-sensitive composition used in the present invention may contain other photoinitiators different from the oxime photoinitiator and the sensitizer having a sensitizing effect in the range of 400 nm to 420 nm, as long as the effects of the present invention are not impaired. It may also contain an agent. Other photoinitiators may be appropriately selected from benzoin ethers, halomethyloxadiazole compounds, α-aminoketones, biimidazoles, halomethyl-S-triazine compounds, acylphosphine oxides, etc. can.
Even when other photoinitiators are included, the total content of the oxime-based photoinitiator may be 50% by mass or more with respect to the total content of the oxime-based photoinitiator and other photoinitiators. , 70% by mass or more.

In the total amount of photoinitiators, the total content of oxime photoinitiators may have a lower limit of 15% by mass or more, and may be 25% by mass or more, and an upper limit of 90% by mass, from the viewpoint of improving curability. or less, and may be less than or equal to 80% by mass.
When the other photoinitiator is included, the lower limit of the total content of the oxime photoinitiator and other photoinitiator may be 15% by mass or more, and 25% by mass or more, from the viewpoint of improving curability. The upper limit may be 90% by mass or less, and may be 80% by mass or less.

In the total amount of photoinitiators, the lower limit of the total content of sensitizers having a sensitizing effect in the range of 400 nm to 420 nm, which is different from oxime photoinitiators, may be 10% by mass or more from the viewpoint of improving curability. , may be 20% by mass or more, and the upper limit may be 85% by mass or less, and may be 75% by mass or less.

In addition, the content ratio of the total of the oxime photoinitiator and other photoinitiators used in the blue photosensitive composition and the sensitizer having a sensitizing effect in the range of 400 nm to 420 nm is determined by the sensitivity and line width shift. In terms of balance, the total content of the sensitizers having a sensitizing effect in the range of 400 nm to 420 nm is preferably set to 100 parts by mass of the oxime photoinitiator and other photoinitiators. It is 20 parts by mass or more, more preferably 50 parts by mass or more, preferably 500 parts by mass or less, and more preferably 300 parts by mass or less.

In the blue photosensitive composition used in the present invention, the total content of sensitizers having a sensitizing effect at 400 nm to 420 nm is not particularly limited as long as the effect of the present invention is not impaired. It is preferably within the range of 0.1% by mass to 5% by mass, more preferably within the range of 0.2% by mass to 3% by mass, based on the total solid content. If this content is above the above lower limit, photocuring will proceed sufficiently, the exposed areas will be prevented from dissolving during development, and the solvent resistance will be good, while if it is below the above upper limit, the coloring obtained will be improved. Decrease in brightness and deterioration in developability due to yellowing of the layer can be suppressed.

In the blue photosensitive composition used in the present invention, the total content of photoinitiators is not particularly limited as long as the effects of the present invention are not impaired, but it is preferably based on the total solid content of the blue photosensitive composition. is within the range of 0.5% by mass to 12.0% by mass, more preferably within the range of 1.0% by mass to 8.0% by mass. If this content is above the above lower limit, photocuring will proceed sufficiently, the exposed areas will be prevented from dissolving during development, and the solvent resistance will be good, while if it is below the above upper limit, the coloring obtained will be improved. Decrease in brightness and deterioration in developability due to yellowing of the layer can be suppressed.

In addition, the content ratio of the photopolymerizable compound and the photoinitiator used in the blue photosensitive composition is such that line width shift is suppressed and the pattern shape is improved. , the total content of the photoinitiator is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, preferably 40 parts by mass or less, and more preferably 30 parts by mass or less. .
In addition, the content ratio of the photopolymerizable compound and the sensitizer having a sensitizing effect in the range of 400 nm to 420 nm used in the blue photosensitive composition is determined from the viewpoint of suppressing line width shift and improving the pattern shape. , with respect to 100 parts by mass of the photopolymerizable compound, the total content of the sensitizer having a sensitizing effect in the wavelength range of 400 nm to 420 nm is preferably 1 part by mass or more, more preferably 5 parts by mass or more, Preferably it is 30 parts by mass or less, more preferably 20 parts by mass or less.

<Solvent>
The blue-sensitive composition used in the present invention may contain a solvent. The solvent is not particularly limited as long as it is an organic solvent that does not react with the components in the blue-sensitive composition and can dissolve or disperse them. Solvents can be used alone or in combination of two or more.
Specific examples of the solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, i-propyl alcohol, methoxy alcohol, and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; Ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, Ester solvents such as ethyl lactate and cyclohexanol acetate; Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1 - Glycol ether acetate solvents such as butyl acetate, 3-methoxybutyl acetate and ethoxyethyl acetate; Carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate and butyl carbitol acetate (BCA); Propylene glycol diacetate , 1,3-butylene glycol diacetate and other diacetates; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, dipropylene glycol Glycol ether solvents such as dimethyl ether; aprotic amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; cyclic ether solvents such as tetrahydrofuran ; Unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; Saturated hydrocarbon solvents such as N-heptane, N-hexane, and N-octane; Organic solvents such as aromatic hydrocarbons such as toluene and xylene can be mentioned. Among these solvents, glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents are preferably used from the viewpoint of solubility of other components. Among them, the solvents used in the present invention include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate, from the viewpoint of solubility of other components and suitability for coating.

In the blue photosensitive composition used in the present invention, the content of the solvent may be appropriately set within a range that allows a blue cured film or a colored layer to be formed with high precision. The content of the solvent is usually preferably in the range of 55% to 95% by weight, more preferably 65% to 88% by weight, based on the total amount of the blue photosensitive composition containing the solvent. When the content of the above-mentioned solvent is within the above-mentioned range, excellent coating properties can be obtained.

<Dispersant>
In the case of dispersing a coloring material in the blue photosensitive composition of the present invention, a dispersant may be further included from the viewpoint of coloring material dispersibility and coloring material dispersion stability.
In the present invention, the dispersant can be appropriately selected from conventionally known dispersants. As the dispersant, for example, cationic, anionic, nonionic, amphoteric, silicone, or fluorine-based surfactants can be used. Among surfactants, polymeric dispersants are preferred because they can be uniformly and finely dispersed.

Examples of polymeric dispersants include (meth)acrylate copolymer dispersants; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; polyethyleneimine derivatives (poly(lower alkyleneimine) and Amides obtained by reaction with polyesters containing free carboxyl groups and their bases); polyallylamine derivatives (three types: polyallylamine and polyesters, polyamides, or co-condensates of esters and amides (polyesteramides) having free carboxyl groups); (a reaction product obtained by reacting one or more compounds selected from among the compounds).

In the present invention, it is preferable to use a (meth)acrylate copolymer-based dispersant as the dispersant from the viewpoint of controlling developability. Since the (meth)acrylate copolymer-based dispersant has good compatibility with the alkali-soluble resin and the photopolymerizable compound, it is presumed that the generation of development residues is suppressed.

In the present invention, the (meth)acrylate copolymer-based dispersant refers to a dispersant that is a copolymer and includes at least a structural unit derived from (meth)acrylate.
The (meth)acrylate copolymer-based dispersant is preferably a copolymer containing a structural unit that functions as a coloring material adsorption site and a constitutional unit that functions as a solvent affinity site, and functions as a solvent affinity site. It is preferable that the structural units include at least (meth)acrylate-derived structural units.

Examples of the structural unit functioning as a coloring material adsorption site include a structural unit derived from an ethylenically unsaturated monomer that is copolymerizable with a structural unit derived from (meth)acrylate. The colorant adsorption site may be a structural unit derived from an ethylenically unsaturated monomer containing an acidic group or a structural unit derived from an ethylenically unsaturated monomer containing a basic group.
As the structural unit derived from the basic group-containing ethylenically unsaturated monomer, a structural unit represented by the following general formula (I) is preferable from the viewpoint of excellent dispersibility of the coloring material.

(In general formula (I), R ⁶¹ is a hydrogen atom or a methyl group, A ¹ is a divalent linking group, R ⁶² and R ⁶³ are each independently a hydrogen atom or a hydrocarbon that may contain a heteroatom) represents a group, and R ⁶² and R ⁶³ may be bonded to each other to form a ring structure.)

In general formula (I), A ¹ is a divalent linking group. Examples of the divalent linking group include a straight chain, branched or cyclic alkylene group, a straight chain, branched or cyclic alkylene group having a hydroxyl group, an arylene group, -CONH- group, -COO- group, -NHCOO- group, ether group (-O- group), thioether group (-S- group), and combinations thereof. In the present invention, the direction of bonding of the divalent linking group is arbitrary. That is, when the divalent linking group contains -CONH-, -CO may be on the carbon atom side of the main chain and -NH may be on the nitrogen atom side of the side chain, or conversely, -NH may be on the side chain nitrogen atom side. -CO may be on the side chain nitrogen atom side.
Among these, from the viewpoint of dispersibility, A ¹ in general formula (I) is preferably a divalent linking group containing a -CONH- group or a -COO- group, and a -CONH- group or a -COO- group is preferably a divalent linking group. , and an alkylene group having 1 to 10 carbon atoms.

Examples of the hydrocarbon group in R ⁶² and R ⁶³ which may include a hetero atom include an alkyl group, an aralkyl group, and an aryl group.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2-ethylhexyl group, a cyclopentyl group, a cyclohexyl group, and the number of carbon atoms in the alkyl group is 1. -18 is preferable, and among them, a methyl group or an ethyl group is more preferable.
Examples of the aralkyl group include benzyl group, phenethyl group, naphthylmethyl group, and biphenylmethyl group. The number of carbon atoms in the aralkyl group is preferably 7 to 20, more preferably 7 to 14.
Furthermore, examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group. The number of carbon atoms in the aryl group is preferably 6 to 24, more preferably 6 to 12. Note that the above preferred carbon number does not include the carbon number of the substituent.
A hydrocarbon group containing a hetero atom has a structure in which a carbon atom in the above hydrocarbon group is replaced with a hetero atom, or a structure in which a hydrogen atom in the above hydrocarbon group is replaced with a substituent containing a hetero atom. has. Examples of the heteroatom that the hydrocarbon group may contain include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom.
Further, the hydrogen atom in the hydrocarbon group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom.

The expression that R ⁶² and R ⁶³ are bonded to each other to form a ring structure means that R ⁶² and R ⁶³ form a ring structure via a nitrogen atom. The ring structure formed by R ⁶² and R ⁶³ may contain a heteroatom. Although the ring structure is not particularly limited, examples thereof include a pyrrolidine ring, a piperidine ring, and a morpholine ring.

In the present invention, among others, R ⁶² and R ⁶³ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, or R ⁶² and R ⁶³ are combined to form a pyrrolidine ring, a piperidine ring, or It is preferable that they form a ring or a morpholine ring.

Monomers for inducing the structural unit represented by the above general formula (I) include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylate, etc. Examples include alkyl group-substituted amino group-containing (meth)acrylates, and alkyl group-substituted amino group-containing (meth)acrylamides such as dimethylaminoethyl (meth)acrylamide and dimethylaminopropyl (meth)acrylamide. Among them, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dimethylaminopropyl (meth)acrylamide are preferably used because they improve dispersibility and dispersion stability.
In the polymer, the structural unit represented by the general formula (I) may consist of one type, or may contain two or more types of structural units.

Furthermore, the structural unit functioning as a colorant adsorption site is selected from the group consisting of at least a part of the nitrogen site possessed by the structural unit represented by the general formula (I), an organic acid compound, and a halogenated hydrocarbon. At least one kind may form a salt.
The organic acid compound is preferably an acidic organic phosphorus compound such as phenylphosphonic acid or phenylphosphinic acid from the viewpoint of excellent dispersibility and dispersion stability of the coloring material. As a specific example of the organic acid compound used in such a dispersant, for example, organic acid compounds described in JP-A-2012-236882 and the like can be mentioned as suitable ones.
Further, the halogenated hydrocarbon is preferably at least one of allyl halides such as allyl bromide and benzyl chloride, and aralkyl halides, from the viewpoint of excellent dispersibility and dispersion stability of the coloring material.

The copolymer having the structural unit represented by the general formula (I) has the structural unit represented by the general formula (I) from the viewpoint of dispersibility and dispersion stability, and has ( A graft copolymer having a structural unit derived from meth)acrylate, and a block having an A block containing a structural unit represented by the general formula (I) and a B block containing a structural unit derived from (meth)acrylate. More preferably, it is at least one type of copolymer.
In the graft copolymer, a conventionally known structure can be appropriately selected and used as the graft polymer chain having a structural unit derived from (meth)acrylate. For example, at least one of the graft copolymers and salt-type graft copolymers described in International Publication No. 2021/006077 may be used.
Moreover, in the block copolymer, as the B block containing a structural unit derived from (meth)acrylate, a conventionally known structure can be appropriately selected and used. For example, at least one of the block copolymers and salt-type block copolymers described in International Publication No. 2016/104493 may be used.

As the (meth)acrylate copolymer-based dispersant, commercially available products may be used, and examples thereof include LP-N6919 (trade name) and LP-N21116 (trade name) manufactured by Big Chemie Japan Co., Ltd.

In the blue-sensitive composition according to the present invention, the content of the dispersant may be selected so as to have excellent dispersibility and dispersion stability of the coloring material, and is not particularly limited. For example, it is preferably in the range of 2% by mass to 30% by mass, more preferably 3% by mass to 25% by mass, based on the total amount. If it is more than the above lower limit, the dispersibility and dispersion stability of the coloring material are excellent, and the storage stability of the blue-sensitive composition is also excellent. Moreover, if it is below the said upper limit, developability will become good. In particular, when forming a cured film with a high concentration of coloring material, the content of the dispersant is preferably 2% to 25% by mass, more preferably 3% by mass, based on the total solid content of the blue-sensitive composition. It is within the range of % by mass to 20% by mass.

<thiol compound>
The blue photosensitive composition of the present invention preferably further contains a thiol compound in order to improve solvent resistance and substrate adhesion after low-temperature heat treatment.
Examples of the thiol compound include monofunctional thiol compounds having one thiol group in one molecule and polyfunctional thiol compounds having two or more thiol groups in one molecule. From the viewpoint of suppressing line width shift and improving adhesion to the substrate, it is more preferable to use a monofunctional thiol compound having one thiol group.
Examples of monofunctional thiol compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, and 3-mercaptobenzimidazole. Examples include propionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, and the like.
Examples of polyfunctional thiol compounds include 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2, 4,6(1H,3H,5H)-trione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), di Examples include pentaerythritol hexakis (3-mercaptopropionate) and tetraethylene glycol bis(3-mercaptopropionate).
The thiol compound may be used alone or in combination of two or more, and among them, 2-mercaptobenzoxazole or 2-mercaptobenzothiazole improves solvent resistance and substrate adhesion after low-temperature heat treatment. Preferable from this point of view.
The content of the thiol compound is usually in the range of 0.5% by mass to 10% by mass, preferably 1% by mass to 5% by mass, based on the total solid content of the blue photosensitive composition. If it is at least the above lower limit, the adhesion to the substrate is excellent. On the other hand, if it is below the above-mentioned upper limit, the blue photosensitive composition of the present invention is likely to have good developability and suppress line width shift.

<Optional addition ingredients>
The blue photosensitive composition may contain various additives as necessary. Examples of additives include antioxidants, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, antifoaming agents, silane coupling agents, ultraviolet absorbers, adhesion promoters, etc. .
Specific examples of surfactants and plasticizers include those described in JP-A No. 2013-029832.

The blue photosensitive composition of the present invention preferably further contains an antioxidant from the viewpoint of suppressing the amount of line width shift. By containing an antioxidant in combination with the specific photoinitiator, the blue photosensitive composition of the present invention can control excessive radical chain reactions without impairing curability when forming a cured film. When forming a thin line pattern, linearity is further improved, and the ability to form a thin line pattern according to the designed mask line width is improved.
The antioxidant used in the present invention is not particularly limited, and may be appropriately selected from conventionally known antioxidants. Specific examples of antioxidants include hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, hydrazine antioxidants, etc. It is preferable to use a hindered phenolic antioxidant from the viewpoint of improving the ability to form a fine line pattern as designed and from the viewpoint of heat resistance. It may also be a latent antioxidant as described in International Publication No. 2014/021023.

Examples of the hindered phenolic antioxidant include pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX1010, manufactured by BASF), 1,3 , 5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate (trade name: Irganox 3114, manufactured by BASF), 2,4,6-tris(4-hydroxy-3,5- Di-tert-butylbenzyl) mesitylene (product name: Irganox 1330, manufactured by BASF), 2,2'-methylenebis(6-tert-butyl-4-methylphenol) (product name: Sumilizer MDP-S, manufactured by Sumitomo Chemical) ), 6,6'-thiobis(2-tert-butyl-4-methylphenol) (trade name: Irganox 1081, manufactured by BASF), diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate ( Trade name: Irgamod 195 (manufactured by BASF), etc. Among them, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX1010, manufactured by BASF) is preferred from the viewpoint of heat resistance and light resistance.

The content of the antioxidant is preferably 0.1% by mass to 10.0% by mass, more preferably 0.5% by mass to 5.0% by mass, based on the total solid content of the blue photosensitive composition. is within the range of If it is more than the above lower limit, the ability to form a fine line pattern according to the designed mask line width is improved and the heat resistance is excellent. On the other hand, if it is below the above upper limit, the blue photosensitive composition of the present invention can be made into a highly sensitive photosensitive composition.

Examples of the silane coupling agent include KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-903, KBE-903, KBM573, KBM-403, KBE-402, KBE-403. , KBM-303, KBM-802, KBM-803, KBE-9007, and X-12-967C (manufactured by Shin-Etsu Silicone Co., Ltd.). Among them, KBM-502, KBM-503, KBE-502, KBE-503, and KBM-5103, which have methacrylic groups and acrylic groups, are preferred from the viewpoint of adhesion to the SiN substrate.

The content of the silane coupling agent is preferably in the range of 0.05% by mass to 10.0% by mass, more preferably 0.1% by mass based on the total solid content of the blue photosensitive composition. It is within the range of ~5.0% by mass. If it is greater than or equal to the lower limit value and less than or equal to the upper limit value, the adhesion to the substrate is excellent.

<Method for producing blue photosensitive composition>
The method for producing the blue photosensitive composition used in the present invention includes a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a sensitizer, and optionally a dispersant and a solvent. , and various additive components used as desired, and the colorant can be uniformly dispersed in the solvent, and can be prepared by mixing using known mixing means.
As a method for preparing a blue photosensitive composition, for example, (1) first, a coloring material and a dispersant are added to a solvent to prepare a coloring material dispersion, and an alkali-soluble resin and an alkali-soluble resin are added to the dispersion. A method of mixing a photopolymerizable compound, a photoinitiator, a sensitizer, and various optional additive components; (2) a coloring material, an alkali-soluble resin, a photopolymerizable compound in a solvent, A method in which a photoinitiator, a sensitizer, a dispersant used if desired, and various additive components are simultaneously added and mixed; (4) A method in which a coloring agent, a sensitizer, a dispersing agent used as desired, and various additive components are added and mixed, and then a coloring material is added and dispersed; (4) a coloring material and a dispersing agent in a solvent; and an alkali-soluble resin to prepare a coloring material dispersion, and to the dispersion, further an alkali-soluble resin, a solvent, a photopolymerizable compound, a photoinitiator, a sensitizer, and optionally an alkali-soluble resin. Examples include a method of adding and mixing various additive components to be used. If the photopolymerizable compound is used in place of the solvent, the solvent may not be used.
Among these methods, methods (1) and (4) above are preferred because they can effectively prevent agglomeration of the coloring material and uniformly disperse it.

The method for preparing the coloring material dispersion can be appropriately selected from conventionally known dispersion methods. For example, (1) a dispersant is mixed in advance with a solvent and stirred to prepare a dispersant solution, and then, if necessary, an organic acid compound is mixed to form a salt between the amino group of the dispersant and the organic acid compound. let A method of mixing this with the coloring material and other components as necessary and dispersing it using a known stirrer or dispersion machine; (2) Mixing the dispersant with a solvent and stirring to prepare a dispersant solution; , a method of mixing a coloring material and an organic acid compound as necessary, and further other components as necessary, and dispersing the mixture using a known stirrer or disperser; (3) mixing a dispersant with a solvent and stirring; , prepare a dispersant solution, then mix the coloring material and other components as necessary, make a dispersion liquid using a known stirrer or dispersion machine, and then add an organic acid compound as necessary. Examples include methods.

Examples of the dispersion machine for performing the dispersion treatment include roll mills such as two-roll and three-roll mills, ball mills such as ball mills and vibrating ball mills, paint conditioners, bead mills such as continuous disc-type bead mills, and continuous annular bead mills. As preferred dispersion conditions for the bead mill, the diameter of the beads used is preferably 0.03 mm to 2.00 mm, more preferably 0.10 mm to 1.0 mm.

<Application>
The blue photosensitive composition according to the present invention can improve the residual film rate after development while suppressing line width shift, and can form a good pattern with suppressed undercuts after development. Since the adhesion of the cured film pattern to the substrate is also improved, it can be suitably used for color filter applications.

III. Color filter and method for manufacturing the same The method for manufacturing a color filter of the present invention is a method for manufacturing a color filter comprising at least a substrate and a colored layer including a blue cured film provided on the substrate,
The present invention is characterized by comprising a step of manufacturing the blue cured film by the method for manufacturing a blue cured film according to the present invention.
Further, the color filter according to the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, and at least one of the colored layers is composed of the blue photosensitive composition according to the present invention. It is characterized by being a cured product.

The color filter according to the present invention will be explained with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of a color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention includes a substrate 1, a light shielding part 2, and a colored layer 3.

<Substrate>
Since the substrate may be the same as the substrate mentioned in the method for manufacturing the blue cured film, the explanation here will be omitted.
The thickness of the transparent substrate is not particularly limited, but may be, for example, about 100 μm to 1 mm depending on the use of the color filter of the present invention.

<Light shielding part>
The light shielding part in the color filter of the present invention is formed in a pattern on the substrate, and can be similar to that used as a light shielding part in a general color filter.
The pattern shape of the light shielding portion is not particularly limited, and examples thereof include stripe shapes, matrix shapes, and the like. The light shielding portion may be a thin film of metal such as chromium formed by sputtering, vacuum evaporation, or the like. Alternatively, the light-shielding portion may be a resin layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in a resin binder. In the case of a resin layer containing light-shielding particles, there are methods such as patterning by development using a photosensitive resist, patterning using an inkjet ink containing light-shielding particles, and thermal transfer of a photosensitive resist. be.

The film thickness of the light-shielding part is set at about 0.2 μm to 0.4 μm in the case of a metal thin film, and set at about 0.5 μm to 2 μm in the case of a black pigment dispersed or dissolved in a binder resin. be done.

<Colored layer>
At least one of the colored layers used in the color filter of the present invention is a cured product of the blue photosensitive composition according to the present invention.
The colored layer is usually formed in the opening of the light shielding part on the substrate, and is usually composed of a colored pattern of three or more colors.
Further, the arrangement of the colored layers is not particularly limited, and may be a general arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type. Furthermore, the width, area, etc. of the colored layer can be set arbitrarily.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, solid content concentration, viscosity, etc. of the blue-sensitive composition, and is usually preferably in the range of 1 μm to 5 μm.

In the colored layer, at least the blue colored layer, that is, the blue cured film has a step of producing it by the method for producing a blue cured film according to the present invention.
Colored layers other than the blue colored layer may be manufactured by conventionally known manufacturing methods, but similarly to the method for manufacturing the blue cured film according to the present invention, the step of forming a coating film on a substrate, the coating The film may include a step of exposing and curing the film using an LED lamp having an emission peak wavelength of 360 nm to 380 nm and 400 nm to 420 nm, and may be produced in the same manner as the blue cured film according to the present invention. It's fine.

Note that the color filter of the present invention may include, for example, an overcoat layer, a transparent electrode layer, an alignment film, a columnar spacer, etc., in addition to the above-described substrate, light shielding portion, and colored layer.

IV. Display Device A display device according to the present invention is characterized by having the color filter according to the present invention. In the present invention, the configuration of the display device is not particularly limited, and can be appropriately selected from conventionally known display devices, such as a liquid crystal display device, an organic light emitting display device, and the like.

[Liquid crystal display device]
Examples of the liquid crystal display device of the present invention include a liquid crystal display device including the color filter according to the present invention described above, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate. .
Such a liquid crystal display device of the present invention will be explained with reference to the drawings. FIG. 2 is a schematic diagram showing an example of a liquid crystal display device of the present invention. As illustrated in FIG. 2, a liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate, etc., and a liquid crystal layer formed between the color filter 10 and the counter substrate 20. 30.
Note that the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, and may have a generally known configuration as a liquid crystal display device using a color filter.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and any driving method generally used for liquid crystal display devices can be adopted. Examples of such driving methods include a TN method, an IPS method, an OCB method, and an MVA method. In the present invention, any of these methods can be suitably used.
Further, the counter substrate can be appropriately selected and used depending on the driving method of the liquid crystal display device of the present invention.
Further, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and mixtures thereof can be used depending on the driving method of the liquid crystal display device of the present invention.

As a method for forming the liquid crystal layer, methods generally used for manufacturing liquid crystal cells can be used, such as a vacuum injection method, a liquid crystal dropping method, and the like. After forming the liquid crystal layer by the method described above, the liquid crystal cell is gradually cooled to room temperature, thereby making it possible to orient the encapsulated liquid crystal.

[Organic light emitting display device]
Examples of the organic light emitting display device of the present invention include an organic light emitting display device having the above-described color filter according to the present invention and an organic light emitter.
The organic light emitting display device of the present invention will be described with reference to the drawings. FIG. 3 is a schematic diagram showing an example of an organic light emitting display device of the present invention. As illustrated in FIG. 3, an organic light emitting display device 100 of the present invention includes a color filter 10 and an organic light emitter 80. An organic protective layer 50 or an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitter 80.

As a method of stacking the organic light emitter 80, for example, a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light emitting layer 74, an electron injection layer 75, and a cathode 76 are sequentially formed on the upper surface of the color filter. Examples include a method in which an organic light emitting body 80 formed on a separate substrate is bonded onto an inorganic oxide film 60, and the like. For the transparent anode 71, hole injection layer 72, hole transport layer 73, light emitting layer 74, electron injection layer 75, cathode 76, and other structures in the organic light emitter 80, publicly known ones can be used as appropriate. The organic light emitting display device 100 manufactured in this manner is applicable to, for example, both a passive drive type organic EL display and an active drive type organic EL display.
Note that the organic light emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and may have a generally known configuration as an organic light emitting display device using a color filter.

Hereinafter, the present invention will be specifically explained by showing examples. The present invention is not limited to these descriptions.

[Preparation of LED light source]
As an LED light source having an emission peak wavelength of 360 nm to 380 nm and 400 nm to 420 nm, an LED chip having an emission peak wavelength of 365 nm and an LED chip having an emission peak wavelength of 405 nm are used, and the number ratio of each LED chip is Accordingly, the intensity ratio (A/B) between the intensity of the emission peak wavelength of 360 nm to 380 nm (A) and the intensity of the emission peak wavelength of 400 nm to 420 nm (B) was adjusted. The LED chips were arranged so that the curing properties were not biased depending on the light irradiation position.
LED light sources with intensity ratios (A/B)=100/0, 90/10, 80/20, 60/40, 40/60, 20/80, 10/90, and 0/100 were prepared.
The intensity ratio (A/B) was confirmed using a spectral irradiance meter (USR-45DA-14 (manufactured by Ushio Inc.)).

(Synthesis Example 1: Preparation of alkali-soluble resin A)
A mixed solution of 40 parts by mass of benzyl methacrylate (BzMA), 15 parts by mass of methyl methacrylate (MMA), 25 parts by mass of methacrylic acid (MAA), and 3 parts by mass of azoisobutyronitrile (AIBN) was added with 150 parts by mass of PGMEA. The mixture was added dropwise into a polymerization tank at 100° C. over a period of 3 hours under a nitrogen stream. After the dropwise addition was completed, the mixture was further heated at 100° C. for 3 hours to obtain a polymer solution. The mass average molecular weight of this polymer solution was 7,000.
Next, 20 parts by mass of glycidyl methacrylate (GMA), 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol were added to the obtained polymer solution, and the mixture was heated at 110°C for 10 hours. Alkali-soluble resin A was obtained by reacting the carboxylic acid group of main chain methacrylic acid with the epoxy group of glycidyl methacrylate. During the reaction, air was bubbled into the reaction solution to prevent polymerization of glycidyl methacrylate. The reaction was tracked by measuring the acid value of the solution. The obtained alkali-soluble resin A is a resin in which a side chain having an ethylenically unsaturated bond is introduced into the main chain formed by copolymerization of BzMA, MMA, and MAA using GMA, and has a solid content of 40% by mass, The acid value was 74 mgKOH/g and the mass average molecular weight was 12,000.
The above mass average molecular weight was determined by using polystyrene as a standard substance and THF as an eluent using Shodex GPC System-21H. The acid value was measured based on JIS K 0070. Further, the glass transition temperature (Tg) was measured using differential scanning calorimetry (EXSTAR DSC 7020, manufactured by SII Nano Technology) according to the method described in JIS K7121.

(Synthesis Example 2: Preparation of block copolymer A (dispersant A))
Add 250 parts by mass of THF and 0.6 parts by mass of lithium chloride to a 500 mL round-bottomed 4-neck separable flask equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, and thoroughly purge with nitrogen. Ta. After cooling the reaction flask to −60° C., 4.9 parts by mass of butyllithium (15% by mass hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 parts by mass of methyl isobutyrate were injected using a syringe. B block monomers 1-ethoxyethyl methacrylate (EEMA) 2.2 parts by mass, 2-hydroxyethyl methacrylate (HEMA) 18.7 parts by mass, 2-ethylhexyl methacrylate (EHMA) 12.8 parts by mass, methacryl 13.7 parts by mass of n-butyl acid (BMA), 9.5 parts by mass of benzyl methacrylate (BzMA), and 17.5 parts by mass of methyl methacrylate (MMA) were added dropwise over 60 minutes using an addition funnel. . After 30 minutes, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA), which is a monomer for A block, was added dropwise over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, purified by filtration and vacuum drying, and diluted with PGMEA to obtain a solution with a solid content of 30% by mass. 32.5 parts by mass of water was added, the temperature was raised to 100° C., and the mixture was reacted for 7 hours to deprotect the structural unit derived from EEMA and obtain a structural unit derived from methacrylic acid (MAA). The obtained block copolymer PGMEA solution is reprecipitated in hexane, purified by filtration and vacuum drying, and the A block containing the structural unit represented by general formula (I) and the structural unit derived from the carboxyl group-containing monomer are extracted. A block copolymer A (acid value: 8 mgKOH/g, Tg: 38° C.) was obtained, which contained a B block having solvent affinity. When the thus obtained block copolymer A was confirmed by GPC (gel permeation chromatography), the mass average molecular weight Mw was 7,730. Moreover, the amine value was 95 mgKOH/g.

(Synthesis example 3: Synthesis of lake color material 1)
(1) Synthesis of Intermediate 1 Referring to the method for producing Intermediate A-2, Intermediate B-1, and Compound 1-3 described in JP-A-2018-3013, Intermediate 1 was obtained (yield 87%).
The obtained compound was confirmed to be the desired compound based on the analysis results described below.
・MS (ESI) (m/z): 677 (+), divalent ・Elemental analysis value: CHN actual value (81.81%, 7.31%, 5.85%); theoretical value (81.77%) , 7.36%, 5.90%)

(2) Synthesis of Lake Colorant 1 2.59 g (0.76 mmol) of Kanto Chemical's 12-tungstophosphoric acid n-hydrate was heated and dissolved in a mixed solution of 40 mL of methanol and 40 mL of water, and 1.6 g of the intermediate 1 was dissolved. (1.19 mmol) was added and stirred for 1 hour. The precipitate was collected by filtration and washed with water. The obtained precipitate was dried under reduced pressure to obtain Lake Coloring Material 1 represented by the following chemical formula (b) (yield: 95%).
The obtained compound was confirmed to be the desired compound based on the analysis results described below.
・31P NMR (d-dmso, ppm) δ-15.15
・MS (MALDI) (m/z): 1355 (M ⁺ ), 2879 (MH ₂ ^- )
・Elemental analysis value: CHN actual value (35.55%, 3.24%, 2.61%); theoretical value (35.61%, 3.20%, 2.57%)
・Fluorescent X-ray analysis: MoW actual measurement ratio (0%, 100%); theoretical value (0%, 100%)

(Synthesis Example 4: Synthesis of oxime photoinitiator compound A-1)
(1) Synthesis of Intermediate A1 0.2 mol of diphenylthioether, 0.22 mol of ground AlCl ₃ and 150 ml of dichloroethane were put into a 500 ml four-necked flask, stirred, and heated in an ice bath under argon gas flow. When the temperature decreased to 0°C, dropwise addition of a solution consisting of 0.22 mol of cyclohexylpropionyl chloride and 42 g of dichloroethane was started, and the addition took about 1.5 hours while adjusting the temperature to below 10°C. After increasing the temperature to 15° C. and stirring continuously for 2 hours, the reaction solution was discharged.
After gradually adding the reaction solution into dilute hydrochloric acid containing 400 g of ice and 65 ml of concentrated hydrochloric acid under stirring, the lower layer was separated using a separatory funnel, the upper layer was extracted with 50 ml of dichloroethane, and the extract and lower layer were separated. Combined with liquid. Thereafter, it was washed with a NaHCO ₃ solution containing 10 g of NaHCO ₃ and 200 g of water, further washed with 200 ml of water three times until the pH value became neutral, and dried with 60 g of anhydrous MgSO ₄ to remove moisture. Afterwards, dichloroethane was evaporated by rotary evaporation. The solid powder remaining in the rotary evaporator was poured into 200 ml of petroleum ether, filtered with suction, and then poured into 150 ml of absolute ethanol, heated, and refluxed. Thereafter, the mixture was cooled to room temperature, further cooled with ice for 2 hours, filtered under suction, and dried in an oven at 50°C for 2 hours to obtain intermediate A1 below.

(2) Synthesis of Intermediate A2 42 g of Intermediate A1, 400 g of tetrahydrofuran, 200 g of concentrated hydrochloric acid, and 24.2 g of isoamyl nitrite were put into a 500 ml four-necked flask, and the mixture was stirred at room temperature for 5 hours. , and the reaction solution was discharged.
The reaction solution was placed in a large beaker, 1000 ml of water was added thereto, stirred, and then allowed to stand overnight to separate the layers to obtain a yellow viscous liquid. The viscous liquid was extracted with dichloroethane, dried by adding 50 g of anhydrous MgSO ₄ , filtered under suction, and the filtrate was rotary evaporated to remove the solvent to obtain an oily viscous substance. Subsequently, the viscous substance was poured into 150 ml of petroleum ether, stirred, precipitated, and filtered under suction to obtain a white powdery solid. Thereafter, it was dried at 60° C. for 5 hours to obtain Intermediate A2 below.

(3) Synthesis of Compound A-1 34 g of the intermediate A2, 350 ml of dichloroethane, and 12.7 g of triethylamine were put into a 1000 ml four-necked flask, stirred, and cooled in an ice bath until the temperature reached 0. When the temperature dropped to 0.degree. C., a solution consisting of 15.7 g of acetic chloride and 15 g of dichloroethane was started to be added dropwise over about 1.5 hours. After stirring for 1 hour, 500 ml of cold water was added dropwise, and the layers were separated using a separatory funnel. Wash once with 200 ml of 5% NaHCO ₃ solution, then twice with 200 ml water until the pH value becomes neutral, then wash once with dilute hydrochloric acid containing 20 g of concentrated hydrochloric acid and 400 ml of water, followed by 200 ml of water. After washing three times with water, drying with 100 g of anhydrous MgSO ₄ and removing the solvent by rotary evaporation, a viscous liquid was obtained. A suitable amount of methanol was added to the viscous liquid, and the precipitated white solid was filtered and dried to obtain compound A-1 represented by the following chemical formula (A-1). Note that the molecular weight of the following compound A-1 is 395.51.

(Synthesis Example 5: Synthesis of oxime photoinitiator represented by formula (B-2))
Compound No. 0114 to 0117 of International Publication No. 2015/152153. In the same manner as in the production of No. 73, an oxime ester photoinitiator represented by the following formula (B-2) was synthesized.

(Synthesis Example 6: Synthesis of oxime ester photoinitiator represented by formula (C-1))
Oxime ester represented by the following formula (C-1) was prepared in the same manner as in the production of photopolymerization initiator W (photopolymerization initiator represented by formula (3)) in paragraph 0080 of JP-A No. 2010-256891. A system photoinitiator was synthesized.

(Preparation example 1: Preparation of coloring material dispersion A)
5.1 parts by mass of block copolymer A of Synthesis Example 2 was used as a dispersant, and C.I. was used as a coloring material. I. Pigment Blue 15:6 (trade name FASTOGEN BLUE A510, manufactured by DIC Corporation) 11.6 parts by mass and C.I. I. Pigment Violet 23 (trade name: Hostaperm Violet RL-NF, manufactured by Clariant) 1.4 parts by mass, 5.1 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 1 in terms of solid content, and 76.8 parts by mass of PGMEA. 100 parts by mass of zirconia beads with a particle size of 2.0 mm were placed in a mayonnaise bottle and shaken for 1 hour in a paint shaker (manufactured by Asada Tekko Co., Ltd.) for preliminary crushing, and then zirconia beads with a particle size of 2.0 mm were placed in a mayonnaise bottle. The mixture was taken out, 200 parts by mass of zirconia beads having a particle size of 0.1 mm were added thereto, and dispersion was similarly carried out for 4 hours in a paint shaker as main disintegration to obtain coloring material dispersion A.

(Preparation example 2: Preparation of coloring material dispersion B)
In Preparation Example 1, C.I. I. Pigment Blue 15:6 and 11.6 parts by mass of C.I. I. Pigment Violet 23 in place of 1.4 parts by mass, C.I. I. Colorant dispersion B was obtained in the same manner as in Preparation Example 1, except that 3.3 parts by mass of Pigment Blue 15:6 and 9.7 parts by mass of Lake Colorant 1 obtained in Synthesis Example 3 were used. .

(Production Example 1: Production of blue photosensitive composition B-1)
22.37 parts by mass of coloring material dispersion A, 7.86 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 1, and a photopolymerizable compound (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.). 5.84 parts by mass, 0.29 parts by mass of the oxime photoinitiator represented by the chemical formula (A-1) of Synthesis Example 4 as a photoinitiator, and diethyl as a sensitizing agent having a sensitizing effect in the wavelength range of 400 nm to 420 nm. 0.29 parts by mass of thioxanthone (DETX-S, manufactured by Nippon Kayaku Co., Ltd.), 0.36 parts by mass of Karenz MT PE1 (manufactured by Showa Denko Co., Ltd.) as a thiol compound, and Megafac R-08MH (manufactured by Showa Denko Co., Ltd.) as a surfactant. Blue photosensitive composition B-1 was prepared by adding 0.15 parts by mass of KBM503 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent and 62.54 parts by mass of PGMEA (manufactured by DIC Corporation). Obtained.

(Production Examples 2 to 22: Production of blue photosensitive compositions B-2 to B-22)
In Production Example 1, a blue photosensitive composition was prepared in the same manner as Blue Photosensitive Composition B-1 of Production Example 1, except that the types and amounts of each component were changed as shown in Tables 1 to 3. Products B-2 to B-22 were obtained.

(Comparative Production Examples 1 and 2: Production of Comparative Blue Photosensitive Compositions CB-1 and CB-2)
The blue sensitivity of Production Example 1 was the same as that of Production Example 1, except that as shown in Table 3, the sensitizer having a sensitizing effect at 400 nm to 420 nm was not used and the types and amounts of each component were changed. Blue photosensitive compositions CB-1 to CB-2 were obtained in the same manner as composition B-1.

(Production Example 23: Production of blue photosensitive composition B-23)
27.09 parts by mass of coloring material dispersion B, 8.186 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 1, and a photopolymerizable compound (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.). 6.08 parts by mass, 0.22 parts by mass of the oxime photoinitiator represented by the chemical formula (A-1) of Synthesis Example 4 as a photoinitiator, and diethyl as a sensitizing agent having a sensitizing effect at 400 nm to 420 nm. 0.12 parts by mass of thioxanthone (DETX-S, manufactured by Nippon Kayaku Co., Ltd.), 0.37 parts by mass of Karenz MT PE1 (manufactured by Showa Denko Co., Ltd.) as a thiol compound, and Irganox 1010 (manufactured by BASF) as an antioxidant. 0.10 parts by mass, 0.15 parts by mass of Megafac R-08MH (manufactured by DIC Corporation) as a surfactant, 0.30 parts by mass of KBM503 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, and PGMEA. 57.41 parts by mass was added to obtain blue photosensitive composition B-23.

(Production Examples 24 to 45: Production of blue photosensitive compositions B-24 to B-45)
In Production Example 23, a blue photosensitive composition was prepared in the same manner as Blue Photosensitive Composition B-23 of Production Example 23, except that the types and amounts of each component were changed as shown in Tables 4 to 6. Products B-24 to B-45 were obtained.

(Comparative Production Example 3: Production of Comparative Blue Photosensitive Composition CB-3)
In Production Example 23, as shown in Table 6, no sensitizer having a sensitizing effect at 400 nm to 420 nm was used and the types and amounts of each component were changed. A blue-sensitive composition CB-3 was obtained in the same manner as composition B-23.

(Example 1: Production of blue cured film)
<Example 1-1>
The blue photosensitive composition obtained in each Example and each Comparative Example was applied onto a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") using a spin coater, and after post-baking, the desired color (blue) was applied. Coating film: Coated so that x=0.100) at light source C. After heating and drying on a hot plate at 80°C for 3 minutes, this blue coating was coated with a photomask having a mask opening width of 2 to 90 μm to measure the intensity of the emission peak wavelength (A) of 360 nm to 380 nm and 400 nm. Using an LED light source with an intensity ratio (A/B) of 90/10 to the intensity (B) of the emission peak wavelength of ~420 nm, ultraviolet rays were irradiated at a cumulative exposure dose of 35 mJ/cm ² . The exposed glass plate on which the blue coating film was formed was subjected to shower development using a 0.05% by mass potassium hydroxide aqueous solution as an alkaline developer. Thereafter, it was post-baked in a clean oven at 230° C. for 25 minutes to produce a blue cured film in the form of an independent thin line pattern.

<Example 1-2 to Example 1-6>
In Example 1-1, the LED lamps were, as shown in Table 1, an LED light source with an A/B ratio of 80/20, an LED light source with an A/B ratio of 60/40, and an LED light source with an A/B ratio of 40/60. Blue curing was carried out in the same manner as in Example 1-1 except that the LED light source was changed to an LED light source with an A/B ratio of 20/80, or an LED light source with an A/B ratio of 10/90. A membrane was produced.

(Examples 2 to 45, Comparative Examples 1 to 3: Production of blue cured film)
A blue cured film was produced in the same manner as in Example 1-1, except that the blue photosensitive composition and/or the LED light source were changed as shown in Tables 1 to 6.
In each example and comparative example, A/B is 90/10, 80/20, 60/40, 40/60, 20/80, corresponding to Example 1-1 to Example 1-6 in Example 1. , 10/90 to produce a blue cured film.

[Evaluation method]
<Evaluation of line width shift of thin line pattern (line width)>
The line width of the obtained blue cured film in the form of an independent thin line pattern was measured using a mask opening of 90 μm and a designed line width of 95 μm. The effect of suppressing line width shift was evaluated using the following evaluation criteria.
(Evaluation criteria for line width shift)
◎: Line width 93 μm or more and 97 μm or less at mask opening 90 μm ○: Line width 90 μm or more and less than 93 μm at mask opening 90 μm, or more than 97 μm and 100 μm or less ×: Line width less than 90 μm or more than 100 μm at mask opening 90 μm Evaluation results If it is ◯, the line width shift suppression effect is good, and if it is ◎, the line width shift suppression effect is excellent.

<Evaluation of residual film rate after development>
When patterning the blue cured film, the film thickness after exposure and the film thickness after baking of the blue colored layer were measured using a stylus profiler P-16 (manufactured by KLA-Tencor), and the film thickness after development/ The film thickness after exposure x 100 was calculated as the residual film rate (%), and evaluated according to the following evaluation criteria. Note that the higher the residual film rate, the higher the sensitivity of the blue-sensitive composition.
◎: Film remaining ratio is 80% or more. ○: Film remaining ratio is 75% or more and less than 80%. △: Film remaining ratio is 65% or more and less than 75%. ×: Film remaining ratio is less than 65%.
If the evaluation result is △, it can be used, but if the evaluation result is ◯, the residual film rate is good, and if the evaluation result is ◎, the residual film rate is excellent.

<Substrate adhesion (minimum adhesion width) evaluation>
The obtained blue cured film was observed with an optical microscope to confirm how many micrometers of the pattern was in close contact with the mask opening width of 2 to 90 micrometers, and the line width of the narrowest pattern.
◎: Pattern remains until the mask opening is 8 μm or less (line width of the thinnest pattern is 8 μm or less)
〇: Line width of the thinnest pattern is 9 μm to 15 μm or less △: Line width of the thinnest pattern is 16 μm to 25 μm or less ×: Line width of the thinnest pattern is 26 μm or more If the evaluation result is △, it can be used. If it is ◎, the adhesion to the substrate is good, and if it is ◎, the adhesion to the substrate is excellent.
<Overall Judgment>
Comprehensive evaluation was performed on the evaluation of the line width shift of the fine line pattern, the evaluation of the residual film rate after development, and the evaluation of substrate adhesion (minimum adhesion width).
◎: All evaluation results are ○ or ◎ 〇: Evaluation results include △ ×: Evaluation results include ×

The abbreviations in the table are as follows.
Alkali-soluble resin: Alkali-soluble resin A of Synthesis Example 1
Photopolymerizable compound: Trade name Aronix M-403, manufactured by Toagosei Co., Ltd. Oxime type (A-1): Oxime type photoinitiator represented by chemical formula (A-1) in Synthesis Example 4 Oxime type (B-2) ): Oxime-based photoinitiator represented by chemical formula (B-2) in Synthesis Example 5 Oxime-based (C-1): Oxime-based photoinitiator represented by chemical formula (C-1) in Synthesis Example 6 IRGACURE369: Product name IRGACURE369, manufactured by BASF Sensitizer 1: Thioxanthone-based sensitizer, diethylthioxanthone (DETX-S, manufactured by Nippon Kayaku Co., Ltd.)
Sensitizer 2: Benzophenone sensitizer, 4,4'-bis(diethylamino)benzophenone (EAB-SS, manufactured by Daido Kasei Kogyo Co., Ltd.)
Sensitizer 3: Anthracene sensitizer, 9,10-dibutoxyanthracene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
Thiol compound: Karenz MT PE1 (manufactured by Showa Denko K.K.)
Surfactant: Megafac R-08MH (manufactured by DIC Corporation)
Silane coupling agent: KBM503 (manufactured by Shin-Etsu Chemical Co., Ltd.)
Solvent: PGMEA

(Comparative Examples 4 to 5: Production of blue cured film)
(1) Synthesis of oxime-based photoinitiator having fluorene skeleton With reference to Synthesis Examples 1 and 2 of JP-A-2017-125972, an oxime-based photoinitiator having the following fluorene skeleton was synthesized.

(2) Production of blue photosensitive composition B-46 In Production Example 1, the fluorene skeleton obtained in the above (1) was substituted for the oxime photoinitiator represented by the chemical formula (A-1) in Synthesis Example 4. Blue photosensitive composition B-1 of Production Example 1, except that an oxime-based photoinitiator having In the same manner as above, blue-sensitive composition B-46 was obtained.

(3) Production of blue cured film In Example 1-1, the blue photosensitive composition was changed to blue photosensitive composition B-46, and the LED light source was changed to have (A/B) of 100 as shown in Table 7. A blue cured film was produced in the same manner as in Example 1-1, except that a single LED light source with an A/B ratio of 0/0 or 0/100 was used.
Table 7 shows the results of evaluation in the same manner as in Example 1.

(Comparative Examples 6 to 15: Production of blue cured film)
A blue cured film was produced in the same manner as in Example 1-1, except that the blue photosensitive composition and the LED light source were changed as shown in Table 7.
Table 7 shows the results of evaluation in the same manner as in Example 1.

[Summary of results]
In Examples 1 to 45, which is the method for producing a blue cured film according to the present invention, the coloring material, the alkali-soluble resin, the photopolymerizable compound, the oxime-based photoinitiator, and the oxime-based photoinitiator were different from 400 nm to A coating film of a blue photosensitive composition containing a photoinitiator containing a sensitizer having a sensitizing effect at 420 nm is exposed using an LED light source having emission peak wavelengths at 360 nm to 380 nm and 400 nm to 420 nm. As the blue cured film is cured, it is possible to improve the residual film rate after development while suppressing line width shift, and it is possible to form a good pattern with suppressed undercuts after development. It was also shown that the adhesion of the pattern to the substrate was improved.
In contrast, a coating film of a blue photosensitive composition that does not contain a sensitizer that has a sensitizing effect in the 400 nm to 420 nm range, which is different from an oxime photoinitiator, has an emission peak wavelength in the 360 nm to 380 nm range and 400 nm to 420 nm. In Comparative Examples 1 to 3, which were exposed and cured using an LED light source, the line width was narrow, the residual film rate after development was poor, and the formed blue cured film pattern had poor adhesion to the substrate.
Furthermore, an oxime photoinitiator having a fluorene skeleton and a sensitizer used in Patent Document 2 were used instead, and exposure was performed using a single LED light source (an LED light source having an emission peak wavelength of 365 nm). In Comparative Example 4, which was cured, although the residual film rate after development was secured, the line width became narrow and the substrate adhesion of the pattern of the formed blue cured film was also poor.
The oxime-based photoinitiator and sensitizer having a fluorene skeleton used in Patent Document 2 were used instead, and the method was exposed to light using a single LED light source (an LED light source having an emission peak wavelength of 405 nm) and cured. In Comparative Example 5, since the blue photosensitive composition easily penetrated the coating film, the light spread and the line width increased, but curing was insufficient and the residual film rate after development was poor.
A single LED light source (an LED light source with an emission peak wavelength of 365 nm, or In Comparative Examples 6 to 15, which were exposed and cured using an LED light source with an emission peak wavelength of 405 nm, the line width became narrower, and the adhesion of the formed blue cured film pattern to the substrate was also poor. .

1 Substrate 2 Light shielding part 3 Colored layer 10 Color filter 20 Counter substrate 30 Liquid crystal layer 40 Liquid crystal display device 50 Organic protective layer 60 Inorganic oxide film 71 Transparent anode 72 Hole injection layer 73 Hole transport layer 74 Light emitting layer 75 Electron injection layer 76 Cathode 80 Organic light emitter 100 Organic light emitting display device

Claims

Contains a coloring material, an alkali-soluble resin, a photopolymerizable compound, an oxime-based photoinitiator, and a photoinitiator including a sensitizer having a sensitizing effect at 400 nm to 420 nm different from the oxime-based photoinitiator. forming a coating film of a blue photosensitive composition on a substrate, and
a step of exposing and curing the coating film using an LED light source having an emission peak wavelength of 360 nm to 380 nm and 400 nm to 420 nm;
A method for producing a blue cured film.
In the LED light source, the intensity ratio (A/B) of the intensity of the emission peak wavelength of 360 nm to 380 nm (A) and the intensity of the emission peak wavelength of 400 nm to 420 nm (B) is 10/90 to 90/10. The method for producing a blue cured film according to claim 1.
The oxime photoinitiator is at least one selected from the group consisting of an oxime photoinitiator having a diphenyl sulfide skeleton, an oxime photoinitiator having an indole skeleton, and an oxime photoinitiator having a carbazole skeleton. The method for producing a blue cured film according to claim 1 or 2.
A coloring material, an alkali-soluble resin, a photopolymerizable compound, an oxime photoinitiator represented by the following general formula (A), and a sensitizer having a sensitizing effect at 400 nm to 420 nm different from the oxime photoinitiator. A blue photosensitive composition for curing by exposure using an LED light source having emission peak wavelengths in the range of 360 nm to 380 nm and 400 nm to 420 nm.

(In general formula (A), Z 1 , Z 3 , Z 4 and Z 5 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a C 3 to 20 represents a cycloalkyl group or a phenyl group, and each of the alkyl group, cycloalkyl group, and phenyl group is substituted with a substituent selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and a phenyl group. ( Z2 represents an alkyl group having 1 to 20 carbon atoms substituted with a cycloalkyl group.)
A method for producing a color filter comprising at least a substrate and a colored layer including a blue cured film provided on the substrate,
A method for producing a color filter, comprising the step of producing the blue cured film by the method for producing a blue cured film according to claim 1 or 2.
A color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is a cured product of the blue photosensitive composition according to claim 4.
A display device comprising the color filter according to claim 6.