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

Abstract

The present invention is a method for producing a blue cured film, comprising a step of forming a coating film of a blue photosensitive composition on a substrate, the blue photosensitive composition containing a colorant, an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator, the photoinitiator comprises an oxime-based photoinitiator and a sensitizing agent which is different from the oxime-based photoinitiator and has a sensitizing effect at 400-420 nm; and curing the coating film by exposing the coating film to light using an LED light source having an emission peak wavelength in the range of 360 nm to 380 nm and in the range of 400 nm to 420 nm.

Description

Technical Field

[0001] 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. Background Art

[0002] 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 portable displays (mobile phones, smartphones, tablet PCs) has also increased, 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 self-luminescence, are also attracting attention as the next generation of image display devices.

[0003] Color filters are used in these liquid crystal display devices and organic light-emitting display devices. For example, in the formation of a color image in a liquid crystal display device, the light passing through the color filter is directly colored into the color of each pixel constituting the color filter, and the light of these colors is synthesized to form a color image. As the light source at this time, in addition to the existing cold cathode tube, white light-emitting organic light-emitting elements and white light-emitting inorganic light-emitting elements are sometimes used. Color filters are used in organic light-emitting display devices for color adjustment, etc.

[0004] Here, the color filter generally includes: a substrate; a coloring layer formed on the substrate and including coloring patterns of three primary colors of red, green, and blue; and a light shielding portion formed on the substrate so as to partition each coloring pattern.

[0005] As a method for forming a color layer in a color filter, for example, a color material is dispersed using a dispersant to form a color material dispersion, a color resin composition to which a binder resin, a photopolymerizable compound, and a photoinitiator are added is applied to a glass substrate, and after drying, it is exposed using a photomask, developed to form a color pattern, and heated to fix the pattern to form a color layer. These steps are repeated for each color to form a color filter.

[0006] In the past, a high-pressure mercury lamp has been used in the above exposure process. The high-pressure mercury lamp has the problems of risk of rupture, high power consumption, and easy deterioration.

[0007] On the other hand, from the viewpoint of energy saving and reduction of environmental load, the use of LED as a light source for exposure is being promoted.

[0008] For example, Patent Document 1 describes a method for forming a pixel pattern, which includes the following steps: (1) forming a coating film of a colored radiation-sensitive linear composition containing at least one selected from the group consisting of a dye and a lake pigment on a substrate; and (2) exposing at least a portion of the above-mentioned coating film using an ultraviolet LED; the ultraviolet LED used in Patent Document 1 has a peak wavelength of 365 nm.

[0009] In addition, Patent Document 2 describes that a photosensitive composition comprising (A) a photopolymerizable compound, (B) a photopolymerization initiator which is an oxime ester compound of a specific structure having a 9,9-disubstituted fluorene group, and (C) a sensitizer is well cured even when exposed by LED. Patent Document 2 uses a commercially available LED lamp.

[0010] Prior art literature

[0011] Patent Literature

[0012] Patent Document 1: Japanese Patent Application Publication No. 2012-189994

[0013] Patent Document 2: Japanese Patent Application Publication No. 2017-125972 Summary of the invention

[0014] Problem that the invention aims to solve

[0015] LED light exposure machines are single wavelength, and mainly use LED lights with a peak emission wavelength of 365 nm in the i-ray. However, when using LED lights with a peak emission wavelength of 365 nm in the i-ray, there is a problem that blue resists (blue photosensitive compositions) are particularly difficult to cure.

[0016] Since i-ray 365 nm is a wavelength region that is easily absorbed by blue resist but not easily transmitted, it is believed that the photoinitiator is difficult to react and difficult to cure. In recent years, blue resists with higher color material concentrations are obviously difficult to cure. If the curing is insufficient, the following problems will occur: the residual film rate after development is reduced, or the line width becomes too thin, which deteriorates the substrate adhesion during pattern formation, or a good pattern cannot be formed.

[0017] On the other hand, if an LED lamp with a peak emission wavelength of h-ray 405 nm, which is longer than i-ray 365 nm, is used, the light range becomes wider and the line width tends to become larger because it becomes a wavelength region that is easily transmitted by the blue resist. However, in terms of energy, h-rays are weaker than i-rays, so there is a problem of difficulty in ensuring the residual film rate after development and difficulty in achieving a balance between the residual film rate and the line width.

[0018] The present invention has been made in view of the above circumstances, and its object is to provide 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 a blue cured film. In addition, the present invention aims to provide a blue photosensitive composition suitable for use in the method for producing a blue cured film, and a color filter and a display device formed using the blue photosensitive composition.

[0019] Technical means of solving problems

[0020] That is, the present invention relates to the following [1] to [7].

[0021] [1] A method for producing a blue cured film, comprising the following steps:

[0022] A coating film of a blue photosensitive composition is formed on a substrate, wherein the blue photosensitive composition contains a colorant, an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator, wherein the photoinitiator includes an oxime-based photoinitiator and a sensitizer different from the oxime-based photoinitiator and having a sensitizing effect at 400 nm to 420 nm; and

[0023] The coating film is exposed to light using an LED light source having emission peak wavelengths of 360 nm to 380 nm and 400 nm to 420 nm to be cured.

[0024] [2] The method for producing a blue cured film as described in [1] above, wherein 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) to the intensity of the emission peak wavelength of 400 nm to 420 nm (B) is 10 / 90 to 90 / 10.

[0025] [3] The method for producing a blue cured film as described in [1] or [2] above, wherein 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.

[0026] [4] A blue photosensitive composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator, wherein the photoinitiator comprises an oxime photoinitiator represented by the following general formula (A) and a sensitizer having a sensitizing effect at 400 nm to 420 nm, which is different from the oxime photoinitiator, and the blue photosensitive composition is used for curing by exposure to an LED light source having a peak emission wavelength at 360 nm to 380 nm and 400 nm to 420 nm.

[0027] [Chemistry 1]

[0028] General formula (A)

[0029]

[0030] (In general formula (A), Z 1 , Z 3 , Z 4 and Z 5 Each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a phenyl group, wherein the alkyl group, the cycloalkyl group, and the phenyl group may be substituted by a substituent selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and a phenyl group, 2 represents an alkyl group having 1 to 20 carbon atoms substituted by a cycloalkyl group.

[0031] [5] A method for manufacturing a color filter, the color filter comprising at least a substrate and a coloring layer including a blue cured film provided on the substrate, the method comprising the following steps:

[0032] The blue cured film is produced by the method for producing a blue cured film according to any one of [1] to [3].

[0033] [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.

[0034] [7] A display device comprising the color filter described in [6] above.

[0035] Effects of the Invention

[0036] According to the present invention, a method for producing a blue cured film capable of forming a good pattern even by LED exposure, and a method for producing a color filter using the method for producing a blue cured film can be provided. In addition, the present invention can provide a blue photosensitive composition suitable for use in the method for producing a blue cured film, and a color filter and a display device formed using the blue photosensitive composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 This is a schematic diagram showing an example of the color filter of the present invention.

[0038] Figure 2 This is a schematic diagram showing an example of a liquid crystal display device of the present invention.

[0039] Figure 3 This is a schematic diagram showing an example of an organic light emitting display device of the present invention. DETAILED DESCRIPTION

[0040] Hereinafter, the method for producing a blue cured film, the blue photosensitive composition, the color filter and the method for producing the same, and the display device of the present invention will be described in detail one by one.

[0041] It should be noted that, in the present invention, light includes electromagnetic waves with wavelengths in the visible and non-visible regions, and radiation, and radiation includes, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves with wavelengths of 5 μm or less, and electron beams.

[0042] In the present invention, (meth)acryloyl means each of acryloyl and methacryloyl, (meth)acrylic acid means each of acrylic acid and methacrylic acid, and (meth)acrylate means each of acrylate and methacrylate.

[0043] In addition, in this specification, "to" which shows a numerical range is used to mean that the numerical values ​​described before and after it are included as a lower limit and an upper limit.

[0044] I. Method for producing blue cured film

[0045] The method for producing a blue cured film of the present invention comprises the following steps: forming a coating film of a blue photosensitive composition on a substrate, the blue photosensitive composition comprising a color material, an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator, the photoinitiator comprising an oxime-based photoinitiator and a sensitizer having a sensitizing effect at 400 nm to 420 nm different from the oxime-based photoinitiator; and

[0046] The coating film is exposed to light using an LED light source having emission peak wavelengths of 360 nm to 380 nm and 400 nm to 420 nm to be cured.

[0047] In the method for producing a blue cured film of the present invention, a coating film of a blue photosensitive composition containing a color material, an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator containing an oxime-based photoinitiator and a sensitizer having a sensitizing effect at 400 nm to 420 nm different from the oxime-based photoinitiator is exposed to light using an LED light source having emission peak wavelengths at 360 nm to 380 nm and 400 nm to 420 nm to cure the coating film, thereby suppressing line width deviation and improving the residual film rate after development, and forming a good pattern with suppressed undercut after development, and the substrate adhesion of the formed blue cured film pattern is also improved. Since an oxime photoinitiator is combined with a sensitizer having a sensitizing effect at 400 nm to 420 nm which is different from the oxime photoinitiator to prepare a blue photosensitive composition capable of effectively using light having a peak emission wavelength of 400 nm to 420 nm, an LED light source having peak emission wavelengths at both 360 nm to 380 nm and 400 nm to 420 nm is used, the disadvantages of insufficient curing and line width deviation are complementary to each other, the line width deviation can be suppressed and good curing can be achieved deep inside, so it is believed that the line width deviation can be suppressed and a good pattern can be formed, and the substrate adhesion is also improved.

[0048] (1) Coating film forming process

[0049] First, the process includes forming a coating film of a blue photosensitive composition on a substrate, wherein the blue photosensitive composition includes a colorant, an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator, wherein the photoinitiator includes an oxime photoinitiator and a sensitizer having a sensitizing effect at 400 nm to 420 nm, which is different from the oxime photoinitiator. Here, the blue photosensitive composition used in the present invention will be described below.

[0050] As the substrate, a transparent substrate, a silicon substrate, and a transparent substrate or a silicon substrate on which a thin film of aluminum, silver, or a silver / copper / palladium alloy is formed are used. Other color filter layers, resin layers, transistors such as TFTs, circuits, etc. may also be formed on these substrates.

[0051] The transparent substrate in the present invention is not particularly limited as long as it is a substrate transparent to visible light, and for example, a transparent substrate used in a general color filter can be used. Specifically, examples include: a non-flexible transparent rigid material such as quartz glass, alkali-free glass, and a synthetic quartz plate, or a flexible transparent flexible material such as a transparent resin film, an optical resin plate, and a flexible glass.

[0052] The thickness of the transparent substrate is not particularly limited, and a substrate having a thickness of, for example, about 100 μm to 1 mm can be used depending on the application of the blue cured film to be produced by the present invention.

[0053] The blue photosensitive composition described below is applied to the substrate to form a wet coating film by using a coating method such as spray coating, dip coating, bar coating, roll coating, spin coating, die coating, etc. Among them, spin coating and die coating are preferably used.

[0054] Next, the wet coating film is dried (pre-baked) using a hot plate, an oven, or the like to form a coating film.

[0055] Prebaking is usually performed by combining reduced pressure drying with heat drying. Reduced pressure drying is usually performed until it reaches 50 Pa to 200 Pa. In addition, the conditions for heat drying are usually to use a hot plate at a temperature of 70°C to 110°C for about 1 minute to 10 minutes. In addition, the thickness of the applied coating film can be appropriately adjusted according to the purpose of the blue cured film. As the thickness of the dried coating film, for example, 0.5 μm to 5.0 μm can be cited, and preferably 1.0 μm to 3.0 μm can be cited.

[0056] (2) Exposure process

[0057] In the present invention, the exposure step is a step of curing the coating film by exposing it to light using an LED light source having a peak emission wavelength of 360 nm to 380 nm and 400 nm to 420 nm.

[0058] Here, the “peak emission wavelength” refers to the wavelength at which the emission intensity reaches a maximum in the LED emission spectrum, and can be measured using a spectral radiometer (eg, USR-45DA-14 (manufactured by Ushio Electric Co., Ltd.)).

[0059] The LED light source having emission peak wavelengths of 360 nm to 380 nm and 400 nm to 420 nm that can be used in the present invention includes both the case where light having the above two emission peak wavelengths is irradiated from one LED irradiation device and the case where light having the above two emission peak wavelengths is irradiated from two or more LED irradiation devices.

[0060] In addition, the LED light source having emission peak wavelengths at 360 nm to 380 nm and 400 nm to 420 nm may have two or more emission peak wavelengths at 360 nm to 380 nm, and may have two or more emission peak wavelengths at 400 nm to 420 nm.

[0061] Furthermore, the LED light source having emission peak wavelengths in the range of 360 nm to 380 nm and 400 nm to 420 nm may or may not further have emission peak wavelengths in other wavelength regions.

[0062] In the LED light source that can be used in the present invention, the intensity ratio (A / B) of the intensity of the emission peak wavelength (A) of 360 nm to 380 nm to the intensity of the emission peak wavelength (B) of 400 nm to 420 nm can be appropriately selected according to the use of the blue photosensitive composition and the cured film thereof, and is not particularly limited. The above intensity ratio (A / B) can be, for example, 1 / 99 to 99 / 1, or 5 / 95 to 95 / 5, preferably 10 / 90 to 90 / 10, and more preferably 10 / 90 to 80 / 20. Depending on the use of the blue photosensitive composition and the cured film thereof, the above intensity ratio (A / B) can be further 20 / 80 to 80 / 20, and further 40 / 60 to 60 / 40.

[0063] The intensity ratio (A / B) can be confirmed using a spectral irradiance meter (for example, USR-45DA-14 (manufactured by Ushio Electric Co., Ltd.)).

[0064] For example, when there are two or more emission peak wavelengths in the range of 360 nm to 380 nm, the total intensities of the two emission peak wavelengths are taken as the intensity (A) of the emission peak wavelengths in the range of 360 nm to 380 nm.

[0065] The LED light source having a peak emission wavelength at 360 nm to 380 nm and 400 nm to 420 nm that can be used in the present invention can be used by combining an LED chip having a peak emission wavelength at 360 nm to 380 nm and an LED chip having a peak emission wavelength at 400 nm to 420 nm. In this case, it is preferred from the viewpoint of being easy to appropriately adjust the intensity ratio (A / B) and the curability of the blue photosensitive composition by the number and ratio of the LED chips having a peak emission wavelength at 360 nm to 380 nm and the LED chips having a peak emission wavelength at 400 nm to 420 nm.

[0066] The LED chip used in the LED light source may further include a focusing lens for the purpose of improving the illumination.

[0067] As LED chips having a peak emission wavelength of 360 nm to 380 nm or 400 nm to 420 nm, commercially available LEDs can be appropriately selected and used. As commercially available LEDs, for example, UV-LEDs 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. can be mentioned, but the present invention is not limited to these.

[0068] When a LED chip having a peak emission wavelength of 360 nm to 380 nm and an LED chip having a peak emission wavelength of 400 nm to 420 nm are used in combination as the LED light source that can be used in the present invention, the arrangement of the LED chips is not particularly limited. The ratio of the number of LED chips can be adjusted according to the above-mentioned intensity ratio (A / B), for example, the arrangement can be performed with or without regularity.

[0069] Alternatively, as the LED light source that can be used in the present invention, an LED irradiation device having a peak emission wavelength of 360 nm to 380 nm and an LED irradiation device having a peak emission wavelength of 400 nm to 420 nm can be used simultaneously or sequentially for exposure. In addition, there is no limitation on the exposure order of each LED irradiation device.

[0070] The illuminance of the LED light source that can be used in the present invention can be adjusted appropriately, and 5 mW / cm 2 LED light source above 15 mW / cm 2 ~60 mW / cm 2 , or 60 mW / cm 2 above.

[0071] In the exposure process, the cumulative amount of ultraviolet light from the LED light source can be appropriately adjusted according to the thickness of the coating film, usually 5 mJ / cm 2 ~200 mJ / cm 2 , or 200 mJ / cm 2 ~1000 mJ / cm 2 .

[0072] In the method for producing a blue cured film of the present invention, after the exposure step, (3) a step of developing the exposed coating film (development step) and / or (4) a step of post-baking the coating film (heating step) may be performed as needed.

[0073] (3) Development process

[0074] After the exposure step, a development treatment is performed using a developer to dissolve and remove the unexposed portion, thereby forming a cured coating film in a desired pattern.

[0075] As the developer, an alkaline developer is preferably used, for example, aqueous solutions of sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, 1,5-diazabicyclo-[4.3.0]-5-nonene, etc. can be used. For example, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, etc. can also be added to the alkaline developer. It should be noted that after the alkaline development treatment, water washing is usually performed.

[0076] As the development treatment method, for example, shower development, spray development, dip development, or flooding development can be applied. The development conditions can be set to, for example, 5 seconds to 300 seconds at room temperature.

[0077] (4) Heating process

[0078] After exposure, the cured coating film may be subjected to a heat treatment to promote the polymerization reaction before the development step. The heating conditions are appropriately selected depending on the heating method used, the mixing ratio of each component in the blue photosensitive composition, the thickness of the cured coating film, and the like.

[0079] In addition, after the development treatment, the developer is usually cleaned and the cured coating of the blue photosensitive composition is dried to form a blue cured film. It should be noted that after the development process, a heat treatment may also be performed to fully cure the cured coating. The heating conditions are not particularly limited and are appropriately selected according to the heating method used, the proportion of each component in the blue photosensitive composition, the thickness of the cured coating, etc. In the case of using a hot air heating furnace, for example, it can be set at 150°C to 250°C for about 20 minutes to 40 minutes.

[0080] The film thickness of the patterned blue cured film formed in this way is, in terms of film thickness after drying, for example, 0.5 μm to 5.0 μm, and preferably 1.0 μm to 3.0 μm.

[0081] The blue cured film thus formed may be a cured film having chromaticity coordinates in the range of x=0.110 to 0.150 and y=0.035 to 0.190 in the XYZ colorimetric system of JIS Z8701 using a C light source for color measurement. In particular, in terms of improving color reproducibility, the blue cured film may be a cured film in the range of x=0.120 to 0.147 and y=0.038 to 0.180, a cured film in the range of x=0.122 to 0.147 and y=0.038 to 0.150, or a cured film in the range of x=0.125 to 0.147 and y=0.038 to 0.120.

[0082] According to the method for producing a blue cured film of the present invention, line width deviation can be suppressed and the residual film rate after development can be improved, a good pattern with suppressed undercut after development can be formed, and the substrate adhesion of the formed blue cured film pattern is also improved. Therefore, the method for producing a blue cured film is suitable for use in a method for producing a color filter.

[0083] II. Blue Photosensitive Composition

[0084] The blue photosensitive composition used in the method for producing a blue cured film of the present invention contains a colorant, an alkali-soluble resin, a photopolymerizable compound and a photoinitiator. The photoinitiator includes an oxime photoinitiator and a sensitizer having a sensitizing effect at 400 nm to 420 nm different from the oxime photoinitiator.

[0085] Among them, the blue photosensitive composition of the present invention, which is suitable for use in the method for producing the blue cured film of the present invention, contains a colorant, an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator, wherein the photoinitiator includes an oxime photoinitiator represented by the following general formula (A) and a sensitizer having a sensitizing effect at 400 nm to 420 nm, which is different from the oxime photoinitiator. The blue photosensitive composition is cured by exposure to an LED lamp having a peak emission wavelength at 360 nm to 380 nm and 400 nm to 420 nm.

[0086] [Chemistry 2]

[0087] General formula (A)

[0088]

[0089] (In general formula (A), Z 1 , Z 3 , Z 4 and Z 5 Z each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a phenyl group, and the alkyl group, cycloalkyl group, and phenyl group may be substituted by a substituent selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and a phenyl group. 2 represents an alkyl group having 1 to 20 carbon atoms substituted by a cycloalkyl group.

[0090] The blue photosensitive composition used in the method for producing a blue cured film of the present invention can be selected by selecting the respective components so that the blue cured film formed by the method for producing a blue cured film of the present invention becomes a cured film having chromaticity coordinates in the range of x=0.110 to 0.150 and y=0.035 to 0.190 in the XYZ colorimetric system of JIS Z8701 using, for example, a C light source for color measurement.

[0091] Hereinafter, each component contained in the blue photosensitive composition used for the manufacturing method of the blue cured film of the present invention mentioned above is demonstrated one by one.

[0092] <Color>

[0093] The color material is not particularly limited as long as the color tone 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.

[0094] As the color material, a blue color material is included, and a violet color material may be further included, and other color materials may be further included.

[0095] The blue color material used in the present invention is a color material having a transmittance of 60% or more at 440 nm, 10% or more at 520 nm, and less than 10% at 580 nm when a coating film of P / V=0.2 and 2.5 μm is formed and a spectral transmittance spectrum is measured.

[0096] It should be noted that, in order to measure the color by coating the blue color material with a single component, it is sufficient to prepare a coating liquid by mixing an appropriate dispersant, a binder component and a solvent in the blue color material, apply it on a transparent substrate and dry it, and solidify it as needed. As a binder component, as long as a transparent coating film capable of color measurement can be formed, a non-curable thermoplastic resin composition can be used, and a photocurable (photosensitive) or thermosetting resin composition can also be used. Specifically, for example, the solid components other than the color material used in the photosensitive composition of Example 1 described later can be used as a dispersant and a binder component.

[0097] As a colorimetric transparent coating film containing a dispersant and a binder component, for example, a film thickness of 2.0 μm and a transmittance of 95% or more in a spectral transmittance spectrum of 380 nm to 780 nm can be used as a standard.

[0098] In addition, the spectral transmittance spectrum can be measured using a spectrophotometer (for example, microspectrophotometer OSP-SP200 manufactured by Olympus).

[0099] The blue color material used in the present invention is not particularly limited, and known blue organic pigments, blue dyes, and blue lake color materials as salt compounds of blue dyes can be used. Here, compared with dyes and lake color materials, blue organic pigments are excellent in heat resistance, light resistance and other tolerances, and blue dyes are soluble, so they have higher transmittance than organic pigments. In addition, lake color materials are derived from dyes, so they have higher transmittance than ordinary pigments, and can meet the requirements of high brightness.

[0100] Examples of the blue organic pigment include CI Pigment Blue 15, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, CI Pigment Blue 16, and CI Pigment Blue 60. Among them, copper phthalocyanine blue pigments are preferred because of their relatively excellent brightness.

[0101] Examples of the blue dye include methine dyes, anthraquinone dyes, azo dyes, triarylmethane dyes and phthalocyanine dyes.

[0102] In the blue lake color material which is a salt-forming compound of the blue dye, the counter ion varies depending on the type of the dye. The counter ion of the acidic dye is a cation, and the counter ion of the basic dye is an anion.

[0103] As the counter cation of the acid dye, in addition to the ammonium cation, a metal cation, an inorganic polymer, etc. may be mentioned.

[0104] Preferred examples of the laking agent that generates ammonium ions include primary amine compounds, secondary amine compounds, and tertiary amine compounds. Among them, secondary amine compounds and tertiary amine compounds are preferably used because they are excellent in heat resistance and light resistance.

[0105] The laking agent that generates metal cations may be appropriately selected from metal salts having desired metal ions.

[0106] The counter cation of the acid dye may be used alone or in combination of two or more.

[0107] On the other hand, the counter anion of the basic dye may be an organic anion or an inorganic anion. As the organic anion, an organic compound having an anionic group as a substituent may be mentioned.

[0108] In addition, known acid dyes can also be used as organic anions. In this case, the lake color material exists in the form of an ion pair of an acid dye and a basic dye. As the lake agent that produces these organic anions, alkali metal salts, alkaline earth metal salts, etc. of the above-mentioned organic anions can be cited.

[0109] On the other hand, examples of inorganic anions include anions of oxygen-containing acids (phosphate ions, sulfate ions, chromate ions, tungstate ions (WO 4 2- ), molybdate ion (MoO 4 2- ) etc.), inorganic anions such as polyacid anions formed by condensation of multiple oxygen-containing acids, and mixtures thereof.

[0110] As the above-mentioned polyacid, it can be an isopolyacid anion (Mm O n ) c- , or a heteropolyacid anion (X l M m O n ) c- In the above ionic formula, M represents a polyatom, X represents a heteroatom, m represents the composition ratio of the polyatom, and n represents the composition ratio of oxygen atoms. Examples of the polyatom M include Mo, W, V, Ti, and Nb. In addition, examples of the heteroatom X include Si, P, As, S, Fe, and Co. c represents a valence number, which may be an integer greater than 2.

[0111] Among them, in terms of heat resistance, a polyacid anion containing at least one of molybdenum (Mo) and tungsten (W) is preferred, and a c-valent polyacid anion containing at least tungsten is more preferred.

[0112] Examples of the laking agent that generates inorganic anions include alkali salts and alkali metal salts of the above-mentioned inorganic anions.

[0113] The counter anion of the basic dye in the lake color material may be used alone or in combination of two or more.

[0114] Examples of the blue lake color material include CI pigment blue 1, CI pigment blue 1:2, CI pigment blue 2, CI pigment blue 3, CI pigment blue 8, CI pigment blue 9, CI pigment blue 10, CI pigment blue 12, CI pigment blue 14, CI pigment blue 17:1, CI pigment blue 18, CI pigment blue 19, CI pigment blue 24, CI pigment blue 24:1, CI pigment blue 53, CI pigment blue 56, CI pigment blue 56:1, CI pigment blue 61, CI pigment blue 61:1, CI pigment blue 62, CI pigment blue 63, and CI pigment blue 78.

[0115] In addition, the blue lake color material may be a triarylmethane-based lake color material or at least one lake color material selected from the group consisting of a color material represented by the following general formula (1) and a color material represented by the following general formula (2) in terms of reliability such as heat resistance and weather resistance.

[0116] [Chemistry 3]

[0117] General formula (1)

[0118]

[0119] (In the general formula (1), A is an a-valent organic group whose carbon atom directly bonded to N does not have a π bond, and the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N, or an aromatic group having the aliphatic hydrocarbon group, and may contain a heteroatom in the carbon chain; B c- Represents a polybasic anion with a C valence; R i ~R v Each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ii With R iii , R iv With R v Can bond to form a ring structure; R vi and R vii Each independently represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom or a cyano group; Ar 1 represents a divalent aromatic group which may have a substituent; when there are multiple R i ~R vii and Ar 1 They can be the same or different from each other;

[0120] a and c represent integers greater than 2, b and d represent integers greater than 1; f and g represent integers greater than 0 and less than 4; plural f and g may be the same or different.

[0121] [Chemistry 4]

[0122] General formula (2)

[0123]

[0124] (In general formula (2), R I ~R VI Each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R I With R II , R III With R IV , R V With R VI Can bond to form a ring structure; R VII and R VIII Each independently represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom or a cyano group; Ar 2 represents a divalent aromatic heterocyclic group which may have a substituent, and there are plural R I ~R VIII and Ar 2 They can be the same or different from each other; E m- It represents the m-valent polyacid anion;

[0125] m represents an integer greater than 2; j is 0 or 1, and when j is 0, there is no bond; k and l represent integers greater than 0 and less than 4, and k+j and l+j are greater than 0 and less than 4; plural j, k, and l may be the same or different.

[0126] For the description of each symbol of at least one lake color material selected from the group consisting of the color material represented by the general formula (1) and the color material represented by the general formula (2), reference can be made to paragraphs 0031 to 0061 of International Publication No. 2020 / 071041.

[0127] The blue colorant may be appropriately selected according to the application of the blue cured film. When used for a color filter, in terms of hue, it is preferably one or more selected from the group consisting of CI Pigment Blue 15:6, CI Pigment Blue 15:3, CI Pigment Blue 15:4, and triarylmethane-based lake colorants.

[0128] As the violet colorant, a colorant having a transmittance of 40% or more at 440 nm, less than 10% at 520 nm, and 40% or more at 680 nm when a coating film of P / V=0.2 and 2.5 μm is formed and a spectral transmittance spectrum is measured was used.

[0129] The purple color material used in the present invention also includes a red-purple color material also referred to as a red dye.

[0130] In addition, the color measurement of the purple color material in the form of a single component coating can be carried out in the same manner as the above-mentioned blue color material.

[0131] The violet color material used in the present invention is not particularly limited, and known violet organic pigments, violet dyes, violet lake color materials, and the like can be used.

[0132] Examples of the violet organic pigment include CI Pigment Violet 1, 14, 15, 19, 23, 29, 32, 33, 36, 37, and 38. Among them, Pigment Violet 23 is preferred because of its relatively excellent coloring power.

[0133] Examples of the purple dye include anthraquinone acid dyes such as CI Acid Violet 29, 31, 33, 34, 36, 36:1, 39, 41, 42, 43, 47, 51, 63, 76, 103, 118, and 126; cyanine acid dyes such as CI Basic Red 12; triarylmethane acid dyes such as Acid Violet 15, 16, 17, 19, 21, 23, 24, 25, 38, 49, and 72; rose red acid dyes such as CI Acid Red 289, CI Acid Violet 9, and CI Acid Violet 30; and triarylmethane basic dyes such as CI Basic Violet 1, 3, and 14, and xanthene basic dyes such as CI Basic Violet 11.

[0134] Examples of the purple lake color material include a color material obtained by laking the purple dye described above using a laking agent.

[0135] In the lake color material, the counter ion varies depending on the type of the dye, the counter ion of the acid dye is a cation, and the counter ion of the basic dye is an anion. As the counter cation of the acid dye and the counter anion of the basic dye, the same ions as those exemplified for the blue dye can be used.

[0136] As the purple lake color material, in terms of hue, one or more selected from the group consisting of anthraquinone-based color materials, cyanine-based color materials, and xanthene-based color materials are preferred.

[0137] In addition, the violet dye and the violet lake color material are preferably xanthene-based color materials containing xanthene as a basic skeleton and containing a rose red-based color material in terms of improving the brightness and contrast of the colored layer.

[0138] As the xanthene-based acid dye in the lake color material, it is preferred to contain a compound represented by the following general formula (3), that is, a rose bengal-based acid dye.

[0139] [Chemistry 5]

[0140] General formula (3)

[0141]

[0142] (In general formula (3), R a ~R d Each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and R a With R b , R c With R d Can bond to form a ring structure; R erepresents an acidic group, X represents a halogen atom; m represents an integer of 0 to 5; in the case of general formula (3) having one or more acidic groups, n is an integer greater than 0.

[0143] For the description 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.

[0144] As the color lake material of the xanthene-based acid dye, a metal color lake material is preferably used. The metal color lake material can use a color lake material containing a metal atom as a color lake agent. By using a color lake agent containing a metal atom, the heat resistance of the color material is improved. As such a color lake agent, a color lake agent containing a metal atom that becomes a metal cation with a valence of more than 2 is preferably used.

[0145] As other color materials used in the present invention, for example, red color materials, orange color materials, green color materials, etc. are preferably used. Among them, red color materials and green color materials can be used in terms of hue.

[0146] As other color materials, the following color materials can be mentioned, for example, but they are not limited to these.

[0147] As red color materials, CI Pigment Red 177, 168, 254, etc.

[0148] As green color materials, CI Pigment Green 7, 36, 58, 59, etc.

[0149] In the blue photosensitive composition used in the present invention, the content ratio of the blue colorant relative to the entire colorant may be appropriately adjusted according to the desired chromaticity and is not particularly limited.

[0150] In terms of the required chromaticity for various light sources, it is preferably containing 50 mass % or more and 100 mass % or less of blue color material relative to the total amount of color material, more preferably containing 60 mass % or more and 90 mass % or less of blue color material, and it may also contain 70 mass % or more and 80 mass % or less of blue color material.

[0151] In the blue photosensitive composition used in the present invention, the content ratio of the violet colorant to the blue colorant may be appropriately adjusted according to the desired chromaticity and is not particularly limited.

[0152] In terms of the required chromaticity for various light sources, the purple color material may be contained in an amount of 3 parts by mass or more and 100 parts by mass or less, or 5 parts by mass or more and 80 parts by mass or less, based on 100 parts by mass of the blue color material.

[0153] Moreover, the purple color material may be contained in an amount of 1% to 50% by mass, 3% to 40% by mass, or 5% to 30% by mass, based on the total amount of the color material.

[0154] The blue photosensitive composition used in the present invention may further contain other color materials in the color material, and the total content of the blue color material and the purple color material is more preferably 70 mass % to 100 mass %, and more preferably 80 mass % to 100 mass % relative to the total amount of the color materials.

[0155] In the blue photosensitive composition of the present invention, the content of the color material is not particularly limited. In terms of dispersibility and dispersion stability, the content of the color material is generally in the range of 3% to 65% by mass, preferably in the range of 4% to 60% by mass, and more preferably in the range of 15% to 60% by mass, relative to the total solid content of the blue photosensitive composition. If it is above the above lower limit, the coloring layer when the blue photosensitive composition is applied to a specified film thickness (usually 1.0 μm to 5.0 μm) has sufficient color concentration. In addition, as long as it is below the above upper limit, a coloring layer with excellent storage stability, sufficient hardness, and adhesion to the substrate can be obtained. In particular, when a coloring layer with a higher concentration of color materials is formed, the total content of the color material is preferably in the range of 20% to 65% by mass, and more preferably in the range of 30% to 60% by mass, relative to the total solid content of the blue photosensitive composition.

[0156] <Alkali-soluble resin>

[0157] The alkali-soluble resin in the present invention is a resin having an acidic group, and can be appropriately selected from resins that function as a binder resin and are soluble in an alkaline developer used in pattern formation.

[0158] In the present invention, the alkali-soluble resin may have an acid value of 40 mgKOH / g or more.

[0159] Preferred alkali-soluble resins in the present invention are resins having an acidic group, usually a carboxyl group, and specific examples thereof include (meth)acrylic resins such as (meth)acrylic copolymers having a carboxyl group and styrene-(meth)acrylic copolymers having a carboxyl group, and epoxy (meth)acrylate resins having a carboxyl group.

[0160] Among these, the resin that is particularly preferred is a resin having a carboxyl group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain. In the case of containing a photopolymerizable functional group, in the exposure process, the alkali-soluble resins can form crosslinking bonds with each other or with photopolymerizable compounds such as the alkali-soluble resin and a multifunctional monomer. In the case of containing a photopolymerizable functional group, the film strength is improved, so in the post-baking, the pigment is not easy to agglomerate, and a state with a low phase difference can be maintained. In addition, the film strength of the cured film is improved, the development tolerance is improved, and the thermal shrinkage of the cured film is suppressed so that the adhesion with the substrate becomes excellent.

[0161] The method of introducing ethylenically unsaturated bonds into the alkali-soluble resin may be appropriately selected from the conventionally known methods. For example, the method may include: 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 the alkali-soluble resin to introduce ethylenically unsaturated bonds into the side chain; introducing a structural unit having a hydroxyl group into a copolymer in advance, and adding the compound having an isocyanate group and an ethylenically unsaturated bond in the molecule to introduce ethylenically unsaturated bonds into the side chain, etc.

[0162] In addition, the alkali-soluble resin preferably further has a hydrocarbon ring in terms of excellent adhesion of the colored layer. The presence of a hydrocarbon ring as a bulking group in the alkali-soluble resin suppresses shrinkage during curing, alleviates peeling from the substrate, and improves adhesion to the substrate.

[0163] Examples of such hydrocarbon rings include an aliphatic hydrocarbon ring which may have a substituent, an aromatic hydrocarbon ring which may have a substituent, and combinations thereof. The hydrocarbon ring may have a substituent such as an alkyl group, a carbonyl group, a carboxyl group, an oxycarbonyl group, an amide group, a hydroxyl group, a nitro group, an amino group, a halogen atom or the like.

[0164] The hydrocarbon ring may be contained as a monovalent group or may be contained as a divalent or higher-valent group.

[0165] Specific examples of hydrocarbon rings include: aliphatic hydrocarbon rings such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, isobornane, tricyclo[5.2.1.0(2,6)]decane (dicyclopentane), and adamantane; aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, and fluorene; chain polycyclic rings such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, and stilbene, or cardo structures (9,9-diarylfluorene); groups in which a part of these groups is substituted by a substituent, etc.

[0166] 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 and a halogen atom.

[0167] In the case of containing an aliphatic hydrocarbon ring as the hydrocarbon ring, it is preferred in that the heat resistance and adhesion of the colored layer are improved and the brightness of the obtained colored layer is improved.

[0168] In the case of including the cardo structure, it is particularly preferred in terms of improving the curability of the colored layer, suppressing fading of the coloring material, and improving the solvent resistance (NMP swelling suppression).

[0169] (Meth)acrylic resins such as (meth)acrylic copolymers containing a structural unit having a carboxyl group and styrene-(meth)acrylic copolymers having a carboxyl group are (co)polymers obtained by, for example, (co)polymerizing a carboxyl group-containing ethylenically unsaturated monomer and, if necessary, other copolymerizable monomers by a known method.

[0170] As the ethylenically unsaturated monomer containing a carboxyl group, for example, (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, etc. can be cited. In addition, the addition reaction product of the monomer having a hydroxyl group such as (meth) 2-hydroxyethyl acrylate and the cyclic anhydride such as maleic anhydride, phthalic anhydride, cyclohexane dicarboxylic anhydride, ω-carboxyl-polycaprolactone mono(meth) acrylate, etc. can also be used. In addition, anhydride-containing monomers such as maleic anhydride, itaconic anhydride, citraconic anhydride, etc. can also be used as precursors of the carboxyl group. Among them, in terms of copolymerizability, cost, solubility, glass transition temperature, etc., (meth) acrylic acid is particularly preferred.

[0171] The alkali-soluble resin in the present invention is preferably a carboxyl group-containing copolymer such as a (meth)acrylic acid copolymer and a styrene-(meth)acrylic acid copolymer containing a structural unit having a carboxyl group and a structural unit having a hydrocarbon ring, and more preferably a carboxyl group-containing copolymer such as a (meth)acrylic acid copolymer and a styrene-(meth)acrylic acid copolymer containing a structural unit having a carboxyl group, a structural unit having a hydrocarbon ring, and a structural unit having an ethylenically unsaturated bond.

[0172] Examples of the ethylenically unsaturated monomer having a hydrocarbon ring include cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and styrene. In terms of a greater effect of maintaining the cross-sectional shape of the colored layer after development even during a heat treatment, it is preferred to use at least one selected from the group consisting of cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, benzyl (meth)acrylate, and styrene.

[0173] The carboxyl group-containing copolymer may further contain other structural units such as structural units having ester groups such as methyl (meth)acrylate and ethyl (meth)acrylate. The structural unit having an ester group functions not only as a component that suppresses the alkali solubility of the photosensitive composition, but also as a component that improves solubility in solvents and further improves solvent resolubility.

[0174] The carboxyl group-containing copolymer can be prepared into an alkali-soluble resin having desired properties by appropriately adjusting the addition amount of each structural unit.

[0175] The amount of the carboxyl-containing ethylenically unsaturated monomer added is preferably 5% by mass or more, more preferably 10% by mass or more, relative to the total amount of monomers, in order to obtain a good pattern. On the other hand, in order to suppress the roughness of the film on the pattern surface after development, the amount of the carboxyl-containing ethylenically unsaturated monomer added is preferably 50% by mass or less, more preferably 40% by mass or less, relative to the total amount of monomers.

[0176] In addition, in the carboxyl group-containing copolymers such as (meth)acrylic copolymers and styrene-(meth)acrylic copolymers containing structural units having ethylenically unsaturated bonds, which are more preferably used as the alkali-soluble resin, the added amount of the compound having both an epoxy group and an ethylenically unsaturated bond relative to the carboxyl group-containing ethylenically unsaturated monomer is preferably 10% by mass or more and 95% by mass or less, and more preferably 15% by mass or more and 90% by mass or less.

[0177] The preferred mass average molecular weight (Mw) of the carboxyl group-containing copolymer is in the range of 1,000 to 50,000, more preferably 3,000 to 20,000. If it is 1,000 or more, the binder function after curing is improved, and if it is 50,000 or less, pattern formation is improved during development with an alkaline developer.

[0178] The mass average molecular weight (Mw) of the alkali-soluble resin can be measured by Shodex GPC system-21H using polystyrene as a standard substance and THF as an eluent.

[0179] The epoxy (meth)acrylate resin having a carboxyl group is not particularly limited, and an epoxy (meth)acrylate compound obtained by reacting a reaction product of an epoxy compound and an unsaturated group-containing monocarboxylic acid with an acid anhydride is suitable.

[0180] The epoxy compound, the unsaturated group-containing monocarboxylic acid, and the acid anhydride can be appropriately selected from known ones and used.

[0181] The epoxy (meth)acrylate resin having a carboxyl group also preferably has the above-mentioned hydrocarbon ring in the molecule, and among them, a resin having a cardo structure is preferred in terms of improving the curability of the colored layer, suppressing fading of the color material, and increasing the residual film rate of the colored layer.

[0182] The epoxy (meth)acrylate resins having a carboxyl group may be used alone or in combination of two or more.

[0183] In terms of the developability (solubility) in the alkaline aqueous solution used in the developer, the alkali-soluble resin preferably has an acid value of 40 mgKOH / g or more. In terms of the developability (solubility) in the alkaline aqueous solution used in the developer and the adhesion to the substrate, the alkali-soluble resin preferably has an acid value of 40 mgKOH / g or more and 300 mgKOH / g or less, and preferably 50 mgKOH / g or more and 280 mgKOH / g or less.

[0184] The ethylenic unsaturated bond equivalent when the side chain of the alkali-soluble resin has an ethylenic unsaturated group is preferably in the range of 100 to 2000, more preferably in the range of 140 to 1500, and may also be in the range of 140 to 1000, in terms of obtaining the effect of improving the film strength of the cured film and easily maintaining a low phase difference, improving the development resistance, and excellent adhesion to the substrate. If the ethylenic unsaturated bond equivalent is below the upper limit, it is easy to maintain a low phase difference, and the development resistance and adhesion are excellent. In addition, if it is above the lower limit, the ratio of other structural units such as the structural unit having a carboxyl group and the structural unit having a hydrocarbon ring can be relatively increased, so the developability and heat resistance are excellent.

[0185] Here, the ethylenically unsaturated bond equivalent refers to the mass average molecular weight per 1 mol of ethylenically unsaturated bonds in the alkali-soluble resin, and is represented by the following mathematical formula (1).

[0186] Mathematical formula (1)

[0187] Ethylenically unsaturated bond equivalent (g / mol) = W (g) / M (mol)

[0188] (In mathematical 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))

[0189] The ethylenically unsaturated bond equivalent can be calculated by measuring the number of ethylenically unsaturated bonds contained per 1 g of the alkali-soluble resin, for example, by a test method for iodine value described in JIS K 0070:1992.

[0190] The alkali-soluble resin used in the blue photosensitive composition can be used alone or in combination of two or more. There is no particular restriction on the content of the alkali-soluble resin, and relative to the total solid content of the blue photosensitive composition, it is preferably in the range of 5% to 60% by mass, and more preferably in the range of 10% to 40% by mass. If the content of the alkali-soluble resin is above the above lower limit, sufficient alkali developability can be obtained. In addition, if the content of the alkali-soluble resin is below the above upper limit, the film roughness and pattern defects during development can be suppressed.

[0191] <Photopolymerizable compounds>

[0192] The photopolymerizable compound used in the blue photosensitive composition of the present invention is not particularly limited as long as it can be polymerized by a photoinitiator. Generally, a compound having two or more ethylenically unsaturated bonds is preferably used, and a polyfunctional (meth)acrylate having two or more acryloyl groups or methacryloyl groups is particularly preferred.

[0193] As such a polyfunctional (meth)acrylate, what is necessary is just to select suitably from conventionally well-known ones and use it. As a specific example, for example, the thing etc. which are described in Unexamined-Japanese-Patent No. 2013-029832 can be mentioned.

[0194] These multifunctional (meth)acrylates may be used alone or in combination of two or more. In addition, in the blue photosensitive composition of the present invention, since excellent photocurability is required, the multifunctional (meth)acrylate is preferably a compound having three or more (trifunctional) ethylenically unsaturated bonds, more preferably a compound containing 3 to 15 ethylenically unsaturated bond groups, and further preferably a compound containing 3 to 6 ethylenically unsaturated bond groups. In addition, the polymerizable compound is preferably a 3-15-functional (meth)acrylate compound, more preferably a 3-6-functional (meth)acrylate compound.

[0195] As the compound having three or more (trifunctional) ethylenically unsaturated bonds, for example, poly(meth)acrylates of trivalent or more polyols and dicarboxylic acid-modified products thereof are preferred, and specifically, trimethylolpropane 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(meth)acrylate, succinic acid-modified product of dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate and the like are preferred.

[0196] The photopolymerizable compound used in the blue photosensitive composition of the present invention may also contain a photopolymerizable compound having an acidic group in terms of developability. Examples of the acidic group include a carboxyl group, a sulfonic group, a phosphoric acid group, and the like, preferably a carboxyl group. Examples of commercially available photopolymerizable compounds having an acidic group include ARONIX M-510, M-520, and ARONIX TO-2349 (manufactured by Toagosei Co., Ltd.).

[0197] In the photopolymerizable compound used in the blue photosensitive composition of the present invention, the content of the photopolymerizable compound having an acidic group may be 20% by mass or less, 10% by mass or less, or 5% by mass or less relative to the total amount of the photopolymerizable compound in terms of developability, and may also be 0% by mass in terms of the acid value of the above-mentioned alkali-soluble resin combined.

[0198] The photopolymerizable compound used in the blue photosensitive composition of the present invention may contain a photopolymerizable compound having a caprolactone structure in terms of good curability adjustment, easy formation of fine patterns, and easy suppression of defects. The photopolymerizable compound having a caprolactone structure may contain a structure in which ε-caprolactone is ring-opened, and may contain a structure in which ε-caprolactone is ring-opened as a repeating unit.

[0199] The photopolymerizable compound having a caprolactone structure can be obtained, for example, by esterifying an alcohol with (meth)acrylic acid and ε-caprolactone. Among them, a compound obtained by esterifying a polyol with (meth)acrylic acid and ε-caprolactone is preferably used.

[0200] As the photopolymerizable compound having a caprolactone structure, a commercially available product may be used as appropriate. As a commercially available product, for example, KAYARAD DPCA series manufactured by Nippon Kayaku Co., Ltd. is commercially available.

[0201] The content of the photopolymerizable compound having a caprolactone structure in the photopolymerizable compound used in the blue photosensitive composition of the present invention may be 0 to 70% by mass, or 10 to 50% by mass, relative to the total amount of the photopolymerizable compound in terms of adjusting curability.

[0202] In addition, the photopolymerizable compound used in the blue photosensitive composition of the present invention may also contain a photopolymerizable compound having an alkyleneoxy group, in terms of good curability adjustment, easy formation of fine patterns, and easy suppression of defects. 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 further preferably a 3-6 functional (meth) acrylate compound having 4 to 20 ethyleneoxy groups. Commercially available products of the photopolymerizable compound having an alkyleneoxy group include, for example, ethoxylated (4) pentaerythritol tetraacrylate (manufactured by Sartomer Co., Ltd., trade name SR-494), trimethylolpropane tripropoxy triacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD TPA-330), ethylene oxide 12 mol modified dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPEA-12), and New Frontier MF-001 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

[0203] The content of the photopolymerizable compound having an alkylene oxide group in the photopolymerizable compound used in the blue photosensitive composition of the present invention may be 0 to 50% by mass, or 5 to 40% by mass, based on the total amount of the photopolymerizable compound from the viewpoint of adjusting curability.

[0204] The mass average molecular weight per 1 mol of the photopolymerizable group of the photopolymerizable compound used in the blue photosensitive composition of the present invention, for example, the unsaturated bond equivalent, is preferably 300 or less, more preferably 250 or less, and further preferably 200 or less in terms of curability. The unsaturated bond equivalent may also be 97 or less in terms of curability. The smaller the unsaturated bond equivalent, the more preferred, and the lower limit may be about 50.

[0205] Here, the unsaturated bond equivalent refers to the mass average molecular weight per 1 mol of the unsaturated bonds in the photopolymerizable compound, and is represented by the following mathematical formula (2).

[0206] Mathematical formula (2)

[0207] Unsaturated bond equivalent (g / mol) = W2 (g) / M2 (mol)

[0208] (In mathematical 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).)

[0209] The content of the photopolymerizable compound used in the blue photosensitive composition is not particularly limited, and is preferably in the range of 5% to 60% by mass, and more preferably 10% to 40% by mass, relative to the total solid content of the blue photosensitive composition. If the content of the photopolymerizable compound is above the lower limit, photocuring is sufficiently advanced, and dissolution during development of the exposed portion can be suppressed. In addition, if the content of the photopolymerizable compound is below the upper limit, alkali developability is sufficient.

[0210] <Photoinitiator>

[0211] The photoinitiator in the blue photosensitive composition used in the method for producing a blue cured film of the present invention includes an oxime-based photoinitiator and a sensitizer having a sensitizing action at 400 nm to 420 nm, which is different from the oxime-based photoinitiator.

[0212] Among them, the blue photosensitive composition of the present invention preferably used in the method for producing a blue cured film of the present invention comprises 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.

[0213] (Oxime photoinitiator)

[0214] In the present invention, the oxime-based photoinitiator refers to a photoinitiator having an oxime ester skeleton.

[0215] As the oxime-based photoinitiator, for example, 1,2-octanedione-1-[4-(phenylthio)phenyl]-, 2-(o-benzoyloxime), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetyloxime), JP-A-2000-80068, JP-A-2001-233842, JP-T-2010-527339, JP-T-2010-527338, JP-A-2013-041153, International Publication No. 2015 / 152153, International Publication No. 2018 / 062105, etc. can be appropriately selected and used.

[0216] As the oxime-based photoinitiator used in the present invention, when a blue color material is combined with an LED light source having the above-mentioned two specific emission peak wavelengths, in terms of sensitivity and the suppression of the undercut width produced after development, it is preferred to select at least one of the group consisting of an oxime-based photoinitiator having a diphenyl sulfide skeleton, an oxime-based photoinitiator having an indole skeleton, and an oxime-based photoinitiator having a carbazole skeleton.

[0217] As the oxime-based photoinitiator having a diphenyl sulfide skeleton, when a blue color material is combined with an LED light source having the above-mentioned two specific emission peak wavelengths, a compound represented by the following general formula (A) is preferably used in terms of sensitivity, suppression of the undercut width generated after development, and improvement of water resistance after development.

[0218] [Chemistry 6]

[0219] General formula (A)

[0220]

[0221] (In general formula (A), Z 1 , Z 3 , Z 4 and Z 5 Each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a phenyl group, wherein the alkyl group, the cycloalkyl group, and the phenyl group may be substituted by a substituent selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and a phenyl group, 2 represents an alkyl group having 1 to 20 carbon atoms substituted by a cycloalkyl group.

[0222] In the above general formula (A), Z 1 , Z 3 , Z 4 and Z 5 The linear or branched alkyl group having 1 to 12 carbon atoms in the alkyl group may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, etc.

[0223] As Z 1 , Z 3 , Z 4 and Z 5 The cycloalkyl group having 3 to 20 carbon atoms in the above-mentioned group may, for example, be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl or cyclooctadecyl.

[0224] As Z 2 The cycloalkyl group in may be the same as the cycloalkyl group having 3 to 20 carbon atoms, and is preferably a cyclopentyl group or a cyclohexyl group.

[0225] As Z 2 The above-mentioned alkyl group having 1 to 20 carbon atoms may include, in addition to the above-mentioned linear or branched alkyl group having 1 to 12 carbon atoms, n-tetradecyl group, n-hexadecyl group, n-octadecyl group and the like.

[0226] In addition, Z 1 , Z 3 , Z4 and Z 5 In the above, examples of the halogen atom which may be substituted on the alkyl group, cycloalkyl group and phenyl group include a fluorine atom, a chlorine atom and a bromine atom.

[0227] Z 1 , Z 3 , Z 4 and Z 5 In the above, examples of the alkoxy group having 1 to 6 carbon atoms which may be substituted in the above alkyl group, cycloalkyl group, and phenyl group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, tert-butoxy group, and the like.

[0228] In the general formula (A), Z 1 In terms of improving sensitivity, an alkyl group having 1 to 6 carbon atoms or a phenyl group is preferred, a methyl group, an ethyl group, or a phenyl group is more preferred, and a methyl group is further preferred.

[0229] In the general formula (A), Z 3 , Z 4 and Z 5 , in terms of brightness, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group is preferred.

[0230] In the general formula (A), Z 2 In terms of solvent solubility and compatibility, an alkyl group having 1 to 14 carbon atoms substituted by a cycloalkyl group having 5 to 6 carbon atoms is preferred, an alkyl group having 1 to 10 carbon atoms substituted by a cycloalkyl group having 5 to 6 carbon atoms is further preferred, a cyclohexylmethyl group or a cyclopentylmethyl group is further preferred, and a cyclohexylmethyl group is particularly preferred.

[0231] As the photoinitiator represented by the general formula (A), an oxime ester compound represented by the following chemical formula (A-1) is preferred because it is less likely to produce sublimates. Examples of commercially available products include TR-PBG-3057 (produced by Changzhou Qiangli Electronic New Materials Co., Ltd.).

[0232] [Chemistry 7]

[0233] Chemical formula (A-1)

[0234]

[0235] The photoinitiator represented by the general formula (A) can be synthesized, for example, by using diphenyl sulfide or its derivatives with reference to JP-A-2012-526185, and appropriately selecting a solvent, reaction temperature, reaction time, purification method, etc. according to the materials used. Alternatively, commercially available products may be appropriately purchased and used.

[0236] As the oxime-based photoinitiator having a diphenyl sulfide skeleton, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(o-benzoyl oxime) (e.g., Irgacure OXE01, manufactured by BASF), 1,2-propanedione, 3-cyclopentyl-1-[4-(phenylthio)phenyl]-, 2-(o-benzoyl oxime) (e.g., TR-PBG-305, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), 1,2-propanedione, 3-cyclopentyl-1-[4-[(2-hydroxyethoxy)phenylthio]phenyl]-, 2-(o-acetyl oxime), 1-pentanone, 1-[4-[4-(2-benzofuranylcarbonyl)phenylthio]phenyl]-4-methyl, 1-(o-acetyl oxime), Adeka Arkles, which is a commercially available product, can also be used. NCI-930 (manufactured by ADEKA), Irgacure OXE04 (manufactured by BASF), etc.

[0237] Examples of the oxime-based photoinitiator having an indole skeleton include compounds represented by the following general formula (B).

[0238] [Chemistry 8]

[0239] General formula (B)

[0240]

[0241] (Where R 1 and R 2 R 11 , OR 11 , COR 11 , SR 11 ,CONR 12 R 13 or CN,

[0242] R 11 , R 12 and R 13 each independently 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,

[0243] R 11 , R 12 and R 13 The hydrogen atoms of the groups represented by may be further replaced by R 21 , OR 21 , COR 21 , SR 21 NR 22 R 23 ,CONR 22 R 23 、-NR 22 -OR23 、-NCOR 22 -OCOR 23 NR 22 COR 21 ,OCOR 21 、COOR 21 SCOR 21 , OCSR 21 、COSR 21 ,CSOR 21 , hydroxyl, nitro, CN, or halogen atoms,

[0244] R 21 , R 22 and R 23 each independently 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,

[0245] R 21 , R 22 and R 23 The hydrogen atoms of the groups represented may be further replaced by hydroxyl groups, nitro groups, CN, halogen atoms, or carboxyl groups.

[0246] R 11 , R 12 , R 13 , R 21 , R 22 and R 23 The alkylene portion of the group represented may contain 1 to 5 -O-, -S-, -COO-, -OCO-, -NR- 24 -、-NR 24 CO-、-NR 24 COO-、-OCONR 24 -, -SCO-, -COS-, -OCS- or -CSO-,

[0247] R 24 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,

[0248] R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 The alkyl portion of the group represented may have a branched side chain or may be a cyclic alkyl group.

[0249] R 3represents 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, and R 3 The alkyl portion of the group represented by may have a branched side chain and may be a cyclic alkyl group. 3 With R 7 , and R 3 With R 8 Each pair can form a ring together.

[0250] R 3 The hydrogen atoms of the groups represented by may be further replaced 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 , hydroxyl, nitro, CN, or halogen atoms,

[0251] R 4 , R 5 , R 6 and R 7 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 , hydroxyl, CN or halogen atom, R 4 With R 5 , R 5 With R 6 , and R 6 With R 7Each pair can form a ring together.

[0252] R 14 , R 15 and R 16 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R 14 , R 15 and R 16 The alkyl part of the group represented by may have a branched side chain or may be a cyclic alkyl group. 8 Represents R 11 , OR 11 , SR 11 , COR 11 ,CONR 12 R 13 NR 12 COR 11 ,OCOR 11 、COOR 11 SCOR 11 , OCSR 11 、COSR 11 ,CSOR 11 , hydroxyl, CN or halogen atoms,

[0253] k represents 0 or 1. )

[0254] The oxime ester compound represented by the general formula (B) has geometric isomers based on the double bond of the oxime, but they are not distinguished. That is, in this specification, the compound represented by the general formula (B) and the preferred embodiment of the compound described later, that is, the compound represented by the following general formula (B') and its exemplary compounds represent a mixture or any one of the two, and are not limited to structures representing isomers.

[0255] As R in the above general formula (B) 3 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 21 , R 22 , R 23 and R 24 The alkyl group having 1 to 20 carbon atoms represented by the group may, for example, be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, and the like.

[0256] As R in the above general formula (B) 3 , R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 Examples of the aryl group having 6 to 30 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthryl, and phenyl substituted with one or more of the above alkyl groups, biphenyl, naphthyl, anthryl, and the like.

[0257] As R in the above general formula (B) 3 , R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 Examples of the arylalkyl group having 7 to 30 carbon atoms include benzyl, α-methylbenzyl, α,α-dimethylbenzyl and phenylethyl.

[0258] As R in the above general formula (B) 3 , R 11 , R 12 , R 13 , R 21 , R 22 , R 23 , and R 24 Examples of the heterocyclic group having 2 to 20 carbon atoms include 5- to 7-membered heterocyclic rings such as pyridyl, pyrimidinyl, furanyl, thienyl, tetrahydrofuranyl, dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, thiazolidinyl, isothiazolidinyl, oxazolidinyl, isoxazolidinyl, piperidinyl, piperazinyl and morpholinyl.

[0259] As R in the above general formula (B) 4 With R 5 , R 5 With R 6 and R 6 With R 7 and R 3 With R 7 and R 3 With R 8 Preferred examples of the ring that can be formed together include 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.

[0260] In addition, as R in the above general formula (B), 4 , R5 , R 6 , R 7 and R 8 The halogen atom represented by and the substitutable R in the above general formula (B) 3 , R 11 , R 12 , R 13 , R 21 , R 22 and R 23 The halogen atom may, for example, be fluorine, chlorine, bromine or iodine.

[0261] In the above general formula (B), R 11 , R 12 , R 13 , R 21 , R 22 and R 23 The alkylene portion of the group represented may contain 1 to 5 -O-, -S-, -COO-, -OCO-, -NR- 24 -、-NR 24 CO-、-NR 24 COO-、-OCONR 24 -, -SCO-, -COS-, -OCS- or -CSO-, and the divalent group contained in this case may be one or more groups, and in the case of groups that can be contained continuously, two or more groups may be contained continuously.

[0262] In addition, R in the above general formula (B) 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 The alkyl (alkylene) part of the represented group may have a branched side chain, or may be a cyclic alkyl group.

[0263] Among the compounds represented by the general formula (B), R 3 An aromatic ring or a compound represented by the following general formula (B') is preferred because of its high sensitivity and easy production.

[0264] [Chemistry 9]

[0265] General formula (B')

[0266]

[0267] (Where R 1 , R 2 , R 4 , R 5 , R 6, R 7 , R 8 and k is the same as in the above general formula (B), R 31 , R 32 , R 33 , R 34 and R 35 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, nitro, CN or halogen atom, R 31 With R 32 , R 32 With R 33 , R 33 With R 34 and R 34 With R 35 Each pair can form a ring together.)

[0268] As R 31 With R 32 , R 32 With R 33 , R 33 With R 34 and R 34 With R 35 Examples of the ring that can be formed together include the above-mentioned R 4 With R 5 , R 5 With R 6 and R 6 With R 7 and R 3 With R 7 and R 3 With R 8 Examples of the rings that can be formed together include the same rings.

[0269] 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, and R 11 The aryl group having 6 to 12 carbon atoms or the alkyl group having 1 to 8 carbon atoms is preferred because of its high solvent solubility. 2The substances which are methyl, ethyl or phenyl are preferred because of their high reactivity. 4 ~R 7 A hydrogen atom or a cyano group, particularly a hydrogen atom, is preferred because of easy synthesis. 8 The substance in which k is a hydrogen atom is preferred because it is easy to synthesize, and the substance in which k is 1 is preferred because of its high sensitivity. In the above general formula (B'), R 31 ~R 35 At least one of them is a nitro group, CN, a halogen atom, COR 11 , and R 11 The aryl group having 6 to 12 carbon atoms or the alkyl group having 1 to 8 carbon atoms is preferred because of its high sensitivity. 31 ~R 35 More preferably, at least one of the R 33 Those which are nitro group, CN, halogen atom, or COPh are particularly preferred.

[0270] Preferred specific examples of the compound represented by the general formula (B) include the following compounds: In addition, compounds No. 1 to No. 212 described in International Publication No. 2015 / 152153 may be mentioned.

[0271] [Chemistry 10]

[0272]

[0273] The compound represented by the general formula (B) can be synthesized, for example, by referring to International Publication No. 2015 / 152153 and appropriately selecting a solvent, reaction temperature, reaction time, purification method, etc. according to the materials used. Alternatively, commercially available products may be appropriately purchased and used.

[0274] Examples of the oxime photoinitiator having a carbazole skeleton include ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime) (e.g., Irgacure OXE02, manufactured by BASF), methyl ketone, [8-[[(acetyloxy)imino][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methyl]-11-(2-ethylhexyl)-11H-benzo[a]carbazole-5-yl]-, (2,4,6-trimethylphenyl) (e.g., Irgacure OXE-03, manufactured by BASF), acetone, 1-[9-ethyl-6-(1,3-dioxolane, 4-(2-methoxyphenoxy)-9H-carbazole-3-yl]-, 1-(o-acetyl oxime), ketone, (9-ethyl-6-nitro-9H-carbazole-3-yl)[4-(2-methoxy-1-methylethoxy-2-methylphenyl]-, o-acetyl oxime, 1-acetone, 3-cyclopentyl-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(o-acetyl oxime) (e.g. TR-PBG-304, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), 1-acetone, 3-cyclopentyl-1-[2- (2-pyrimidinylthio)-9H-carbazol-3-yl]-, 1-(o-acetyl oxime), ethyl ketone, 2-cyclohexyl-1-[2-(2-pyrimidinyloxy)-9H-carbazol-3-yl]-, 1-(o-acetyl oxime), ethyl ketone, 2-cyclohexyl-1-[2-(2-pyrimidinylthio)-9H-carbazol-3-yl]-, 1-(o-acetyl oxime), 1-octanone, 1-[4-[3-[1-[(acetoxy)imino]ethyl]-6-[4-[(4,6-dimethyl-2-pyrimidinyl)thio]-2-methylbenzoyl]-9H-carbazol-9-yl]phenyl]-, 1-(o-acetyl oxime) (e.g. EXTA-9, UNION Chemical), ADEKA OPT-N-1919 (manufactured by ADEKA Corporation), Adeka Arkles NCI-831 (manufactured by ADEKA Corporation), and the like are commercially available.

[0275] Among them, the oxime-based photoinitiator having a carbazole skeleton is preferably a compound represented by the following general formula (C).

[0276] [Chemistry 11]

[0277] General formula (C)

[0278]

[0279] (In formula (C), X 1 , X 3 and X 6 R 41 , OR41 , COR 41 , SR 41 ,CONR 42 R 43 or CN, X 2 represents 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, and X 4 and X 5 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, halogen atoms or hydroxyl groups;

[0280] R 41 , R 42 and R 43 each independently 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,

[0281] R 41 , R 42 and R 43 , and X 2 The hydrogen atoms of the groups represented by may be further replaced by R 51 , OR 51 , COR 51 , SR 51 NR 52 R 53 ,CONR 52 R 53 、-NR 52 -OR 53 、-NCOR 52 -OCOR 53 NR 52 COR 51 ,OCOR 51 、COOR 51 SCOR 51 , OCSR 51 、COSR 51 ,CSOR 51 , hydroxyl, nitro, CN, or halogen atoms,

[0282] R 51 , R 52 and R 53 each independently 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,

[0283] R 51 , R 52 and R 53 The hydrogen atoms of the groups represented may be further replaced by hydroxyl groups, nitro groups, CN, halogen atoms, or carboxyl groups.

[0284] R 41 , R 42 , R 43 , X 2 , R 51 , R 52 and R 53 The alkylene portion of the group represented may contain 1 to 5 -O-, -S-, -COO-, -OCO-, -NR- 54 -、-NR 54 CO-、-NR 54 COO-、-OCONR 54 -, -SCO-, -COS-, -OCS- or -CSO-,

[0285] 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,

[0286] R 41 , R 42 , R 43 , R 51 , R 52 , R 53 and R 54 The alkyl portion of the group represented may have a branched side chain or may be a cyclic alkyl group.

[0287] a and b are each independently an integer from 0 to 3.)

[0288] The oxime ester compound represented by the general formula (C) also has geometric isomers based on the double bond of the oxime, but they are not distinguished. That is, in this specification, the compound represented by the general formula (C) and its exemplary compounds represent a mixture or any one of the two, and are not limited to structures representing isomers.

[0289] As X in the above general formula (C) 2 , R 41 , R42 , R 43 , R 51 , R 52 , R 53 and R 54 The alkyl group having 1 to 20 carbon atoms represented by may be the same group as the alkyl group having 1 to 20 carbon atoms in the above general formula (B).

[0290] As X in the above general formula (C) 2 , R 41 , R 42 , R 43 , R 51 , R 52 , R 53 and R 54 The aryl group having 6 to 30 carbon atoms represented by may be the same group as the aryl group having 6 to 30 carbon atoms in the above general formula (B).

[0291] As X in the above general formula (C) 2 , R 41 , R 42 , R 43 , R 51 , R 52 , R 53 and R 54 Examples of the arylalkyl group having 7 to 30 carbon atoms represented by include the same groups as the arylalkyl group having 7 to 30 carbon atoms in the above general formula (B).

[0292] As X in the above general formula (C) 2 , R 41 , R 42 , R 43 , R 51 , R 52 , R 53 and R 54 The heterocyclic group having 2 to 20 carbon atoms represented by may be the same group as the heterocyclic group having 2 to 20 carbon atoms in the above general formula (B).

[0293] In addition, examples of the halogen atom in the general formula (C) include the same atoms as the halogen atom in the general formula (B).

[0294] In the above general formula (C), R 41 , R 42 , R 43 , X 2 , R 51 , R 52 and R 53 The alkylene portion of the group represented may contain 1 to 5 -O-, -S-, -COO-, -OCO-, -NR- 54-、-NR 54 CO-、-NR 54 COO-、-OCONR 54 -, -SCO-, -COS-, -OCS- or -CSO-, and the divalent group contained in this case may be one or more groups, and when it is a group that can be contained continuously, two or more groups may be contained continuously.

[0295] In terms of sensitivity, solubility, and compatibility, X in the above general formula (C) 1 More preferred are alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, and 2-ethylhexyl; cyclic alkyl groups having 5 to 10 carbon atoms, such as cyclopentyl and cyclohexyl, which may have a side chain; or alkyl groups having 2 to 10 carbon atoms and having one ether bond in the methylene chain, such as methoxymethyl, ethoxymethyl, ethoxyethyl, 2-(1-methoxypropyl), and 2-(1-ethoxypropyl); and even more preferred are alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, and 2-ethylhexyl.

[0296] In terms of sensitivity, solubility, and compatibility, X in the above general formula (C) 2 , X 3 and X 6 Particularly preferred are independently an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl and n-hexyl, a cyclic alkyl group having 5 to 6 carbon atoms, such as cyclopentyl and cyclohexyl, or an alkyl group having 2 to 6 carbon atoms and having one ether bond in the methylene chain, such as methoxymethyl, ethoxymethyl, ethoxyethyl, 2-(1-methoxypropyl) and 2-(1-ethoxypropyl), and further preferably an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 2 to 6 carbon atoms and having one ether bond in the methylene chain.

[0297] In terms of sensitivity, solubility and compatibility, X 3 , and X 6 Each of them independently is more preferably an alkyl group having 1 to 6 carbon atoms.

[0298] In terms of sensitivity, solubility and compatibility, X 2 More preferably, it is an alkyl group having 2 to 6 carbon atoms and having one ether bond in the methylene chain.

[0299] In terms of sensitivity, solubility, and compatibility, X in the above general formula (C) 4 , and X 5 Particularly preferably, each independently represents hydrogen or an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl and n-hexyl.

[0300] Preferred specific examples of the compound represented by the general formula (C) include the following compounds.

[0301] [Chemistry 12]

[0302]

[0303] [Chemistry 13]

[0304]

[0305] The compound represented by the general formula (C) can be synthesized, for example, by referring to JP-A-2010-256891 and appropriately selecting a solvent, reaction temperature, reaction time, purification method, etc. according to the materials used. Alternatively, commercially available products may be appropriately purchased and used.

[0306] In the blue photosensitive composition used in the present invention, the oxime-based photoinitiator may be used alone or in combination of two or more.

[0307] (Sensitizer with sensitizing effect at 400 nm to 420 nm)

[0308] Since an LED lamp having a peak emission wavelength at 400 nm to 420 nm is used, the blue photosensitive composition used in the present invention contains, in addition to the above-mentioned oxime photoinitiator, a sensitizer having a sensitizing effect at 400 nm to 420 nm different from the above-mentioned oxime photoinitiator.

[0309] As a sensitizer having a sensitizing effect at 400 nm to 420 nm, which is different from the above-mentioned oxime-based photoinitiator, any sensitizer having an absorption at 400 nm to 420 nm can be used without particular limitation. As to whether the sensitizer used in the present invention has a sensitizing effect at 400 nm to 420 nm, the absorption spectrum of a solution obtained by dissolving the sensitizer at a concentration of 0.01 mg / ml in a solvent such as acetonitrile can be measured using an ultraviolet-visible spectrophotometer, with absorption at 400 nm to 420 nm being used as a standard. The sensitizer used in the present invention preferably has an absorbance of 0.1 or more when the absorption spectrum of a solution obtained by dissolving the sensitizer at a concentration of 0.01 mg / ml in a solvent such as acetonitrile is measured using an ultraviolet-visible spectrophotometer.

[0310] As the sensitizer having a sensitizing effect at 400 nm to 420 nm used in the present invention, for example, at least one selected from the group consisting of thioxanthone sensitizers, aromatic ketone sensitizers, anthracene sensitizers, and naphthalene sensitizers can be appropriately selected and used.

[0311] Examples of the thioxanthone-based sensitizer include 2,4-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone and 2,4-dichlorothioxanthone.

[0312] As the aromatic ketone-based sensitizer, a benzophenone-based sensitizer may be mentioned, for example, benzophenone, 4,4′-bisdiethylaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, etc. may be mentioned.

[0313] Examples of the anthracene sensitizer include anthracene compounds substituted with an alkoxy group or an acyloxy group, such as 9,10-bis(acetoxy)anthracene, 9,10-bis(propionyloxy)anthracene, 9,10-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-ethylhexanoyloxy)anthracene, 9,10-bis(n-nonanoyloxy)anthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-dibutoxyanthracene.

[0314] As the naphthalene-based sensitizer, a naphthalene compound substituted with an alkoxy group or an acyloxy group may be mentioned, for example, 1,4-diethoxynaphthalene may be mentioned.

[0315] The sensitizer having a sensitizing effect at 400 nm to 420 nm used in the blue photosensitive composition of the present invention may be used alone or in combination of two or more.

[0316] (Other photoinitiators)

[0317] As long as the effects of the present invention are not impaired, the blue photosensitive composition used in the present invention may also contain other photoinitiators different from the above-mentioned oxime-based photoinitiator and the above-mentioned sensitizer having a sensitizing effect at 400 nm to 420 nm. As other photoinitiators, they can be appropriately selected from benzoin ethers, halomethyl oxadiazole compounds, α-aminoketones, biimidazoles, halomethyl-S-triazine compounds, acylphosphine oxides, etc.

[0318] Even when other photoinitiators are included, the total content of the oxime photoinitiator may be 50% by mass or more, or 70% by mass or more, relative to the total content of the oxime photoinitiator and the other photoinitiators.

[0319] The total content of the oxime photoinitiator in the total amount of the photoinitiator may be 15% by mass or more, 25% by mass or more, and 90% by mass or less, 80% by mass or less in terms of improving curability.

[0320] When the above-mentioned other photoinitiators are included, the total content of the above-mentioned oxime-based photoinitiator and other photoinitiators can be 15% by mass or more, 25% by mass or more, and the upper limit can be 90% by mass or less, 80% by mass or less in terms of improving curability.

[0321] In the total amount of the photoinitiator, the total content of the sensitizer having a sensitizing effect at 400 nm to 420 nm, which is different from the oxime-based photoinitiator, can be 10% by mass or more, 20% by mass or more, and 85% by mass or less, 75% by mass or less in terms of improving curability.

[0322] In addition, regarding the content ratio of the total of the above-mentioned oxime photoinitiator and other photoinitiators to the above-mentioned sensitizer having a sensitizing effect at 400 nm to 420 nm used in the blue photosensitive composition, from the aspects of sensitivity and the balance with line width shift, the total content of the above-mentioned sensitizer having a sensitizing effect at 400 nm to 420 nm is preferably 20 parts by mass or more, more preferably 50 parts by mass or more, and preferably 500 parts by mass or less, and more preferably 300 parts by mass or less, relative to 100 parts by mass of the total content of the above-mentioned oxime photoinitiator and other photoinitiators.

[0323] In the blue photosensitive composition used in the present invention, the total content of the sensitizer 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, and is preferably in the range of 0.1% to 5% by mass, more preferably in the range of 0.2% to 3% by mass, relative to the total solid content of the blue photosensitive composition. If the content is above the lower limit, photocuring is sufficiently promoted, dissolution of the exposed part during development is suppressed, and solvent resistance becomes good. On the other hand, if it is below the upper limit, the brightness reduction and deterioration of developability caused by yellowing of the obtained color layer can be suppressed.

[0324] In the blue photosensitive composition used in the present invention, the total content of the photoinitiator is not particularly limited as long as the effect of the present invention is not impaired, and is preferably in the range of 0.5% to 12.0% by mass, and more preferably in the range of 1.0% to 8.0% by mass, relative to the total solid content of the blue photosensitive composition. If the content is above the lower limit, photocuring is sufficiently promoted, dissolution of the exposed part during development is suppressed, and solvent resistance becomes good. On the other hand, if it is below the upper limit, the brightness reduction and deterioration of developability caused by yellowing of the obtained color layer can be suppressed.

[0325] In addition, in terms of suppressing line width deviation and improving pattern shape, the content ratio of the above-mentioned photopolymerizable compound and the above-mentioned photoinitiator used in the blue photosensitive composition 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, relative to 100 parts by mass of the above-mentioned photopolymerizable compound.

[0326] In addition, regarding the content ratio of the above-mentioned photopolymerizable compound and the above-mentioned sensitizer having a sensitizing effect at 400 nm to 420 nm used in the blue photosensitive composition, in terms of suppressing line width deviation and making the pattern shape good, the total content ratio of the above-mentioned sensitizer having a sensitizing effect at 400 nm to 420 nm is preferably 1 mass part or more, more preferably 5 mass parts or more, preferably 30 mass parts or less, and more preferably 20 mass parts or less, relative to 100 mass parts of the above-mentioned photopolymerizable compound.

[0327] <Solvent>

[0328] The blue photosensitive composition used in the present invention may also 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 photosensitive composition and can dissolve or disperse them. The solvent may be used alone or in combination of two or more.

[0329] Specific examples of the solvent include: alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, methoxy alcohol, and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ester solvents such as 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, ethyl lactate, and cyclohexanol acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; glycol ether acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, and ethoxyethyl acetate; Carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butyl carbitol acetate (BCA); diacetates such as propylene glycol diacetate and 1,3-butylene glycol diacetate; glycol ether solvents such as 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 dimethyl ether; aprotic amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; cyclic ether solvents such as tetrahydrofuran; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, naphthalene; saturated hydrocarbon solvents such as n-heptane, n-hexane, n-octane; aromatic hydrocarbons such as toluene and xylene, and other organic solvents. Among these solvents, glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents are preferably used in terms of solubility of other components. Among them, as the solvent used in the present invention, in terms of solubility of other components and coating suitability, it is preferred to use at least one selected from the group consisting of 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.

[0330] In the blue photosensitive composition used in the present invention, the content of the solvent can be appropriately set within the range that can form a blue cured film or a colored layer with high precision. The content of the solvent is generally preferably within the range of 55% to 95% by mass, and more preferably within the range of 65% to 88% by mass, relative to the total amount of the blue photosensitive composition containing the solvent. By making the content of the above-mentioned solvent within the above-mentioned range, it is possible to make the coating property excellent.

[0331] <Dispersant>

[0332] When a color material is dispersed in the blue photosensitive composition of the present invention, a dispersant may be further contained from the viewpoint of the dispersibility of the color material and the dispersion stability of the color material.

[0333] In the present invention, the dispersant can be appropriately selected from existing known dispersants. As the dispersant, for example, a cationic, anionic, nonionic, amphoteric, silicone, fluorine-based surfactant can be used. Among the surfactants, a polymer dispersant is preferably used in terms of being able to be evenly and finely dispersed.

[0334] Examples of the polymer dispersant include: (meth)acrylate copolymer dispersants; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; polyethyleneimine derivatives (amides obtained by reacting poly(lower alkylene imine) with a polyester containing a free carboxyl group, and their bases); polyallylamine derivatives (reaction products obtained by reacting polyallylamine with one or more compounds selected from three compounds selected from polyesters having free carboxyl groups, polyamides, or co-condensates of esters and amides (polyester amides)).

[0335] In the present invention, from the perspective of controlling the developability, it is preferred to use a (meth)acrylate copolymer dispersant as the dispersant. Since the (meth)acrylate copolymer dispersant has good compatibility with the alkali-soluble resin and the photopolymerizable compound, it is estimated that the generation of development residues can be suppressed.

[0336] In the present invention, the (meth)acrylate copolymer-based dispersant refers to a dispersant which is a copolymer and contains at least a structural unit derived from a (meth)acrylate.

[0337] The (meth)acrylate copolymer dispersant is preferably a copolymer containing a structural unit functioning as a color material adsorption site and a structural unit functioning as a solvent affinity site, and the structural unit functioning as a solvent affinity site preferably contains at least a structural unit derived from (meth)acrylate.

[0338] The structural unit that functions as the color material adsorption site may be a structural unit derived from an ethylenically unsaturated monomer that can be copolymerized with the structural unit derived from the (meth)acrylate. The color material 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.

[0339] As the structural unit derived from the ethylenically unsaturated monomer containing a basic group, a structural unit represented by the following general formula (I) is preferred in terms of excellent dispersibility of the color material.

[0340] [Chemistry 14]

[0341]

[0342] (In the general formula (I), R 61A represents a hydrogen atom or a methyl group. 1 represents a divalent linking group, R 62 and R 63 Each independently represents a hydrogen atom or a hydrocarbon group which may contain a hetero atom, R 62 and R 63 Can bond to each other to form a ring structure. )

[0343] In the general formula (I), A 1 It is a divalent linking group. As a divalent linking group, for example, a straight chain, branched or cyclic alkylene, a straight chain, branched or cyclic alkylene with a hydroxyl group, an arylene group, -CONH- group, -COO- group, -NHCOO- group, an ether group (-O- group), a thioether group (-S- group), and a combination thereof can be cited. It should be noted that in the present invention, the bonding direction of the divalent linking group is arbitrary. That is, when the divalent linking group includes -CONH-, it can be -CO on the carbon atom side of the main chain and -NH on the nitrogen atom side of the side chain, and vice versa, it can also be -NH on the carbon atom side of the main chain and -CO on the nitrogen atom side of the side chain.

[0344] In terms of dispersibility, A in the general formula (I) 1 Preferably, it is a divalent linking group containing a -CONH- group or a -COO- group, and more preferably, it is a divalent linking group containing a -CONH- group or a -COO- group and an alkylene group having 1 to 10 carbon atoms.

[0345] R 62 and R 63 The hydrocarbon group in the hydrocarbon group which may contain a hetero atom may, for example, be an alkyl group, an aralkyl group, an aryl group, or the like.

[0346] Examples of the alkyl group include methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2-ethylhexyl, cyclopentyl and cyclohexyl. The alkyl group preferably has 1 to 18 carbon atoms, and more preferably is methyl or ethyl.

[0347] Examples of the aralkyl group include benzyl, phenethyl, naphthylmethyl, biphenylmethyl, etc. The aralkyl group preferably has 7 to 20 carbon atoms, more preferably 7 to 14 carbon atoms.

[0348] Examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl, etc. The aryl group preferably has 6 to 24 carbon atoms, more preferably 6 to 12 carbon atoms. The preferred carbon atoms do not include the carbon atoms of the substituent.

[0349] The so-called hydrocarbon group containing heteroatoms refers to a structure in which a carbon atom in the above hydrocarbon group is substituted by a heteroatom, or a structure in which a hydrogen atom in the above hydrocarbon group is substituted by a substituent containing a heteroatom. Examples of heteroatoms that the hydrocarbon group may contain include oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, and the like.

[0350] Furthermore, the hydrogen atoms in the hydrocarbon group may be substituted with halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms.

[0351] What is R 62 and R 63 Bonded to each other to form a ring structure, refers to R 62 and R 63 A ring structure is formed via the nitrogen atom. 62 and R 63 The formed ring structure may contain a hetero atom. The ring structure is not particularly limited, and examples thereof include a pyrrolidine ring, a piperidine ring, and a morpholine ring.

[0352] In the present invention, R is particularly preferred 62 and R 63 are independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R 62 and R 63 Bonding to form a pyrrolidine ring, piperidine ring, and morpholine ring.

[0353] Examples of monomers from which the structural unit represented by the general formula (I) can be derived include (meth)acrylates containing an alkyl-substituted amino group such as dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and diethylaminopropyl (meth)acrylate; and (meth)acrylamides containing an alkyl-substituted amino group such as dimethylaminoethyl (meth)acrylamide and dimethylaminopropyl (meth)acrylamide. Among them, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dimethylaminopropyl (meth)acrylamide are preferably used in terms of improving dispersibility and dispersion stability.

[0354] In the polymer, the structural unit represented by the general formula (I) may be composed of only one type, or may contain two or more types of structural units.

[0355] In addition, regarding the structural unit functioning as a color material adsorption site, at least a part of the nitrogen sites of the structural unit represented by the general formula (I) may form a salt with at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons.

[0356] As the organic acid compound, acidic organic phosphorus compounds such as phenylphosphonic acid and phenylphosphinic acid are preferred in terms of excellent dispersibility and dispersion stability of the color material. Specific examples of organic acid compounds used as such dispersants include organic acid compounds described in Japanese Patent Application Laid-Open No. 2012-236882.

[0357] In addition, the halogenated hydrocarbon is preferably at least one of allyl halides such as allyl bromide and benzyl chloride, and aralkyl halides, in terms of excellent dispersibility and dispersion stability of the color material.

[0358] The copolymer having the structural unit represented by the general formula (I) is more preferably at least one of a graft copolymer having the structural unit represented by the general formula (I) and having a structural unit derived from (meth)acrylate in the graft polymer chain, and a block copolymer having an A block containing the structural unit represented by the general formula (I) and a B block containing a structural unit derived from (meth)acrylate in terms of dispersibility and dispersion stability.

[0359] In the above-mentioned graft copolymer, as the graft polymer chain having a structural unit derived from a (meth)acrylate, a conventionally known structure can be appropriately selected and used. For example, at least one of the graft copolymers and salt-type graft copolymers described in International Publication No. 2021 / 006077 can also be used.

[0360] In the block copolymer, a conventionally known structure may be appropriately selected as the B block containing a structural unit derived from a (meth)acrylate, and for example, at least one of the block copolymers described in International Publication No. 2016 / 104493 and a salt-type block copolymer may be used.

[0361] As the (meth)acrylate copolymer-based dispersant, a commercially available product may be used, and examples thereof include LP-N6919 and LP-N21116, both of which are trade names and manufactured by BYK-Chemie Japan Co., Ltd.

[0362] In the blue photosensitive composition of the present invention, the content of the dispersant can be selected in a manner that the dispersibility and dispersion stability of the color material are excellent, and there is no particular limitation. Relative to the total solid content in the blue photosensitive composition, for example, preferably 2% by mass to 30% by mass, more preferably in the range of 3% by mass to 25% by mass. If it is above the above lower limit, the dispersibility and dispersion stability of the color material are excellent, and the storage stability of the blue photosensitive composition is more excellent. In addition, if it is below the above upper limit, the developability becomes good. Especially in the case of forming a cured film with a higher concentration of the color material, the content of the dispersant is relative to the total solid content of the blue photosensitive composition, for example, preferably 2% by mass to 25% by mass, more preferably in the range of 3% by mass to 20% by mass.

[0363] <Thiol compounds>

[0364] The blue photosensitive composition of the present invention preferably further contains a thiol compound from the viewpoint of improving solvent resistance after low-temperature heat treatment and substrate adhesion.

[0365] 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. In terms of suppressing line width deviation and improving substrate adhesion, it is more preferable to use a monofunctional thiol compound having one thiol group.

[0366] Examples of the monofunctional thiol compound include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, and octyl 3-mercaptopropionate.

[0367] Examples of the polyfunctional thiol compound include 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), and tetraethylene glycol bis(3-mercaptopropionate).

[0368] The thiol compound may be used alone or in combination of two or more. Among them, 2-mercaptobenzoxazole or 2-mercaptobenzothiazole is preferred from the viewpoint of improving solvent resistance after low-temperature heat treatment and substrate adhesion.

[0369] As the content of the thiol compound, relative to the total solid content of the blue photosensitive composition, it is usually 0.5% by mass to 10% by mass, preferably in the range of 1% by mass to 5% by mass. If it is above the above lower limit, the substrate adhesion is excellent. On the other hand, if it is below the above upper limit, it is easy to make the blue photosensitive composition of the present invention a composition with good developability and suppressed line width deviation.

[0370] <Optional Additives>

[0371] The blue photosensitive composition may contain various additives as required, such as antioxidants, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, defoamers, silane coupling agents, ultraviolet absorbers, adhesion promoters, and the like.

[0372] Specific examples of the surfactant and the plasticizer include those described in Japanese Patent Application Laid-Open No. 2013-029832.

[0373] In terms of suppressing the line width deviation, it is preferred that the blue photosensitive composition of the present invention further comprises an antioxidant. The blue photosensitive composition of the present invention comprises the above-mentioned specific photoinitiator and antioxidant in combination, and can control excessive free radical chain reaction when forming a cured film without damaging the curability, so when forming a fine line pattern, the linearity is further improved, or the ability to form a fine line pattern as designed by the mask line width is improved.

[0374] As the antioxidant used in the present invention, there is no particular limitation, as long as it is appropriately selected from the existing known ones. As a specific example of an antioxidant, for example, hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, hydrazine antioxidants, etc. can be cited. In terms of the ability to form a fine line pattern as designed by the mask line width and heat resistance, hindered phenol antioxidants are preferably used. It can also be a latent antioxidant as described in International Publication No. 2014 / 021023.

[0375] Examples of the hindered phenol antioxidant include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, 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 (trade name: Irganox 1330, manufactured by BASF), 2,2'-methylenebis(6-tert-butyl-4-methylphenol) (trade 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: IRGANOX 1010, manufactured by BASF) is preferred in terms of heat resistance and light resistance.

[0376] The content of the antioxidant is preferably 0.1% to 10.0% by mass, more preferably 0.5% to 5.0% by mass, relative to the total solid content of the blue photosensitive composition. If it is above the above lower limit, the ability to form a fine line pattern as designed by the 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.

[0377] In addition, examples of silane coupling agents 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 having a methacryloyl group or an acryloyl group are preferred in terms of adhesion to SiN substrates.

[0378] The content of the silane coupling agent is preferably in the range of 0.05 to 10.0 mass %, more preferably in the range of 0.1 to 5.0 mass %, relative to the total solid content of the blue photosensitive composition. When it is at least the lower limit and at most the upper limit, the substrate adhesion is excellent.

[0379] <Method for producing blue photosensitive composition>

[0380] The method for producing the blue photosensitive composition used in the present invention preferably contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a sensitizer, a dispersant as required, a solvent, and various additives used as required, and the colorant can be uniformly dispersed in the solvent. It can be prepared by mixing using a known mixing mechanism.

[0381] The preparation method of the blue photosensitive composition may be, for example: (1) first, a colorant and a dispersant are added to a solvent to prepare a colorant dispersion, and an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a sensitizer, and various additives used as required are mixed into the dispersion; (2) a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a sensitizer, and a dispersant used as required, and various additives are added to a solvent at the same time and mixed; (3) an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a sensitizer, a dispersant used as required, and various additives are added to a solvent, mixed, and then the colorant is added and dispersed; (4) a colorant, a dispersant, and an alkali-soluble resin are added to a solvent to prepare a colorant dispersion, and then an alkali-soluble resin, a solvent, a photopolymerizable compound, a photoinitiator, a sensitizer, and various additives used as required are added to the dispersion and mixed. When the photopolymerizable compound is used as a substitute for the solvent, the solvent may not be used.

[0382] Among these methods, the methods (1) and (4) are preferred because they can effectively prevent the color material from agglomerating and uniformly disperse the color material.

[0383] The method for preparing the color material dispersion liquid can be appropriately selected from the existing known dispersion methods. For example, the following can be mentioned: (1) a method in which a dispersant is mixed in advance with a solvent and stirred to prepare a dispersant solution, then an organic acid compound is mixed as needed to form a salt of an amino group of the dispersant and the organic acid compound, the salt is mixed with the color material and other components as needed, and the salt is dispersed using a known stirrer or disperser; (2) a method in which a dispersant is mixed in a solvent and stirred to prepare a dispersant solution, then a color material and an organic acid compound as needed, and other components as needed are mixed, and the salt is dispersed using a known stirrer or disperser; (3) a method in which a dispersant is mixed in a solvent and stirred to prepare a dispersant solution, then a color material and other components as needed are mixed, a dispersion liquid is prepared using a known stirrer or disperser, and then an organic acid compound is added as needed.

[0384] Examples of the dispersing machine used for the dispersion treatment include roller mills such as two-roll mills and three-roll mills, ball mills such as ball mills and vibration ball mills, paint conditioners, continuous disc type bead mills, continuous ring bead mills, etc. As a preferred dispersion condition 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.

[0385] <Application>

[0386] The blue photosensitive composition of the present invention can suppress line width deviation and improve the residual film rate after development, can form a good pattern with suppressed undercut after development, and the substrate adhesion of the formed blue cured film pattern is also improved, so it can be suitably used for color filter applications.

[0387] III. Color filter and its manufacturing method

[0388] The method for producing a color filter of the present invention is characterized in that the color filter comprises at least a substrate and a coloring layer including a blue cured film provided on the substrate, and the method for producing the color filter comprises the following steps:

[0389] This blue cured film is produced by the method for producing a blue cured film of the present invention.

[0390] The color filter of the present invention comprises 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 of the present invention.

[0391] Such a color filter of the present invention will be described with reference to the drawings. Figure 1 1 is a schematic cross-sectional view showing an example of the color filter of the present invention. Figure 1 The color filter 10 of the present invention includes a substrate 1 , a light shielding portion 2 , and a coloring layer 3 .

[0392] <Substrate>

[0393] The substrate may be the same as the substrate exemplified in the above-mentioned method for producing a blue cured film, and thus the description thereof will be omitted here.

[0394] The thickness of the transparent substrate is not particularly limited, and a substrate having a thickness of, for example, about 100 μm to 1 mm can be used depending on the application of the color filter of the present invention.

[0395] <Light shielding part>

[0396] The light shielding portion in the color filter of the present invention is a member formed in a pattern on a substrate, and may be the same as a member used as a light shielding portion in a general color filter.

[0397] The pattern shape of the light-shielding portion is not particularly limited, and for example, stripe shape, matrix shape, etc. can be cited. The light-shielding portion can also be a metal film such as chromium formed by sputtering, vacuum evaporation, etc. Alternatively, the light-shielding portion can also be a resin layer containing light-shielding particles such as carbon 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: a method of patterning it by developing using a photosensitive resist, a method of patterning it using an inkjet ink containing light-shielding particles, a method of thermally transferring a photosensitive resist, etc.

[0398] The film thickness of the light shielding portion is set to about 0.2 μm to 0.4 μm in the case of a metal thin film, and is set to about 0.5 μm to 2 μm in the case of a member obtained by dispersing or dissolving a black pigment in a binder resin.

[0399] <Coloring layer>

[0400] The colored layer used in the color filter of the present invention is at least one colored layer which is a cured product of the blue photosensitive composition of the present invention.

[0401] The colored layer is usually formed in the opening of the light shielding portion on the substrate, and usually includes colored patterns of three or more colors.

[0402] The arrangement of the coloring layer is not particularly limited, and may be, for example, a stripe type, a mosaic type, a triangle type, a 4-pixel arrangement type, etc. In addition, the width and area of ​​the coloring layer may be arbitrarily set.

[0403] The thickness of the colored layer can be appropriately controlled by adjusting the coating method, the solid content concentration of the blue photosensitive composition, the viscosity, etc., and is usually preferably in the range of 1 μm to 5 μm.

[0404] Among the colored layers, at least the blue colored layer, that is, the blue cured film has a process of being produced by the above-mentioned method for producing a blue cured film of the present invention.

[0405] Colored layers other than the blue colored layer can also be produced by a conventionally known production method, and can include the steps of forming a coating film on a substrate, and exposing the coating film to light using an LED lamp having a peak emission wavelength at 360 nm to 380 nm and 400 nm to 420 nm to cure the coating film, similarly to the production method of the blue cured film of the present invention. The blue cured film of the present invention can be produced in the same manner as the blue cured film of the present invention.

[0406] It should be noted that the color filter of the present invention may include, in addition to the substrate, light shielding portion, and coloring layer, an overcoat layer, a transparent electrode layer, and further an alignment film, a columnar spacer, and the like.

[0407] IV. Display device

[0408] The display device of the present invention is characterized by having the color filter of 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 liquid crystal display devices and organic light emitting display devices.

[0409] [Liquid crystal display device]

[0410] Examples of the liquid crystal display device of the present invention include a liquid crystal display device including the color filter of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.

[0411] Such a liquid crystal display device of the present invention will be described with reference to the drawings. Figure 2 1 is a schematic diagram showing an example of a liquid crystal display device of the present invention. Figure 2 As shown, the liquid crystal display device 40 of the present invention includes a color filter 10 , a counter substrate 20 including a TFT array substrate, and a liquid crystal layer 30 formed between the color filter 10 and the counter substrate 20 .

[0412] It should be noted that the liquid crystal display device of the present invention is not limited to the Figure 2 The structure shown can adopt a known structure generally used as a liquid crystal display device using a color filter.

[0413] The driving method of the liquid crystal display device of the present invention is not particularly limited, and generally the driving method used in the liquid crystal display device can be adopted. As such driving method, for example, TN method, IPS method, OCB method, and MVA method can be cited. In the present invention, any of these methods can be appropriately used.

[0414] In addition, the counter substrate can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention.

[0415] Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropies and mixtures thereof can be used depending on the driving method of the liquid crystal display device of the present invention.

[0416] As a method for forming a liquid crystal layer, a method generally used as a method for preparing a liquid crystal cell can be used, for example, a vacuum injection method, a liquid crystal dropping method, etc. After forming a liquid crystal layer by the above method, the sealed liquid crystal can be oriented by gradually cooling the liquid crystal cell to room temperature.

[0417] [Organic light emitting display device]

[0418] As an example of the organic light emitting display device of the present invention, there can be mentioned an organic light emitting display device including the color filter of the present invention and an organic light emitting body.

[0419] The organic light emitting display device of the present invention will be described with reference to the drawings. Figure 3 FIG. 1 is a schematic diagram showing an example of an organic light emitting display device of the present invention. Figure 3 As shown, the organic light emitting display device 100 of the present invention includes a color filter 10 and an organic light emitting body 80. An organic protective layer 50 and an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitting body 80.

[0420] As a stacking method of the organic light emitting body 80, for example, there can be cited: a method of sequentially forming 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 on the upper surface of a color filter; a method of laminating an organic light emitting body 80 formed on another substrate on an inorganic oxide film 60, etc. The transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, and the cathode 76 in the organic light emitting body 80, and other components can appropriately use known components. The organic light emitting display device 100 manufactured in this way can be used, for example, for both a passively driven organic EL display and an actively driven organic EL display.

[0421] It should be noted that the organic light emitting display device of the present invention is not limited to the Figure 3 The structure shown can adopt a known structure generally used as an organic light emitting display device using a color filter.

[0422] Example

[0423] Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these descriptions.

[0424] [Preparation of LED light source]

[0425] As LED light sources having emission peak wavelengths at 360 nm to 380 nm and 400 nm to 420 nm, LED chips having emission peak wavelengths at 365 nm and LED chips having emission peak wavelengths at 405 nm are used, and the intensity ratio (A / B) of the intensity of the emission peak wavelengths at 360 nm to 380 nm (A) and the intensity of the emission peak wavelengths at 400 nm to 420 nm (B) is adjusted according to the ratio of the number of each LED chip. The LED chips are arranged so that the curing property does not vary depending on the light irradiation position.

[0426] Prepare 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.

[0427] In addition, the intensity ratio (A / B) was confirmed by a spectral irradiance meter (USR-45DA-14 (manufactured by Ushio Electric Co., Ltd.)).

[0428] (Synthesis Example 1: Preparation of Alkali-Soluble Resin A)

[0429] 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 dropwise to a polymerization tank containing 150 parts by mass of PGMEA at 100°C for 3 hours under a nitrogen flow. After the 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 the polymer solution was 7000.

[0430] 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 heated at 110°C for 10 hours to react the carboxylic acid group of the main chain methacrylic acid with the epoxy group of glycidyl methacrylate to obtain an alkali-soluble resin A. During the reaction, air was passed into the reaction solution to prevent polymerization of glycidyl methacrylate. It should be noted that the reaction was tracked by measuring the acid value of the solution. The obtained alkali-soluble resin A is a resin obtained by introducing a side chain having an ethylenically unsaturated bond into the main chain formed by copolymerization of BzMA, MMA, and MAA using GMA, and has a solid content of 40% by mass, an acid value of 74 mgKOH / g, and a mass average molecular weight of 12,000.

[0431] It should be noted that, regarding the above-mentioned mass average molecular weight, polystyrene was used as a standard substance and THF was used as an eluent, and the mass average molecular weight was measured by Shodex GPC System-21H. The acid value was measured based on JIS K 0070. In addition, regarding the glass transition temperature (Tg), it was measured using differential scanning calorimetry (manufactured by SII Nanotechnologies, EXSTAR DSC 7020) according to the method described in JIS K7121.

[0432] (Synthesis Example 2: Preparation of Block Copolymer A (Dispersant A))

[0433] In a 500 mL round-bottom four-necked separable flask equipped with a condenser, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 250 parts by mass of THF and 0.6 parts by mass of lithium chloride were added, and nitrogen replacement was performed thoroughly. After the reaction flask was cooled to -60°C, 4.9 parts by mass of butyl lithium (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. Using an addition funnel, 2.2 parts by mass of 1-ethoxyethyl methacrylate (EEMA), 18.7 parts by mass of 2-hydroxyethyl methacrylate (HEMA), 12.8 parts by mass of 2-ethylhexyl methacrylate (EHMA), 13.7 parts by mass of n-butyl methacrylate (BMA), 9.5 parts by mass of benzyl methacrylate (BzMA), and 17.5 parts by mass of methyl methacrylate (MMA) as monomers for B block were added dropwise over 60 minutes. After 30 minutes, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA) as a monomer for block A was added dropwise over a period of 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to terminate the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, purified by filtration and vacuum drying, and diluted with PGMEA to prepare a 30% by mass solution of solid content. 32.5 parts by mass of water was added, the temperature was raised to 100°C, and the reaction was carried out for 7 hours to deprotect the structural unit derived from EEMA to obtain a structural unit derived from methacrylic acid (MAA). The obtained block copolymer PGMEA solution was reprecipitated in hexane, purified by filtration and vacuum drying to obtain a block copolymer A (acid value 8 mgKOH / g, Tg38°C) containing a structural unit represented by the general formula (I) and a solvophilic B block containing a structural unit derived from a carboxyl-containing monomer. The block copolymer A thus obtained was confirmed by GPC (gel permeation chromatography), and the mass average molecular weight Mw was 7730. The amine value was 95 mgKOH / g.

[0434] (Synthesis Example 3: Synthesis of Lake Color Material 1)

[0435] (1) Synthesis of intermediate 1

[0436] Referring to the production methods of intermediate A-2, intermediate B-1, and compound 1-3 described in JP-A-2018-3013, intermediate 1 represented by the following chemical formula (a) was obtained (yield 87%).

[0437] From the following analysis results, it was confirmed that the obtained compound was the target compound.

[0438] ·MS (ESI) (m / z): 677 (+), divalent

[0439] Element analysis values: CHN measured values ​​(81.81%, 7.31%, 5.85%); theoretical values ​​(81.77%, 7.36%, 5.90%)

[0440] [Chemistry 15]

[0441] Chemical formula (a)

[0442]

[0443] (2) Synthesis of Lake Color Material 1

[0444] 2.59 g (0.76 mmol) of 1,2-phosphotungstic acid n-hydrate manufactured by Kanto Chemical was dissolved in a mixture of 40 mL of methanol and 40 mL of water by heating, and 1.6 g (1.19 mmol) of the intermediate 1 was added and stirred for 1 hour. The precipitate was filtered out and washed with water. The obtained precipitate was dried under reduced pressure to obtain a lake color material 1 represented by the following chemical formula (b) (yield 95%).

[0445] From the following analysis results, it was confirmed that the obtained compound was the target compound.

[0446] ·31P NMR (d-dmso, ppm) δ-15.15

[0447] ·MS (MALDI) (m / z): 1355 (M + )、2879(MH 2 - )

[0448] Element analysis value: CHN measured value (35.55%, 3.24%, 2.61%); theoretical value (35.61%, 3.20%, 2.57%)

[0449] Fluorescence X-ray analysis: MoW measured ratio (0%, 100%); theoretical value (0%, 100%)

[0450] [Chemistry 16]

[0451] Chemical formula (b)

[0452]

[0453] (Synthesis Example 4: Synthesis of Oxime Photoinitiator Compound A-1)

[0454] (1) Synthesis of intermediate A1

[0455] In a 500 ml four-necked flask, 0.2 mol of diphenyl sulfide and 0.22 mol of crushed AlCl 3 The mixture was stirred with 150 ml of dichloroethane, and argon was introduced. When the temperature was lowered to 0°C by ice-cooling, a solution containing 0.22 mol of cyclohexylpropionyl chloride and 42 g of dichloroethane was added dropwise over about 1.5 hours while adjusting the temperature to below 10°C. The temperature was raised to 15°C, and stirring was continued for 2 hours, and the reaction solution was discharged.

[0456] The reaction solution was slowly added to dilute hydrochloric acid prepared by mixing 400 g of ice and 65 ml of concentrated hydrochloric acid under stirring, and the lower layer was separated using a separatory funnel. The upper layer was extracted with 50 ml of dichloroethane, and the extract and the lower layer were combined. 3 and water 200 g NaHCO 3 The solution was washed with 200 ml of water three times until the pH value was neutral, and 60 g of anhydrous MgSO 4 After drying to remove water, dichloroethane was evaporated by rotary evaporation. The solid powder remaining in the rotary evaporation bottle was added to 200 ml of petroleum ether, suction filtered, and then put into 150 ml of anhydrous ethanol and heated to reflux. It was then cooled to room temperature, and then cooled with ice for 2 hours, suction filtered, and dried in an oven at 50°C for 2 hours to obtain the following intermediate A1.

[0457] [Chemistry 17]

[0458] Intermediate A1

[0459]

[0460] (2) Synthesis of intermediate A2

[0461] In a 500 ml four-necked flask, 42 ​​g of the intermediate A1, 400 g of tetrahydrofuran, 200 g of concentrated hydrochloric acid and 24.2 g of isoamyl nitrite were placed, and the mixture was stirred at room temperature for 5 hours, and then the reaction liquid was discharged.

[0462] The reaction solution was added to a large beaker, 1000 ml of water was added and stirred, and then allowed to stand overnight to separate the layers, obtaining a yellow viscous liquid. The viscous liquid was extracted with dichloroethane and 50 g of anhydrous MgSO 4 After drying, suction filtration was performed, and the filtrate was rotary evaporated to remove the solvent to obtain an oily viscous substance. Next, the viscous substance was added to 150 ml of petroleum ether, stirred, precipitated, and suction filtration was performed to obtain a white powdery solid. Thereafter, it was dried at 60° C. for 5 hours to obtain the following intermediate A2.

[0463] [Chemistry 18]

[0464] Intermediate A2

[0465]

[0466] (3) Synthesis of Compound A-1

[0467] In a 1000 ml four-necked flask, 34 g of the intermediate A2, 350 ml of dichloroethane and 12.7 g of triethylamine were added, stirred and cooled in an ice bath. When the temperature dropped to 0°C, a solution containing 15.7 g of acetyl chloride and 15 g of dichloroethane was added dropwise for 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. 5% NaHCO 3 The solution was washed once with 200 ml of water and then twice with 200 ml of water until the pH value was neutral. After that, it was washed once with dilute hydrochloric acid prepared by mixing 20 g of concentrated hydrochloric acid and 400 ml of water, and then washed three times with 200 ml of water. Then, 100 g of anhydrous MgSO 4 The mixture was dried and the solvent was removed by rotary evaporation to obtain a viscous liquid. An appropriate amount of methanol was added to the viscous liquid, and the precipitated white solid was filtered and dried to obtain a compound A-1 represented by the following chemical formula (A-1). It should be noted that the molecular weight of the following compound A-1 is 395.51.

[0468] [Chemistry 19]

[0469] Chemical formula (A-1)

[0470]

[0471] (Synthesis Example 5: Synthesis of the Oxime Photoinitiator Represented by Formula (B-2))

[0472] An oxime ester-based photoinitiator represented by the following formula (B-2) was synthesized in the same manner as in the preparation of Compound No. 73 in paragraphs 0114 to 0117 of International Publication No. 2015 / 152153.

[0473] [Chemistry 20]

[0474] Chemical formula (B-2)

[0475]

[0476] (Synthesis Example 6: Synthesis of the Oxime Ester Photoinitiator Represented by Formula (C-1))

[0477] An oxime ester photoinitiator represented by the following formula (C-1) was synthesized in the same manner as in the preparation of the photopolymerization initiator W (photopolymerization initiator represented by formula (3)) in paragraph 0080 of JP-A-2010-256891.

[0478] [Chemistry 21]

[0479] Chemical formula (C-1)

[0480]

[0481] (Preparation Example 1: Preparation of Color Material Dispersion Liquid A)

[0482] 5.1 parts by mass of the block copolymer A of Synthesis Example 2 as a dispersant, 11.6 parts by mass of CI Pigment Blue 15:6 (trade name FASTOGEN BLUE A510, manufactured by DIC Corporation) and 1.4 parts by mass of CI Pigment Violet 23 (trade name Hostaperm Violet RL-NF, manufactured by Clariant Corporation) as color materials, 5.1 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 1 in terms of solid content, 76.8 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a particle size of 2.0 mm were added to a mayonnaise bottle, and the mixture was shaken for 1 hour using a paint shaker (manufactured by Asada Iron Works Co., Ltd.) as preliminary crushing. Subsequently, the zirconia beads with a particle size of 2.0 mm were removed, and 200 parts by mass of zirconia beads with a particle size of 0.1 mm were added. Similarly, the mixture was dispersed for 4 hours using a paint shaker as final crushing to obtain a color material dispersion A.

[0483] (Preparation Example 2: Preparation of Color Material Dispersion Liquid B)

[0484] In Preparation Example 1, a color material dispersion B was obtained in the same manner as in Preparation Example 1, except that 3.3 parts by mass of CI Pigment Blue 15:6 and 9.7 parts by mass of the lake color material 1 obtained in Synthesis Example 3 were used instead of 11.6 parts by mass of CI Pigment Blue 15:6 and 1.4 parts by mass of CI Pigment Violet 23 as the color material.

[0485] (Manufacturing Example 1: Manufacture of Blue Photosensitive Composition B-1)

[0486] 22.37 parts by mass of the color material dispersion A, 7.86 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 1, 5.84 parts by mass of a photopolymerizable compound (trade name ARONIX M-403, manufactured by Toagosei Co., Ltd.), 0.29 parts by mass of an oxime-based photoinitiator represented by the chemical formula (A-1) of Synthesis Example 4 as a photoinitiator, 0.29 parts by mass of diethylthioxanthone (DETX-S, manufactured by Nippon Kayaku Co., Ltd.) as a sensitizer having a sensitizing effect at 400 nm to 420 nm, 0.36 parts by mass of Karenz MT PE1 (manufactured by Showa Denko Co., Ltd.) as a thiol compound, 0.15 parts by mass of MEGAFAC R-08MH (manufactured by DIC Co., Ltd.) as a surfactant, 0.30 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 were added to obtain a blue photosensitive composition B-1.

[0487] (Manufacturing Examples 2 to 22: Manufacture of Blue Photosensitive Compositions B-2 to B-22)

[0488] In Production Example 1, except that the types and amounts of the components were changed as shown in Tables 1 to 3, blue photosensitive compositions B-2 to B-22 were obtained in the same manner as in the blue photosensitive composition B-1 of Production Example 1.

[0489] (Comparative Production Examples 1 and 2: Production of Comparative Blue Photosensitive Compositions CB-1 and CB-2)

[0490] In Preparation Example 1, as shown in Table 3, a sensitizer having a sensitizing effect at 400 nm to 420 nm was not used, and the types and amounts of the components were changed. Blue photosensitive compositions CB-1 and CB-2 were obtained in the same manner as in the blue photosensitive composition B-1 of Preparation Example 1.

[0491] (Manufacturing Example 23: Manufacture of Blue Photosensitive Composition B-23)

[0492] 27.09 parts by mass of the color material dispersion B, 8.186 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 1, 6.08 parts by mass of a photopolymerizable compound (trade name ARONIX M-403, manufactured by Toagosei Co., Ltd.), 0.22 parts by mass of an oxime-based photoinitiator represented by the chemical formula (A-1) of Synthesis Example 4 as a photoinitiator, 0.12 parts by mass of diethylthioxanthone (DETX-S, manufactured by Nippon Kayaku Co., Ltd.) as a sensitizer having a sensitizing effect at 400 nm to 420 nm, 0.37 parts by mass of Karenz MT PE1 (manufactured by Showa Denko K.K.) as a thiol compound, 0.10 parts by mass of Irganox 1010 (manufactured by BASF) as an antioxidant, and 0.20 parts by mass of MEGAFAC as a surfactant were added. 0.15 parts by mass of R-08MH (manufactured by DIC Corporation), 0.30 parts by mass of KBM503 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, and 57.41 parts by mass of PGMEA were added to obtain a blue photosensitive composition B-23.

[0493] (Manufacturing Examples 24 to 45: Manufacture of Blue Photosensitive Compositions B-24 to B-45)

[0494] In Production Example 23, except that the types and amounts of the components were changed as shown in Tables 4 to 6, blue photosensitive compositions B-24 to B-45 were obtained in the same manner as in the blue photosensitive composition B-23 of Production Example 23.

[0495] (Comparative Production Example 3: Production of Comparative Blue Photosensitive Composition CB-3)

[0496] In Preparation Example 23, a blue photosensitive composition CB-3 was obtained in the same manner as in the blue photosensitive composition B-23 of Preparation Example 23, except that the sensitizer having a sensitizing effect at 400 nm to 420 nm was not used and the types and amounts of the components were changed as shown in Table 6.

[0497] (Example 1: Production of blue cured film)

[0498] <Example 1-1>

[0499] The blue photosensitive composition obtained in each example and each comparative example was applied on a glass substrate (NHTechno Glass Co., Ltd., "NA35") using a spin coater so that the desired color (blue coating: x=0.100 under C light source) was obtained after post-baking. After heating and drying on a hot plate at 80°C for 3 minutes, the blue coating was irradiated with a cumulative exposure of 35 mJ / cm using an LED light source having an intensity ratio (A / B) of 90 / 10 between the intensity of the emission peak wavelength (A) of 360 nm to 380 nm and the intensity of the emission peak wavelength (B) of 400 nm to 420 nm through a photomask having a mask opening width of 2 to 90 μm. 2 The glass plate with the blue coating film formed thereon after the exposure was spray-developed using a 0.05 mass % potassium hydroxide aqueous solution as an alkaline developer. Thereafter, the glass plate 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 fine line pattern.

[0500] <Example 1-2 to Example 1-6>

[0501] In Example 1-1, a blue cured film was produced in the same manner as in Example 1-1, except that the LED lamp was changed to an LED light source with A / B of 80 / 20, an LED light source with A / B of 60 / 40, an LED light source with A / B of 40 / 60, an LED light source with A / B of 20 / 80, or an LED light source with A / B of 10 / 90 as shown in Table 1.

[0502] (Examples 2 to 45, Comparative Examples 1 to 3: Production of Blue Cured Films)

[0503] In Example 1-1, except having changed the blue photosensitive composition and / or the LED light source as shown in Tables 1 to 6, a blue cured film was produced in the same manner as in Example 1-1.

[0504] In each of the examples and comparative examples, corresponding to Examples 1-1 to 1-6 in Example 1, the LED light source was changed to have A / B of 90 / 10, 80 / 20, 60 / 40, 40 / 60, 20 / 80, and 10 / 90 to produce a blue cured film.

[0505] [Evaluation method]

[0506] <Evaluation of line width deviation of fine line pattern (line width)>

[0507] The line width of the obtained blue cured film in the form of an independent fine line pattern was measured at a mask opening of 90 μm when the designed line width was 95 μm. The effect of suppressing line width deviation was evaluated according to the following evaluation criteria.

[0508] (Evaluation criteria for line width deviation)

[0509] ◎: Line width is 93 μm or more and 97 μm or less at a mask opening of 90 μm

[0510] ○: Line width is 90 μm or more and less than 93 μm, or more than 97 μm and less than 100 μm at a mask opening of 90 μm

[0511] ×: The line width is less than 90 μm or more than 100 μm at a mask opening of 90 μm

[0512] If the evaluation result is 0, the effect of suppressing line width deviation is good, and if it is ◎, the effect of suppressing line width deviation is excellent.

[0513] <Evaluation of residual film ratio after development>

[0514] When the blue cured film is patterned, the film thickness after exposure and the film thickness after firing are measured for the blue coloring layer using a stylus profiler P-16 (manufactured by KLA-Tencor), and the film thickness after development / film thickness after exposure × 100 is calculated as the residual film rate (%), and the evaluation is performed according to the following evaluation criteria. It should be noted that the higher the residual film rate, the higher the sensitivity of the blue photosensitive composition.

[0515] ◎: Residual film rate is more than 80%

[0516] 0: The residual film rate is 75% or more and less than 80%

[0517] △: The residual film rate is 65% or more and less than 75%

[0518] ×: The residual film rate is less than 65%.

[0519] If the evaluation result is △, it is usable, if it is 0, the residual film rate is good, and if it is ◎, the residual film rate is excellent.

[0520] <Evaluation of substrate adhesion (minimum adhesion width)>

[0521] The obtained blue cured film was observed with an optical microscope to confirm how many μm of pattern was in close contact with respect to the mask opening width of 2 to 90 μm, or to confirm the line width of the thinnest pattern.

[0522] ◎: When the mask opening is less than 8 μm, the remaining pattern (the line width of the thinnest pattern is less than 8 μm)

[0523] ○: The line width of the finest pattern is 9 μm to less than 15 μm

[0524] △: The line width of the finest pattern is 16 μm to less than 25 μm

[0525] ×: The line width of the thinnest pattern is 26 μm or more

[0526] If the evaluation result is △, it can be used, if it is ○, the substrate adhesion is good, and if it is ◎, the substrate adhesion is excellent.

[0527] <Comprehensive judgment>

[0528] Comprehensive evaluation was performed on the evaluation of line width deviation of the thin line pattern, the evaluation of residual film ratio after development, and the evaluation of substrate adhesion (minimum adhesion width).

[0529] ◎: The evaluation results are all ○ or ◎

[0530] 0:Evaluation results include △

[0531] ×: The evaluation results contain ×

[0532] [Table 1]

[0533]

[0534] [Table 2]

[0535]

[0536] [Table 3]

[0537]

[0538] [Table 4]

[0539]

[0540] [Table 5]

[0541]

[0542] [Table 6]

[0543]

[0544] The abbreviations in the table are as follows.

[0545] Alkali-soluble resin: Alkali-soluble resin A of Synthesis Example 1

[0546] Photopolymerizable compound: Trade name ARONIX M-403, manufactured by Toagosei Co., Ltd.

[0547] Oxime-based (A-1): Oxime-based photoinitiator represented by the chemical formula (A-1) of Synthesis Example 4

[0548] Oxime-based (B-2): Oxime-based photoinitiator represented by the chemical formula (B-2) of Synthesis Example 5

[0549] Oxime-based (C-1): Oxime-based photoinitiator represented by the chemical formula (C-1) of Synthesis Example 6

[0550] IRGACURE369: Trade name IRGACURE369, manufactured by BASF

[0551] Sensitizer 1: Thioxanthone sensitizer, diethylthioxanthone (DETX-S, manufactured by Nippon Kayaku Co., Ltd.)

[0552] Sensitizer 2: Benzophenone sensitizer, 4,4'-bis(diethylamino)benzophenone (EAB-SS, manufactured by Daido Chemical Industry Co., Ltd.)

[0553] Sensitizer 3: Anthracene sensitizer, 9,10-dibutoxyanthracene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0554] Thiol compound: Karenz MT PE1 (manufactured by Showa Denko Co., Ltd.)

[0555] Surfactant: MEGAFAC R-08MH (manufactured by DIC Corporation)

[0556] Silane coupling agent: KBM503 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0557] Solvent: PGMEA

[0558] (Comparative Examples 4 and 5: Production of Blue Cured Film)

[0559] (1) Synthesis of oxime-based photoinitiators with a fluorene skeleton

[0560] With reference to Synthesis Examples 1 and 2 of JP-A-2017-125972, an oxime-based photoinitiator having the following fluorene skeleton was synthesized.

[0561] [Chemistry 22]

[0562]

[0563] (2) Preparation of blue photosensitive composition B-46

[0564] In Preparation Example 1, the oxime photoinitiator having a fluorene skeleton obtained in the above (1) was used instead of the oxime photoinitiator represented by the chemical formula (A-1) of Synthesis Example 4, and 2-isopropyl-9H-thioxanthen-9-one was used instead of diethylthioxanthone as the sensitizer. A blue photosensitive composition B-46 was obtained in the same manner as the blue photosensitive composition B-1 of Preparation Example 1.

[0565] (3) Production of blue cured film

[0566] In Example 1-1, a blue cured film was produced in the same manner as in Example 1-1 except that the blue photosensitive composition was changed to the blue photosensitive composition B-46, and the LED light source was changed to a single LED light source with (A / B) of 100 / 0 or (A / B) of 0 / 100 as shown in Table 7.

[0567] Table 7 shows the results of the evaluation carried out in the same manner as in Example 1.

[0568] (Comparative Examples 6 to 15: Production of Blue Cured Films)

[0569] In Example 1-1, except having changed the blue photosensitive composition and the LED light source as shown in Table 7, it carried out similarly to Example 1-1, and produced a blue cured film.

[0570] Table 7 shows the results of the evaluation carried out in the same manner as in Example 1.

[0571] [Table 7]

[0572]

[0573] [Summary of results]

[0574] In Examples 1 to 45, which are methods for producing a blue cured film of the present invention, a coating film of a blue photosensitive composition containing a color material, an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator containing an oxime-based photoinitiator and a sensitizer having a sensitizing effect at 400 nm to 420 nm different from the oxime-based photoinitiator is exposed and cured using an LED light source having emission peak wavelengths at 360 nm to 380 nm and 400 nm to 420 nm. This shows that line width deviation can be suppressed and the residual film rate after development can be improved, and a good pattern with suppressed undercut after development can be formed, and the substrate adhesion of the pattern of the formed blue cured film is also improved.

[0575] On the other hand, in Comparative Examples 1 to 3 in which the coating film of the blue photosensitive composition not containing a sensitizer having a sensitizing effect at 400 nm to 420 nm other than the oxime-based photoinitiator was cured by exposure using an LED light source having a peak emission wavelength at 360 nm to 380 nm and 400 nm to 420 nm, the line width became thinner, the residual film rate after development was also poor, and the substrate adhesion of the pattern of the formed blue cured film was also poor.

[0576] In addition, in Comparative Example 4, in which the oxime-based photoinitiator and sensitizer having a fluorene skeleton used in Patent Document 2 were used instead and a single LED light source (an LED light source having a peak emission wavelength at 365 nm) was used for exposure and curing, although curing and a residual film rate after development were ensured, the line width became thinner and the substrate adhesion of the pattern of the formed blue cured film was also poor.

[0577] In Comparative Example 5, in which the oxime-based photoinitiator and sensitizer having a fluorene skeleton used in Patent Document 2 were used instead and a single LED light source (an LED light source having a peak emission wavelength at 405 nm) was used for exposure and curing, the light range was expanded and the line width was increased because the coating film of the blue photosensitive composition was easily transmitted, but the curing was insufficient and the residual film rate after development was poor.

[0578] In Comparative Examples 6 to 15 in which the coating films of the blue photosensitive composition not containing a sensitizer having a sensitizing effect at 400 nm to 420 nm other than the oxime-based photoinitiator were exposed and cured using a single LED light source (an LED light source having an emission peak wavelength at 365 nm or an LED light source having an emission peak wavelength at 405 nm), the line widths were all reduced and the substrate adhesion of the patterns of the formed blue cured films was also deteriorated.

[0579] Description of Reference Numerals

[0580] 1: Substrate

[0581] 2: Shading part

[0582] 3: Coloring layer

[0583] 10: Color filter

[0584] 20: Opposite substrate

[0585] 30: Liquid crystal layer

[0586] 40: Liquid crystal display device

[0587] 50: Organic protective layer

[0588] 60: Inorganic oxide film

[0589] 71: Transparent anode

[0590] 72: Hole injection layer

[0591] 73: Hole transport layer

[0592] 74: Luminous layer

[0593] 75: Electron injection layer

[0594] 76: Cathode

[0595] 80: Organic light emitting body

[0596] 100: Organic light-emitting display device

Claims

1. A method for producing a blue cured film, comprising the following steps: forming a coating film of a blue photosensitive composition on a substrate, wherein the blue photosensitive composition contains a colorant, an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator, wherein the photoinitiator includes an oxime-based photoinitiator and a sensitizer having a sensitizing effect at 400 nm to 420 nm, which is different from the oxime-based photoinitiator; and The coating film is exposed to light using an LED light source having emission peak wavelengths of 360 nm to 380 nm and 400 nm to 420 nm to be cured.

2. The method for producing a blue cured film according to claim 1, wherein: In the LED light source, an intensity ratio A / B of an intensity A of a light emission peak wavelength of 360 nm to 380 nm to an intensity B of a light emission peak wavelength of 400 nm to 420 nm is 10 / 90 to 90 / 10.

3. The method for producing a blue cured film according to claim 1 or 2, wherein: 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.

4. A blue photosensitive composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound and a photoinitiator, wherein the photoinitiator comprises 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, The blue photosensitive composition is used to be cured by exposing it to an LED light source having a peak emission wavelength of 360 nm to 380 nm and 400 nm to 420 nm. General formula (A) In the general formula (A), Z 1 , Z 3 , Z 4 and Z 5 Each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a phenyl group, wherein the alkyl group, the cycloalkyl group, and the phenyl group are each optionally 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, and Z 2 It represents an alkyl group having 1 to 20 carbon atoms substituted with a cycloalkyl group.

5. A method for producing a color filter, the color filter comprising at least a substrate and a coloring layer including a blue cured film provided on the substrate, The method for manufacturing the color filter comprises the following steps: The blue cured film is produced by the method for producing a blue cured film according to claim 1 or 2.

6. A color filter comprising at least a substrate and a coloring layer provided on the substrate, At least one of the colored layers is a cured product of the blue photosensitive composition according to claim 4 .

7. A display device comprising the color filter according to claim 6.

Images