Colored photosensitive resin composition, colored photosensitive resin substrate, color filter and element

Abstract

To form a colored photosensitive resin film which is applicable to a color filter composed of a substrate material having non-high heat resistance and an element composed of a pixel material having non-high heat resistance, has a small half-value width of a green transmission spectrum, and has high parallel light transmittance at a green peak wavelength, enable formation of a green pixel having high color reproducibility and excellent low reflection characteristics, lower a driving voltage of a green light-emitting element, and improve durability of the green pixel.SOLUTION: A colored photosensitive resin composition contains C.I. pigment green 59 or C.I. pigment green 58, a yellow coloring material, a binder resin, a polymerizable compound, and a photopolymerization initiator, wherein a weight ratio of the C.I. pigment green 59 to the yellow coloring material is 60:40 to 90:10, the polymerizable compound contains dipentaerythritol hexaacrylate and pentaerythritol triacrylate, and a ratio of a weight (A) of dipentaerythritol hexa(meth)acrylate to a weight (B) of the pentaerythritol tri(meth)acrylate is 0.15<A / B<3.20.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a colored photosensitive resin composition, a colored photosensitive resin substrate having a colored photosensitive resin film formed thereon, which is made of a cured product of the colored photosensitive resin composition, and a color filter and element. In particular, the colored photosensitive resin film formed of a cured product of the colored photosensitive resin composition is suitable for an organic light-emitting element or a micro LED element formed on an upper portion of a green light-emitting pixel. [Background technology]

[0002] In recent years, the use of self-luminous displays such as organic electroluminescence (EL) displays has been increasing in mobile devices such as smartphones, and circular polarizing plates are used in these displays to prevent surface reflection. However, circular polarizing plates are relatively thick and lack flexibility, making them difficult to apply to flexible display elements that can be used in foldable applications, which have recently been in the spotlight. Therefore, the invention of Patent Document 1 has been disclosed as an invention consisting of a photosensitive resin composition that can be used as a polarizing plate or a substitute for a polarizing plate for such flexible display elements.

[0003] The invention of Patent Document 1 is an invention of a green photosensitive resin composition containing a pigment dispersion composition containing a green pigment, a yellow pigment, and a black pigment, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and by setting the weight ratio of the green pigment and the yellow pigment to the black pigment at 99.9-80:20-0.1, the problems of high green color reproducibility and insufficient processability are solved, and the invention is said to be an invention that can replace a polarizing plate while also having an excellent external light anti-reflection effect.

[0004] In the invention of Patent Document 1, after exposure and development, it is necessary to blow nitrogen gas onto the substrate to dry it and then heat it in a heating oven at 200°C for 25 minutes. Therefore, a heat-resistant glass substrate (manufactured by Corning Incorporated, "EAGLE XG") that can withstand such temperatures is used as the substrate on which the green photosensitive resin composition is coated (see [Patent Document 1]

[0113]

[0114] and Experimental Example 1). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 6755822 Summary of the Invention [Problem to be solved by the invention]

[0006] However, for color filters with a glass substrate thickness of 0.3 mm or more, the applicable flexible display elements are limited to those with a large radius of curvature, making them inapplicable to foldable applications. For foldable applications, the glass substrate needs to be as thin as possible, but it is difficult to process the glass substrate thin, and it is also difficult to apply coating to such a very thin glass substrate.

[0007] One possible method to address this issue is to directly coat the photosensitive resin composition on the surface of the sealing film of an organic EL display without using a glass substrate. However, the pixel materials used in organic EL displays and the like generally have poor heat resistance and are highly susceptible to damage from heat, and therefore there is a problem that the durability of the display element is significantly reduced if the photosensitive resin composition is coated and then baked at high temperatures.

[0008] Furthermore, the invention of Patent Document 1 adds a black pigment to reduce the half-width of the green spectrum, thereby improving the green color reproducibility and also achieving the effect of preventing external light reflection. However, the inclusion of a black pigment not only makes the color dull (becoming a dark, subdued color), but also reduces the transmittance of the green spectrum in the wavelength range of 500 nm to 560 nm, posing the problem that the drive voltage of the green light-emitting element must be increased to compensate for this.

[0009] Therefore, in the present invention, the above problems have been solved by carefully devising the composition of the colored photosensitive resin composition so that after the colored photosensitive resin composition is applied and formed, it can be heated and baked at a relatively low temperature, and high green color reproducibility and external light antireflection effect can be obtained without containing a black pigment. [Means for solving the problem]

[0010] That is, the present invention is as follows. (1) A colored photosensitive resin composition comprising CI Pigment Green 59 or CI Pigment Green 58, a yellow colorant, a binder resin, a polymerizable compound, and a photopolymerization initiator, wherein the weight ratio of the CI Pigment Green 59 to the yellow colorant is 60:40 to 90:10, the polymerizable compound comprises dipentaerythritol hexaacrylate and pentaerythritol triacrylate, and the ratio of the weight (A) of the dipentaerythritol hexa(meth)acrylate to the weight (B) of the pentaerythritol tri(meth)acrylate is 0.15 (2) The colored photosensitive resin composition according to (1), in which the solid content is diluted with propylene glycol monomethyl ether acetate at a weight ratio of (10,000 / 2.3) and filled into a spectrophotometer cell having an optical path length of 1 cm, and the parallel light transmittance measured is 20% or less at wavelengths of 460 nm and 620 nm and 70% or more at a wavelength of 530 nm. (3) The colored photosensitive resin composition according to (1) or (2), wherein a weight ratio of the CI Pigment Green 59 and the CI Pigment Green 58 to the yellow colorant is 75:25 to 90:10, and the yellow colorant is CI Pigment Yellow 150 or CI Pigment Yellow 185. (4) The colored photosensitive resin composition according to any one of (1) to (3), which contains a photopolymerization initiator having a melting point of 72°C to 96°C. (5) The colored photosensitive resin composition according to any one of (1) to (4), which contains a transparent filler. (6) The colored photosensitive resin composition according to (5), wherein the transparent filler is any particle selected from the group consisting of silicon-based resins, fluorine-based resins, acrylic resins, urethane resins, polyvinyl alcohol resins, polypropylene resins, and polyacetal resins. ​(7) A colored photosensitive resin substrate comprising a colored photosensitive resin film formed on a substrate, the colored photosensitive resin film being made of a cured product of the colored photosensitive resin composition according to any one of (1) to (6), wherein the L* value of the surface of the colored photosensitive resin film in the Lab color system of the CIE International Commission on Illumination is 27 to 31. (8) A color filter comprising a colored photosensitive resin film formed on a substrate, the colored photosensitive resin film being made of a cured product of the colored photosensitive resin composition according to any one of (1) to (6), wherein the L* value of the surface of the colored photosensitive resin film in the Lab color system of the CIE International Commission on Illumination is 27 to 31. (9) A light-emitting element having a colored photosensitive resin film made of a cured product of the colored photosensitive resin composition according to any one of (1) to (6) formed on an upper portion of a green-emitting pixel, wherein the L* value of the surface of the colored photosensitive resin film in the Lab color system of the CIE International Commission on Illumination is 27 to 31. (10) A method for producing a colored photosensitive resin substrate, comprising applying the colored photosensitive resin composition according to any one of (1) to (6) onto a substrate to form a colored photosensitive resin film, placing a mask on the colored photosensitive resin film, exposing the film to light, developing the film to form a pattern, and then baking the film at 150° C. or lower. (11) A method for producing a color filter, comprising applying the colored photosensitive resin composition according to any one of (1) to (6) onto a substrate to form a colored photosensitive resin film, placing a mask on the colored photosensitive resin film, exposing the film to light, developing the film to form a pattern, and then baking the film at 150° C. or lower. (12) A method for producing a light-emitting element, comprising applying the colored photosensitive resin composition according to any one of (1) to (6) onto an upper portion of a green-light-emitting pixel to form a colored photosensitive resin film, placing a mask on the colored photosensitive resin film, exposing the film to light, developing the film to form a pattern, and then baking the film at 150° C. or lower. Effect of the Invention

[0011] When the photosensitive resin composition of the present invention is used, after forming a colored photosensitive resin film by coating, a mask can be placed on the colored photosensitive resin film, exposed to light, developed to form a pattern, and then baked at 150° C. or less. Therefore, it has an effect that it can be applied to color filters made of substrate materials that are not highly heat resistant and elements made of pixel materials that are not highly heat resistant.

[0012] In addition, by using the photosensitive resin composition of the present invention, a colored photosensitive resin film can be formed that has a small half-width of the green transmission spectrum and a high parallel light transmittance at the green peak wavelength, even without containing a black pigment. Therefore, a green pixel with high color reproducibility and excellent low reflection characteristics can be formed without the color becoming dull (dark and subdued). As a result, the driving voltage of the green light-emitting element can be lowered, and the durability of the green pixel can be improved. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The photosensitive resin composition of the present invention will be described in detail below. The photosensitive resin composition of the present invention is a colored photosensitive resin composition containing CI Pigment Green 59 or CI Pigment Green 58, a yellow coloring material, a polymerizable compound, a binder resin, and a photopolymerization initiator, in which the weight ratio of the CI Pigment Green 59 or CI Pigment Green 58 to the yellow coloring material is 60:40 to 90:10, the polymerizable compound contains dipentaerythritol hexaacrylate and pentaerythritol triacrylate, and the ratio of the weight (A) of the dipentaerythritol hexa(meth)acrylate to the weight (B) of the pentaerythritol tri(meth)acrylate is 0.15

[0014] <C.I.ピグメントグリーン59、C.I.ピグメントグリーン58> ​Since CI Pigment Green 59 has a peak parallel light transmittance at 520 nm and CI Pigment Green 58 has a peak parallel light transmittance at 550 nm, by selecting CI Pigment Green 59 or CI Pigment Green 58 from among various green colorants, it is possible to specifically bring the peak wavelength of the parallel light transmittance of the colored photosensitive resin film close to 530 nm, which is the ideal peak wavelength for a green pixel.

[0015] Furthermore, if a green colorant is made by mixing CI Pigment Green 59 and CI Pigment Green 58 in a weight ratio of 5:1 to 2:1, the peak wavelength will be closer to 530 nm, making it easier to obtain the desired transmission spectrum, which is preferable. On the other hand, since the peak wavelength of CI Pigment Green 7, which has been widely used in the past, is 500 nm, it is difficult to adjust the peak wavelength to 530 nm.

[0016] Each of the red, green, and blue coloring materials has a wide transmission bandwidth, and the green and blue coloring materials have a tendency to easily mix together because their peak wavelengths are close to each other. In the present invention, therefore, in order to suppress the transmission of bluish light with a wavelength of 500 nm or less, a yellow coloring material is added in a weight ratio of 60:40 to 90:10 between the green and yellow coloring materials. That is, the weight ratio between CI Pigment Green 59 or CI Pigment Green 58 and the yellow coloring material is 60:40 to 90:10. When the above coloring materials are formulated in the above ratio, the half-width of the peak of the transmission spectrum between the wavelengths of 490 and 570 nm is approximately 70 nm or less, and a colored photosensitive resin film with high green color purity can be obtained.

[0017] <Yellow color material> Examples of yellow colorants include organic pigments, inorganic pigments, and dyes, such as CI Pigment Yellow (hereinafter, "PY") 12, PY13, PY17, PY20, PY24, PY83, PY86, PY93, PY95, PY109, PY110, PY117, PY125, PY129, PY137, PY139, PY147, PY148, PY150, PY153, PY154, PY166, and PY168 (all numbers are color index numbers). Two or more of these may be contained.

[0018] Among them, from the viewpoints of color purity, parallel light transmittance and contrast, PY138, PY139, PY150 and PY185 are preferred, and PY150 and PY185 are more preferred. PY150 and PY185 have a greater suppressing effect on the parallel light transmittance of light with wavelengths of 450 to 500 nm than other yellow colorants, and therefore have a greater effect of improving the color purity of the green spectrum.

[0019] <Metal-containing porphyrin compounds> In addition to these yellow coloring materials, a metal-containing porphyrin compound may be added. The maximum absorption of general porphyrin is 400 to 500 nm, and the half-width of the peak wavelength of the green coloring material can be narrowed in the same way as by adding a yellow coloring material, thereby further increasing the color purity.

[0020] The absorption maximum wavelength of a metal-containing porphyrin compound depends on the central metal, and for example, the absorption maximum wavelength can be easily adjusted by using Co, Cu, Ni, or Pb as the metal. Examples of such metal-containing porphyrin compounds include tetraazaporphyrin compounds and specific wavelength absorbing dyes FDG-005(Pd), FDG-006(Co), and FDG-007(Cu) (all trade names) manufactured by Yamada Chemical Co., Ltd. Two or more of these may be included.

[0021] The content of the metal-containing porphyrin compound is preferably 1 to 10 parts by weight per 100 parts by weight of the green color material. By setting the content in this range, the color purity can be increased and the surface smoothness of the colored resin composition film can be improved.

[0022] The colored photosensitive resin composition is preferably a composition that, when the solid content is diluted with propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) at a weight ratio of (10000 / 2.3) and filled in a spectrophotometer cell with an optical path length of 1 cm, has a parallel light transmittance of 20% or less at wavelengths of 460 nm and 620 nm and 70% or more at a wavelength of 530 nm. From the viewpoint of reducing reflectance, the parallel light transmittance is more preferably 14% or less at wavelengths of 460 nm and 620 nm, and from the viewpoint of parallel light transmittance in the green region, the parallel light transmittance is preferably 70% or more at a wavelength of 530 nm, and more preferably 73% or more.

[0023] It is clear that the colored photosensitive resin composition having such characteristics becomes a homogeneous solution to which the Lambert-Beer law can be applied when diluted with PGMEA, and therefore each component of CI Pigment Green 59 or CI Pigment Green 58, yellow colorant, polymerizable compound, binder resin, and photopolymerization initiator can be uniformly dispersed by the organic solvent, etc. As a result, the colored photosensitive resin composition having the above characteristics becomes a colored photosensitive resin composition having excellent coating properties.

[0024] Furthermore, the characteristics are also reflected in the colored photosensitive resin film that is applied, and when the colored photosensitive resin composition is applied to an element or the like in a thickness of 2.3 μm, a colored photosensitive resin film can be formed that has a high parallel light transmittance at wavelengths of 500 nm to 560 nm and a low parallel light transmittance at wavelengths of 500 nm or less and 560 nm or more, that is, a green spectrum with a narrow half-width and a sharp peak with very high color purity. Note that the solid content refers to all components of the colored photosensitive resin composition excluding the solvent.

[0025] And, when the weight ratio of CI Pigment Green 59 or CI Pigment Green 58 to the yellow colorant in the colored photosensitive resin composition is 75:25 to 90:10, the L* value in the Lab color system of the CIE International Commission on Illumination when the photosensitive resin film is formed is preferably lowered. The lowering of the L* value means that the same phenomenon as that of adding a black pigment without adding a black pigment as described in Patent Document 1 is manifested, and therefore the reflectance can be further reduced without lowering the peak value of the transmission spectrum at wavelengths of 500 nm to 560 nm.

[0026] <Polymerizable compound> In addition, the colored photosensitive resin composition of the present invention contains a predetermined polymerizable compound. The polymerizable compound is a compound having an ethylenically unsaturated double bond. The binder resin described below has a relatively high molecular weight and is somewhat inferior in development solubility, i.e., patterning characteristics when forming a fine pattern. Even if an ethylenically unsaturated group is introduced into the side chain or the acid value or solid content is optimized, a film residue (development residue) is likely to remain.

[0027] In particular, the metal phthalocyanine green coloring material used in the present invention is preferably made into a relatively thick film in order to increase color purity, but the thicker the film, the more likely it is that film residue will occur. This problem can be alleviated by using a compound containing a hydroxyl group as the polymerizable compound. Hydroxy groups have a high affinity for alkaline developers, and polymerizable compounds having such groups have high solubility in alkaline developers.

[0028] Therefore, in the development step, by containing a polymerizable compound containing a hydroxyl group in the colored photosensitive resin composition, the alkaline developer can easily penetrate into the fine details of the obtained colored photosensitive resin film, and the film residue can be reduced. As a result, the patterning characteristics of the colored photosensitive resin film are improved, and a colored photosensitive resin film having a highly accurate pattern can be formed.

[0029] Furthermore, from the viewpoint of effectively promoting internal curing during low-temperature baking and further suppressing grain defects, those having three or more ethylenically unsaturated bonds in one molecule are preferred, and those having five or more ethylenically unsaturated bonds in one molecule are more preferred. A polymerizable compound having such a hydroxy group, capable of being baked at a low temperature, and having effective internal curing during baking is a mixture of dipentaerythritol hexaacrylate and pentaerythritol triacrylate. That is, in the colored photosensitive resin composition of the present invention, the polymerizable compound contains dipentaerythritol hexaacrylate and pentaerythritol triacrylate.

[0030] The ratio of the weight (A) of the dipentaerythritol hexa(meth)acrylate to the weight (B) of the pentaerythritol tri(meth)acrylate is 0.15

[0031] Generally, when firing is performed at a low temperature, pattern peeling is likely to occur during overcoating, but by setting the weight ratio at this level, the phenomenon is suppressed, patterning performance is improved, color mixing during patterning can be suppressed, and high color purity is maintained when the material is made into a colored photosensitive resin film. Furthermore, from the viewpoint of further improving the suppression of pattern peeling during overcoating and further improving the prevention of color mixing, the weight ratio (A / B) is preferably 0.30 or more and 2.0 or less.

[0032] ​The content of the polymerizable compound is preferably 25% by mass or more in the solid content of the colored photosensitive resin composition, and more preferably 30% by mass or more in the solid content. By containing 25% by mass or more of the polymerizable compound, the alkali developer can penetrate into the fine parts, and the solubility of the binder resin can be improved. On the other hand, from the viewpoint of suppressing unevenness in the film thickness when forming the colored photosensitive resin film and suppressing deformation of the pattern due to flow during baking, the content of the polymerizable compound is preferably 90% by mass or less in the solid content of the colored photosensitive resin composition, more preferably 70% by mass or less, and even more preferably 60% by mass or less.

[0033] <Binder resin> The binder resin is not particularly limited as long as it is a component that can be easily diluted with an organic solvent such as PGMEA, and examples thereof include acrylic resin, epoxy resin, polyimide resin, urethane resin, urea resin, polyvinyl alcohol resin, melamine resin, polyamide resin, polyamideimide resin, polyester resin, polyolefin resin, etc. Two or more of these may be contained. In particular, acrylic resin is preferably used in terms of ease of dissolution in the organic solvent, transparency, and stability.

[0034] The acrylic resin is preferably a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound.The unsaturated carboxylic acid may be, for example, a monocarboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, or vinylacetic acid, or a dicarboxylic acid such as itaconic acid, maleic acid, or fumaric acid, or an acid anhydride thereof.It is particularly preferable that the resin contains a unit derived from acrylic acid or methacrylic acid.

[0035] Examples of the ethylenically unsaturated compound include ethylenically unsaturated compounds having a glycidyl group or an alicyclic epoxy group, unsaturated carboxylic acid amino alkyl esters, unsaturated carboxylic acid glycidyl esters, carboxylic acid vinyl esters, vinyl cyanide compounds, and aliphatic conjugated dienes, as well as polystyrene, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, and polybutyl methacrylate having a (meth)acryloyl group at the terminal.

[0036] Particularly, ethylenically unsaturated compounds having a glycidyl group or an alicyclic epoxy group are preferred. Examples of ethylenically unsaturated compounds having a glycidyl group or an alicyclic epoxy group include glycidyl acrylate, glycidyl (meth)acrylate, allyl glycidyl ether, α-ethyl acrylate glycidyl, crotonyl glycidyl ether, (iso)crotonic acid glycidyl ether, N-(3,5-dimethyl-4-glycidyl)benzyl acrylamide, and (3,4-epoxycyclohexyl)methyl (meth)acrylate.

[0037] In order to improve the sensitivity during exposure and development to form a fine pattern, it is preferable that the binder resin has an ethylenically unsaturated group such as a vinyl group, an allyl group, an acrylic group, or a methacrylic group in the side chain. As a method for introducing an ethylenically unsaturated group into the side chain of the binder resin, for example, a method of adding an ethylenically unsaturated compound having an epoxy group, or acrylic acid or methacrylic acid chloride to a carboxyl group or a hydroxyl group of the binder resin can be mentioned.

[0038] The weight average molecular weight of the binder resin is preferably 3,000 or more, more preferably 9,000 or more, from the viewpoint of the strength of the colored photosensitive resin film. On the other hand, from the viewpoint of the stability of the colored photosensitive resin composition, the weight average molecular weight of the binder resin is preferably 200,000 or less, more preferably 100,000 or less. Here, the weight average molecular weight of the binder resin refers to a standard polystyrene equivalent value measured by gel permeation chromatography.

[0039] The content of the binder resin is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, based on the solid content, from the viewpoint of suppressing unevenness in the film thickness when forming a colored photosensitive resin film. On the other hand, from the viewpoint of patterning properties, the content of the binder resin is preferably 60% by mass or less, more preferably 50% by mass or less, based on the solid content. In order to obtain a suitable alkali developability, the acid value of the binder resin is preferably 20 to 200 (mgKOH / g), more preferably 30 to 150 (mgKOH / g). In addition, the content of the binder resin is preferably 30% by mass or more and 70% by mass or less, based on the solid content of the colored photosensitive resin composition, and more preferably 35% by mass or more and 65% by mass or less, based on the solid content.

[0040] <Transparent filler> Furthermore, a transparent filler may be added to the colored photosensitive resin composition of the present invention. As described above, by making the weight ratio of CI Pigment Green 59 or CI Pigment Green 58 to the yellow colorant 75:25 to 90:10, the reflectance of the colored photosensitive resin film can be reduced, but by adding a transparent filler to the colored photosensitive resin composition, the reflectance can be reduced without the weight ratio, or the reflectance can be further reduced in addition to the weight ratio.

[0041] The transparent filler reduces the reflectance by scattering visible light in various directions, but has almost no property of absorbing visible light like the black pigment in Reference 1. Therefore, it is possible to reduce the reflectance of the green spectrum with wavelengths of 500 nm to 560 nm.

[0042] The transparent filler is not particularly limited, but is preferably a low refractive index particle having a refractive index in the range of 1.10 to 1.52. This is because not only the reflectance is reduced by the scattering, but also the reflectance is reduced by the reduction in the refractive index difference with air. Examples of such low refractive index particles include particles of silicon-based resin, fluorine-based resin, acrylic resin (refractive index 1.49), urethane resin, polyvinyl alcohol resin (refractive index 1.49), polypropylene resin (refractive index 1.49), polyacetal resin (refractive index 1.48), etc. Alternatively, it may be a composite of these, such as fluorinated acrylic resin particles.

[0043] In particular, silicon-based resins such as silica (refractive index 1.46), fluorine-based resins such as magnesium fluoride (refractive index 1.38), calcium fluoride (refractive index 1.40), sodium fluoride (refractive index 1.33), lithium fluoride (refractive index 1.39) and aluminum fluoride (refractive index 1.38), and urethane resins (refractive index 1.43) have a lower refractive index and a higher anti-reflection effect than the binder resins and polymerizable compounds, and are therefore preferred.

[0044] The surface of the transparent filler may be treated with an organometallic compound such as a coupling agent of a silane system, an aluminum system, etc. For example, examples of compounds treated with a silane system include silane compounds such as tetraalkoxysilanes, trialkoxysilanes, and dialkoxysilanes.

[0045] The transparent filler may be a solid particle, a hollow particle having a structure in which a shell covers one cavity, such as a hollow silica particle, or a porous particle. The transparent filler may be spherical or irregular in shape. The average primary particle size of the transparent filler is appropriately selected depending on the type of yellow colorant, but is preferably in the range of nanoparticles of 10 to 200 nm. When the primary particle size of the transparent filler is 10 nm or more, the dispersion stability in the colored photosensitive resin composition is sufficiently ensured, and when it is 200 nm or less, a colored photosensitive resin film with good surface roughness can be formed.

[0046] In addition, the ratio of the average value of the primary particle diameter of the yellow colorant to the transparent filler is preferably in the range of 1:5 to 5:1, more preferably in the range of 1:4 to 4:1. Within this range, long-term dispersion stability is ensured, and even after coating on a substrate and exposure and development, substrate adhesion is guaranteed, and a high anti-reflection effect is exhibited. In addition, the content of the transparent filler is preferably 2% by mass or more and 60% by mass or less of the solid content of the colored photosensitive resin composition, and more preferably 5% by mass or more and 30% by mass or less of the solid content. By setting the content within this range, the refractive index of the colored photosensitive resin film is reduced, and the abrasion resistance of the colored photosensitive resin film is guaranteed.

[0047] <Photopolymerization initiator> The colored photosensitive resin composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator triggers the reaction of the unsaturated double bonds present in the alkali-soluble resin and the polymerizable compound contained in the colored photosensitive resin composition, and has the effect of preventing the adverse effects of unreacted double bonds. If the curing reaction is insufficient and a large amount of unreacted double bond residues remain, the residues will gasify and become outgassed, reducing the adhesion, so the selection of the photopolymerization initiator is an important factor.

[0048] The generation of outgassing is correlated with the weight loss rate measured by TG-DTA, and the weight loss rate measured by TG-DTA decreases as the melting point of the photopolymerization initiator increases. On the other hand, as the melting point of the photopolymerization initiator increases, the absorbance in the visible region increases, and the color tends to become yellowish. In addition, if the curing temperature is lower than the melting point of the photopolymerization initiator, uneven curing (the degree of curing varies depending on the location) is likely to occur if the dispersion of the photopolymerization initiator is insufficient. However, if the photopolymerization initiator melts and becomes liquid when heated during curing, the photopolymerization initiator will spread and uneven curing will be reduced even if the dispersion of the photopolymerization initiator is insufficient.

[0049] In this regard, a photopolymerization initiator with a melting point of 72°C to 96°C has low absorbance in the visible light region and can suppress the generation of outgassing to a low level, and by curing and baking the colored photosensitive resin composition at a temperature slightly higher than the melting point, the amount of photopolymerization initiator remaining in a solid state is reduced, the haze is reduced, and the transparency is improved. In other words, it is preferable to select a photopolymerization initiator with a melting point of 72°C to 96°C, which allows curing and baking at a relatively low temperature.

[0050] The photopolymerization initiator is preferably one that allows the exposure light to reach not only the surface but also the deep portion uniformly. The colored photosensitive resin composition of the present invention is baked at a low temperature, so there is a possibility that double bond residues will remain, but by including a photopolymerization initiator having this function, it is possible to prevent variation in the degree of photocuring between the surface and the deep portion of the film (i.e., variation in the ratio of double bond residues), and as a result, the possibility of double bond residues remaining can be reduced.

[0051] Photopolymerization initiators having such a function include photobleach-based photopolymerization initiators. Photobleach-based photopolymerization initiators are photopolymerization initiators in which the light absorption decreases as the reaction of the double bond progresses by cleavage. Specifically, monoacylphosphine oxide-based photopolymerization initiators, bisacylphosphine oxide-based photopolymerization initiators, metallocene (titanocene)-based photopolymerization initiators, polysilane-based photopolymerization initiators, and oxime-based photopolymerization initiators are included. Among these, oxime-based photopolymerization initiators are preferred.

[0052] Examples of commercially available oxime-based photopolymerization initiators having a melting point of 72° C. to 96° C. include, for example, “Irgacure OXE-04” manufactured by BASF Japan Ltd., “ADEKA CRUISE NCI-803”, “ADEKA CRUISE NCI-930”, and “ADEKA CRUISE NCI-730” manufactured by ADEKA Corporation. These may be used alone or in combination of two or more kinds.

[0053] The content of the photopolymerization initiator is preferably 1% by mass or more and 10% by mass or less in the solid content. When the content of the photopolymerization initiator is 1% by mass or more, photocuring defects are less likely to occur. On the other hand, when the content of the photopolymerization initiator is 10% by mass or less, the amount of precipitation of impurities in the colored photosensitive resin film is small, and the color purity of the green pixel can be maintained.

[0054] The colored photosensitive resin composition of the present invention may contain a solvent as appropriate. The solvent can adjust the viscosity of the colored photosensitive resin composition to an easy-to-apply viscosity, and after application, the solvent is evaporated by air drying or by heating and drying at a temperature lower than that of baking, so that only a small amount of the solvent remains on the colored photosensitive resin film.

[0055] Examples of the solvent include ethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, ethylene glycol alkyl ether acetates, alkylene glycol alkyl ether acetates, aromatic hydrocarbons, ketones, alcohols, esters, etc. Preferred are alkylene glycol alkyl ether acetates, ketones, and esters, and more preferred are alkylene glycol alkyl ether acetates such as PGMEA, propylene glycol monoethyl ether acetate, and cyclohexanone.

[0056] The colored photosensitive resin composition of the present invention may further contain a chain transfer agent, a sensitizer, a polymer dispersant, an adhesion improver, a surfactant, a dispersant, etc. Examples of the chain transfer agent include thioglycolic acid, thiomalic acid, thiosalicylic acid, various propionic acids, 3-mercaptobutyric acid, various nicotinic acids, various sulfonic acids, various mercapto compounds, disulfide compounds obtained by oxidizing the mercapto compounds, and various iodized alkyl compounds. Two or more of these may be contained.

[0057] Examples of the sensitizer include thioxanthone-based sensitizers and aromatic or aliphatic tertiary amines. Specific examples include thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthen-9-one ("KAYACURE" (registered trademark) DETX-S (Nippon Kayaku Co., Ltd.) and the like. Two or more of these may be included. Examples of polymer dispersants include "DISPERBYK" (registered trademark)-102, 103, 106, 108, 109, 110, 111, 112, 116, 130, 140, 142, 145, 161, 162, 163, 164, 166, 167, 168, 170, 171174, 180, 182, 2000, 2001, 2050, 2070, 2150, 6919, and 21116 (all trade names, BYK-Chemie). Two or more of these may be used.

[0058] Examples of the adhesion improver include silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane. Two or more of these may be included.

[0059] Examples of the surfactant include anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether triethanolamine sulfate, cationic surfactants such as stearylamine acetate and lauryl trimethylammonium chloride, amphoteric surfactants such as lauryl dimethylamine oxide, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and sorbitan monostearate, fluorine-based surfactants, silicone-based surfactants, etc. Two or more of these may be included.

[0060] Examples of dispersants include pigment derivatives such as alkylamine modified pigment skeletons, carboxylic acid derivatives, and sulfonic acid derivatives, which are effective as synergists in wetting pigments and stabilizing fine pigments. Two or more of these may be included. By including a dispersant, the dispersion stability can be improved. Among these, sulfonic acid derivatives of organic pigments are more preferred, and the dispersion stability of fine pigments can be further improved.

[0061] The method for producing the colored photosensitive resin composition of the present invention is not particularly limited, and may be produced by a general-purpose method. For example, the colorant, photopolymerization initiator, and solvent are placed in a container such as a flask, and other additives are added as necessary, and then the mixture is stirred to dissolve, and the binder resin and polymerizable compound are placed, and other additives are added as necessary, and the mixture is further stirred for 20 minutes to 3 hours. The obtained colored photosensitive resin composition may be filtered.

[0062] When the colored photosensitive resin composition described above is applied onto a substrate, patterned, and baked, a colored photosensitive resin substrate is obtained in which a colored photosensitive resin film made of a cured product of the colored photosensitive resin composition is formed. That is, the colored photosensitive resin substrate of the present invention is a colored photosensitive resin substrate in which a colored photosensitive resin film made of a cured product of the colored photosensitive resin composition of the present invention is formed on a substrate. Then, a color filter is obtained by selecting a transparent substrate and patterning the colored photosensitive resin film as a green pixel, and forming blue pixels and red pixels in parallel to the green pixel. That is, the color filter of the present invention is a color filter in which a colored photosensitive resin film made of a cured product of the colored photosensitive resin composition of the present invention is formed on a substrate.

[0063] Among them, the colored photosensitive resin substrate or color filter preferably has an L* value of 27 to 31 on the surface of the colored photosensitive resin film in the Lab color system of the CIE International Commission on Illumination. That is, the colored photosensitive resin substrate of the present invention has an L* value of 27 to 31 on the surface of the colored photosensitive resin film in the Lab color system of the CIE International Commission on Illumination. Also, the color filter of the present invention has an L* value of 27 to 31 on the surface of the colored photosensitive resin film in the Lab color system of the CIE International Commission on Illumination. When the L* value is within this range, reflection on the surface of the colored photosensitive resin film is prevented, and the contrast of the pixels is improved. This L* value is also an index equivalent to the reflectance Y in the XYZ color system that is the basis of the CIE standard color system, and it can be said that the lower the L* value, the lower the reflection color tone.

[0064] The method for producing a colored photosensitive resin substrate of the present invention includes applying the colored photosensitive resin composition of the present invention onto a substrate to form a colored photosensitive resin film, placing a mask on the colored photosensitive resin film, exposing the film to light, developing the film to form a pattern, and then baking the film at a temperature of 150° C. or lower.

[0065] Methods for applying the colored photosensitive resin composition onto a substrate to form a colored photosensitive resin film include methods using a spin coater, a bar coater, a blade coater, a roll coater, a die coater, inkjet printing, screen printing, dipping, spraying, and the like.

[0066] As a method for patterning a colored photosensitive resin film, a photomask is placed on the colored photosensitive resin film, selectively exposing the film to ultraviolet light or the like, and developing the film with an alkaline developer.

[0067] Examples of exposure light sources include ultraviolet rays such as i-line, h-line, and g-line, KrF (wavelength 248 nm) laser, and ArF (wavelength 193 nm) laser. The exposure dose is 10 to 500 mJ / cm. 2 The exposure device is preferably a stepper, a mirror projection mask aligner (MPA), a parallel light mask aligner (PLA), a lens scan, etc. Among these, the lens scan method is preferable from the viewpoint of accuracy.

[0068] Examples of the developing method in the developing step include showering, dipping, and puddling. A method in which the exposed film is immersed in a developer for 5 seconds to 10 minutes is preferred. Examples of the developer include alkaline developers such as inorganic alkalis such as hydroxides, carbonates, phosphates, silicates, and borates of alkali metals such as sodium hydroxide and potassium hydroxide; amines such as 2-diethylaminoethanol, monoethanolamine, and diethanolamine; and aqueous solutions containing quaternary ammonium salts such as tetramethylammonium hydroxide and choline. After development, it is preferred to rinse with water.

[0069] Examples of alkaline substances used in the alkaline developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; and organic alkalis such as tetramethylammonium hydroxide.

[0070] After development, the resulting pattern is baked to cure the unreacted components of the colored photosensitive resin composition, forming a colored resin film. Baking can be performed in air, a nitrogen atmosphere, or a vacuum. The baking temperature is 150° C. or less, preferably 80 to 130° C., and more preferably 100 to 120° C. The baking time is preferably 0.2 to 5 hours, and the heating may be continuous or stepwise. Examples of the heating device include a hot plate and an oven. The thickness of the colored resin film is preferably 1.5 μm or more from the viewpoint of surface smoothness, and is preferably 3 μm or less, more preferably 2.6 μm or less, from the viewpoint of adjusting the peak half-width and chromaticity of the transmission spectrum to the above-mentioned preferred range and suppressing pixel defects.

[0071] The substrate may be glass or a plastic film, and may be transparent or opaque. Examples of the glass substrate include soda glass and non-alkali glass, and examples of the plastic film include polyester, polyurethane, acrylic, polycarbonate, polyimide, ethylene vinyl alcohol, olefin, polyacetal, etc. The thickness of the substrate may be appropriately selected between 10 μm and 3 mm.

[0072] The method for producing a color filter of the present invention includes applying the colored photosensitive resin composition of the present invention onto a substrate to form a colored photosensitive resin film, placing a mask on the colored photosensitive resin film, exposing the film to light, developing the film to form a pattern, and then baking the film at a temperature of 150°C or lower.

[0073] In the color filter, a transparent substrate such as glass or a transparent plastic film is used as the substrate, and the above-mentioned colored photosensitive resin film forming process is sequentially performed for each pixel of 3 to 6 primary colors and a black matrix. Since the baking temperature of the colored photosensitive resin composition of the present invention is 150°C or less, it is also possible to manufacture a color filter made of a rollable transparent plastic film, which was not applicable in the past.

[0074] Examples of the pattern shape of the color filter include a stripe shape and an island shape. The pixel width in the color filter is preferably 20 μm to 200 μm. Here, the pixel width refers to the width of the narrowest part of the pixel. Since pixel defects in a display device are less likely to occur when the pattern is thicker, pixel defects can be further suppressed by making the pixel width 20 μm or more. On the other hand, high-definition pixels can be obtained by making the pixel width 200 μm or less. Such a color filter can be preferably used in liquid crystal display devices ranging from small screen applications such as smartphones to large screen applications such as televisions.

[0075] The color filter and the driving element substrate are then placed opposite each other and bonded together with a spacer interposed between them. Liquid crystal is injected through an injection port provided in the sealing portion and then the injection port is sealed. An IC driver and the like are then mounted, and thin film transistor (TFT) elements or thin film diode (TFD) elements in addition to scanning lines and signal lines are provided on the driving element substrate, thereby producing a TFT liquid crystal display device or a TFD liquid crystal display device.

[0076] Although a liquid crystal display device generally has the color filter, a colored photosensitive resin layer can also be formed directly on the surface of the display pixel of the display device without using the color filter. That is, when the colored photosensitive resin composition described above is applied to the upper part of the green light-emitting pixel of an already formed light-emitting element, patterned, and baked at 150° C. or less, a light-emitting element is obtained in which a colored photosensitive resin film made of a cured product of the colored photosensitive resin composition is formed on the upper part of the green light-emitting pixel.

[0077] Among these, it is preferable that the colored photosensitive resin film surface formed on the surface of the light-emitting element has an L* value in the Lab color system of the CIE International Commission on Illumination of 27 to 31. That is, the light-emitting element of the present invention is a light-emitting element in which a colored photosensitive resin film made of a cured product of the colored photosensitive resin composition of the present invention is formed on the top of a green-emitting pixel, and the colored photosensitive resin film surface has an L* value in the Lab color system of the CIE International Commission on Illumination of 27 to 31. When the L* value is within this range, reflection on the surface of the colored photosensitive resin film is prevented, and the contrast of the pixels of the light-emitting element is also improved.

[0078] The light-emitting element may be an organic light-emitting element or an inorganic light-emitting element, the former of which may be applied to an organic electroluminescence display, and the latter of which may be applied to a micro LED display. In particular, the light-emitting pixel material of an organic electroluminescence display has a relatively low heat resistance, and there is a problem that it will deteriorate due to heat if a protective layer is formed on the surface and then baked, but this problem can be solved by the present invention. In addition, the formed green pixel exhibits high color reproducibility and excellent low reflection characteristics, and can also function as a protective layer. EXAMPLES

[0079] The present invention will be described below with reference to examples, but these examples are merely illustrative and the present invention is not limited to these examples. The materials used in each example and each comparative example are as follows.

[0080] <Production Example 1 (Preparation of Polymerizable Compound Solutions (A1) and (B1))> A polymerizable compound solution (A1) was prepared by dissolving and diluting 50 g of KAYARD DPHA (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd. in 50 g of PGMEA. A polymerizable compound solution (B1) was prepared by dissolving and diluting 50 g of PETRA (pentaerythritol triacrylate) manufactured by Daicel Allnex Co., Ltd. in 50 g of PGMEA.

[0081] <Production Example 2 (Preparation of Green Colorant Dispersion (C1))> A slurry was prepared by mixing 150 g of "FASTOGEN" (registered trademark) Green A110 (CI Pigment Green 58) manufactured by DIC Corporation, 70 g of polymer dispersant solution (60 mass% propylene glycol monomethyl ether solution) "BYK" (registered trademark) LPN6919 manufactured by BYK Japan Co., Ltd., 90 g of acrylic resin "Cyclomer" (registered trademark) ACA250 (45 mass% dipropylene glycol monomethyl ether solution) manufactured by Daicel Chemical Industries, Ltd., and 700 g of propylene glycol monomethyl ether. The beaker containing the slurry was connected to a dyno mill with a tube, and a dispersion process was performed for 8 hours at a peripheral speed of 14 m / s using zirconia beads with a diameter of 0.5 mm as a medium, to prepare a green colorant dispersion liquid (C1).

[0082] <Production Example 3 (Preparation of Yellow Colorant Dispersion (C2))> A yellow colorant dispersion (C2) was prepared in the same manner as in Production Example 1, except that "LIONOGEN" (registered trademark) YELLOW 1010 (CI Pigment Yellow 138) manufactured by Toyo Ink SC Holding Co., Ltd. was used instead of the CI Pigment Green 58.

[0083] <Production Example 4 (Synthesis of Binder Resin Solution (D1))> A 500 mL three-neck flask was charged with 33 g (0.3 mol) of methyl methacrylate, 33 g (0.3 mol) of styrene, 35 g (0.5 mol) of methacrylic acid, 3 g (0.02 mol) of 2,2'-azobis(2-methylbutyronitrile), and 150 g of PGMEA, and the mixture was stirred at 90°C for 2 hours, after which the internal temperature was raised to 100°C and the mixture was stirred for an additional hour to obtain a reaction solution.

[0084] To the obtained reaction solution, 33 g (0.2 mol) of glycidyl methacrylate, 1.2 g (0.01 mol) of dimethylbenzylamine, and 0.2 g (0.002 mol) of p-methoxyphenol were added and stirred at 90°C for 4 hours, and then PGMEA was added to obtain a binder resin solution (D1) with a solid content concentration of 40 mass%.

[0085] The acid value of the binder resin was measured in a 0.1 mol / L potassium hydroxide-ethanol solution using an automatic potentiometer AT-610 manufactured by Kyoto Electronics Manufacturing Co., Ltd., and was found to be 119 (mgKOH / g). The weight average molecular weight calculated in terms of polystyrene was calculated using a GPC device and was found to be 22,000.

[0086] <Production Example 5 (Preparation of Transparent Filler Dispersion Solution (E1))> A transparent filler dispersion solution (E1) was prepared by dispersing acrylic resin particles "Fine Square" (registered trademark) FS-106 manufactured by Nippon Paint Industrial Coatings Co., Ltd. together with 5% by mass of polymer dispersant "Hinoact" manufactured by Kawasaki Fine Chemical Co., Ltd. in isopropyl alcohol / toluene = 50 parts by weight: 50 parts by weight using a bead mill.

[0087] <Production Example 6 (Preparation of Transparent Filler Dispersion Solution (E2))> Polypropylene microparticles "Flow Beads" RP manufactured by Sumitomo Seika Chemicals Co., Ltd. were dispersed in a xylene / toluene mixture of 50 parts by weight:50 parts by weight using a beads mill together with 5% by mass of polymer dispersant "Hinoact" manufactured by Kawasaki Fine Chemicals Co., Ltd. to prepare a transparent filler dispersion solution (E2).

[0088] <Production Example 7 (Preparation of Transparent Filler Dispersion Solution (E3))> A transparent filler dispersion solution (E3) was prepared by dispersing polyurethane microparticles Granpearl GU-0700P manufactured by Aica Kogyo Co., Ltd. together with 5% by mass of polymer dispersant "Hinoact" manufactured by Kawasaki Fine Chemical Co., Ltd. in xylene / toluene = 50 parts by weight: 50 parts by weight using a bead mill.

[0089] <Production Example 8 (Preparation of Transparent Filler Dispersion Solution (E4))> Sodium fluoride nanoparticles manufactured by Stella Chemifa Co., Ltd. were dispersed in isopropyl alcohol together with 5% by mass of a polymer dispersant "Hinoact" manufactured by Kawasaki Fine Chemical Co., Ltd. using a beads mill to prepare a transparent filler dispersion solution (E4).

[0090] <Production Examples 9 to 12 (Preparation of Transparent Filler Dispersion Solutions (E5) to (E8))> As the other transparent filler dispersion solutions, the following commercially available dispersion solutions were used.

[0091] E5: Nissan Chemical Industries, Ltd. Colloidal silica fine particle dispersion "Organosilica sol" E6: Lithium fluoride nanoparticle dispersion liquid manufactured by Stella Chemifa Co., Ltd. E7: Magnesium fluoride nanoparticle dispersion liquid manufactured by Stella Chemifa Co., Ltd. E8: Calcium fluoride nanoparticle dispersion liquid manufactured by Stella Chemifa Co., Ltd. <Example 1 (Preparation of Colored Photosensitive Resin Composition (J1))> Into a 50 mL plastic bottle, 0.45 g of the polymerizable compound solution (A1) obtained in Production Example 1, 3.0 g of the polymerizable compound solution (B1), 6.6 g of the dispersion (C1) obtained in Production Example 2, 4.4 g of the dispersion (C2) obtained in Production Example 3, 1.0 g of the binder resin solution (D1) obtained in Production Example 4, 0.01 g of "ADEKA ARCLES" (registered trademark) NCI831 (manufactured by ADEKA CORPORATION) and 0.01 g of "IRGACURE" (registered trademark) 379 (manufactured by BASF Japan Ltd.) as photopolymerization initiators, and 15.0 g of PGMEA as an organic solvent were added and stirred for 3 hours to prepare a colored photosensitive resin composition (J1).

[0092] <Examples 2 to 23 (Preparation of Colored Photosensitive Resin Compositions (J2) to (J23) and Comparative Examples 1 to 12)> Colored photosensitive resin compositions (J2) to (J23) and a comparative colored photosensitive resin composition were prepared in the same manner as in Example 1, except that the components and weights of the green colorant dispersion liquid (C1), the yellow colorant dispersion liquid (C2), the polymerizable compound solution (A1), and the polymerizable compound solution (B1) were changed as shown in Tables 1 and 4.

[0093] <Example 24 (Preparation of Colored Photosensitive Resin Composition (J24))> Into a 50 mL plastic bottle, 0.45 g of the transparent filler dispersion solution (E1) obtained in Production Example 5, 0.45 g of the polymerizable compound solution (A1) obtained in Production Example 1, 3.0 g of the polymerizable compound solution (B1), 6.6 g of the dispersion solution (C1) obtained in Production Example 2, 4.4 g of the dispersion solution (C2) obtained in Production Example 3, 1.0 g of the binder resin solution (D1) obtained in Production Example 4, 0.01 g of "ADEKA ARCLES" (registered trademark) NCI831 manufactured by ADEKA Corporation and 0.01 g of "IRGACURE" (registered trademark) 379 manufactured by BASF Japan Ltd. as photopolymerization initiators, and 15.0 g of PGMEA as an organic solvent were added and stirred for 3 hours to prepare a colored photosensitive resin composition (J24).

[0094] <Examples 25 to 57 (Preparation of Colored Photosensitive Resin Compositions (J25) to (J57))> Colored photosensitive resin compositions (J25) to (J57) were prepared in the same manner as in Example 24, except that the components and weights of the transparent filler dispersion solutions (E1 to E8), the green colorant dispersion solution (C1), the yellow colorant dispersion solution (C2), the polymerizable compound solution (A1), and the polymerizable compound solution (B1) were changed as shown in Tables 2 and 3.

[0095] <Low-temperature baking property (peelability) evaluation> The colored photosensitive resin compositions (J1) to (J57) obtained in Examples 1 to 57 and the colored photosensitive resin compositions of Comparative Examples 1 to 12 were applied onto a glass substrate and dried at 70°C for 10 minutes. Thereafter, the substrate was exposed to 40 mJ of i-line through a photomask having a 20 μm line and space pattern. Next, the substrate was shower-developed with a 0.3 mass% tetramethylammonium hydroxide aqueous solution at 23°C for 50 seconds, and then washed with pure water. The sample was divided into three portions and baked at 80°C, 100°C, and 150°C for 30 minutes each to obtain a colored photosensitive resin substrate consisting of a colored photosensitive resin film having a thickness of 2.3 μm.

[0096] The same colored photosensitive resin composition was applied again on the colored photosensitive resin film thus formed, and the same process as above was carried out to obtain a colored photosensitive resin substrate consisting of a colored photosensitive resin film with a total thickness of 2.3 μm. The presence or absence of interlayer peeling or cohesive failure of the pattern of the colored photosensitive resin film on the substrate was confirmed under a microscope, and the low-temperature baking property (peelability) was evaluated according to the following evaluation criteria, and the results are shown in Tables 1 to 4.

[0097] A: No delamination or cohesive failure when baked at 80℃, 100℃, or 150℃ B: Slight delamination or cohesive failure occurs when baked at 80°C, but no delamination or cohesive failure occurs when baked at 100°C or 150°C. C: Slight delamination or cohesive failure occurs when fired at 80°C and 100°C, but no delamination or cohesive failure occurs when fired at 150°C. D: Delamination or cohesive failure occurs when fired at 80°C, 100°C, or 150°C. <Solubility evaluation and parallel light transmittance measurement> 1 g of each of the colored photosensitive resin compositions (J1) to (J57) obtained in Examples 1 to 57 and the colored photosensitive resin compositions of Comparative Examples 1 to 12 was sampled and diluted with organic solvent G1 to a solid content weight ratio of (10000 / 2.3), and the solubility was evaluated according to the following evaluation criteria.

[0098] A: No visible suspended matter, and no residue on the filtration media with a pore size of 1 μm. B: A small amount of suspended solids can be seen by visual inspection, but no residues can be seen on the 1 μm pore size filter media. C: Suspended matter was observed by visual inspection, and residues were also observed on the filter media with a pore size of 1 μm. The diluted colored photosensitive resin composition solution was then filled into a spectrophotometer cell with an optical path length of 1 cm, and the parallel light transmittance at wavelengths of 460 nm, 530 nm, and 620 nm was measured using a Shimadzu UV-2500PC spectrophotometer. The results are shown in Tables 1 to 4.

[0099] <Reflectance measurement> The colored photosensitive resin compositions (J1) to (J57) obtained in Examples 1 to 57 and the colored photosensitive resin compositions of Comparative Examples 1 to 12 were entirely coated on a glass substrate and dried at 70°C for 10 minutes. Then, after overall exposure with i-line at 40 mJ, it was shower-developed for 50 seconds with a 0.3 mass% aqueous solution of tetramethylammonium hydroxide at 23°C and then washed with pure water. The sample was baked at 150°C for 30 minutes to obtain a colored photosensitive resin substrate composed of a colored photosensitive resin film with a thickness of 2.3 μm. The reflectance of the surface of the sample was measured by SCI (including regular reflected light) with a measuring diameter of φ8 mm using a spectrophotometer CM-3700A manufactured by Konica Minolta, Inc., and the results are shown in Tables 1 to 4.

[0100] <Measurement of L*> The colored photosensitive resin compositions (J1) to (J57) obtained in Examples 1 to 57 and the colored photosensitive resin compositions of Comparative Examples 1 to 12 were entirely coated on a glass substrate and dried at 70°C for 10 minutes. Then, after overall exposure with i-line at 40 mJ, it was shower-developed for 50 seconds with a 0.3 mass% aqueous solution of tetramethylammonium hydroxide at 23°C and then washed with pure water. The sample was baked at 150°C for 30 minutes to obtain a sample of a colored photosensitive resin film with a thickness of 2.3 μm, and the L* of the surface of the sample was measured using a spectrophotometer CM-2600d manufactured by Konica Minolta, Inc. under a D65 light source and a 10° field of view, and the results are shown in Tables 1 to 4.

[0101]

Table 1

[0102]

Table 2

[0103]

Table 3

[0104]

Table 4

[0105] From the results of the above Examples and Comparative Examples, it was confirmed that the colored photosensitive resin film of the Examples has a superior external light reflection effect compared to the Comparative Examples, and is excellent in that there is no interlayer delamination or cohesive failure in the low-temperature baking evaluation.

[0106] <Example 58 (Production of Color Filter)> Color filters were manufactured using the colored photosensitive resin compositions manufactured in Examples 17 to 23 and Examples 42 to 57. Specifically, each of the colored photosensitive resin compositions was applied to a 2-inch square glass substrate (manufactured by Corning, "EAGLE XG") by spin coating, and then placed on a heating plate and maintained at a temperature of 80°C for 3 minutes to form a colored photosensitive resin film. Next, a test photomask having an exposure portion pattern of 3 x 3 cm was placed on the colored photosensitive resin film, and ultraviolet rays were irradiated at a distance of 100 μm from the test photomask.

[0107] The ultraviolet light source is a 1KW high-pressure mercury lamp containing g, h, and i rays, and has an output of 100mJ / cm 2 The colored photosensitive resin film irradiated with ultraviolet light was developed by immersing it in a KOH aqueous solution developer with a pH of 10.5 for 2 minutes. The glass plate coated with the colored photosensitive resin film was washed with distilled water, dried by blowing nitrogen gas, and baked in a heating oven at 120°C for 30 minutes to produce a green pixel of a color filter. The thickness of the cured green pixel was measured using a film thickness measuring device (DEKTAK6M; manufactured by Veeco) and found to be 2.3 μm.

[0108] The color filter exhibited excellent low reflection performance, with a reflectance of 6.4% or less without a transparent filler and 5.0% or less with a transparent filler, and also had high contrast. In both cases, the low-temperature firing evaluation showed no interlayer delamination or cohesive failure.

[0109] <Example 59 (Production of organic electroluminescence device)> Instead of the glass substrate ("EAGLE XG" manufactured by Corning Incorporated), an organic electroluminescence element having red, green, and blue light-emitting pixels already formed thereon and a sealing film formed thereon was used, and an organic electroluminescence element having a hardened green photosensitive resin film formed on the green light-emitting pixel pattern was manufactured in the same manner as in Example 56, except that the baking temperature was set to 80°C.

[0110] The organic electroluminescence element exhibited excellent low reflection performance, with a reflectance of 6.4% or less without a transparent filler and 5.0% or less with a transparent filler, and also had high contrast. In both cases, the low-temperature firing evaluation showed no interlayer delamination or cohesive failure.

[0111] <Example 60 (manufacturing of micro LED element)> Instead of the glass substrate (manufactured by Corning, "EAGLE XG"), a micro LED element on which red, green and blue light emitting pixels were already formed and a protective film was formed thereon was used, and a cured green photosensitive resin film was formed on the green light emitting pixel pattern in the same manner as in Example 56, except that the baking temperature was 100° C. The micro LED element showed excellent low reflection performance with a reflectance of 6.4% or less without a transparent filler and 5.0% or less with a transparent filler, and also had high contrast, and was excellent in both cases with no interlayer peeling or cohesive failure in the low temperature baking evaluation.

Claims

1. A colored photosensitive resin composition comprising C.I. Pigment Green 59 or C.I. Pigment Green 58, a yellow colorant, a polymerizable compound, a binder resin, and a photopolymerization initiator, wherein the weight ratio of the C.I. Pigment Green 59 or C.I. Pigment Green 58 to the yellow colorant is 60:40 to 90:10, the polymerizable compound comprises dipentaerythritol hexaacrylate and pentaerythritol triacrylate, and the ratio of the weight (A) of the dipentaerythritol hexa(meth)acrylate to the weight (B) of the pentaerythritol tri(meth)acrylate is 0.15<A / B<3.

20.

2. 2. The colored photosensitive resin composition according to claim 1, wherein the solid content is diluted with propylene glycol monomethyl ether acetate to a weight ratio of (10,000 / 2.3) and filled into a spectrophotometer cell having an optical path length of 1 cm, and the parallel light transmittance measured is 20% or less at wavelengths of 460 nm and 620 nm and 70% or more at a wavelength of 530 nm.

3. The colored photosensitive resin composition according to claim 1 or 2, wherein the weight ratio of the C.I. Pigment Green 59 and the C.I. Pigment Green 58 to the yellow colorant is 75:25 to 90:10, and the yellow colorant is C.I. Pigment Yellow 150 or C.I. Pigment Yellow 185.

4. 3. The colored photosensitive resin composition according to claim 1, further comprising a photopolymerization initiator having a melting point of 72° C. to 96° C.

5. 3. The colored photosensitive resin composition according to claim 1, further comprising a transparent filler.

6. 6. The colored photosensitive resin composition according to claim 5, wherein the transparent filler is any particle selected from the group consisting of silicon-based resins, fluorine-based resins, acrylic resins, urethane resins, polyvinyl alcohol resins, polypropylene resins, and polyacetal resins.

7. 3. A colored photosensitive resin substrate comprising a colored photosensitive resin film formed on a substrate, the colored photosensitive resin film being made of a cured product of the colored photosensitive resin composition according to claim 1 or 2, wherein the L* value of the surface of the colored photosensitive resin film in the Lab color system of the CIE International Commission on Illumination is 27 to 31.

8. 3. A color filter comprising a colored photosensitive resin film formed on a substrate, the colored photosensitive resin film being made of a cured product of the colored photosensitive resin composition according to claim 1 or 2, wherein the L* value of the surface of the colored photosensitive resin film in the Lab color system of the CIE International Commission on Illumination is 27 to 31.

9. 3. A light-emitting element comprising a colored photosensitive resin film made of a cured product of the colored photosensitive resin composition according to claim 1 or 2 formed on an upper portion of a green light-emitting pixel, wherein the L* value of the surface of the colored photosensitive resin film in the Lab color system of the CIE International Commission on Illumination is 27 to 31.

10. 3. A method for producing a colored photosensitive resin substrate, comprising: applying the colored photosensitive resin composition according to claim 1 or 2 onto a substrate to form a colored photosensitive resin film; placing a mask on the colored photosensitive resin film, exposing the film to light, developing the film to form a pattern, and then baking the film at a temperature of 150° C. or lower.

11. 3. A method for producing a color filter, comprising: applying the colored photosensitive resin composition according to claim 1 or 2 onto a substrate to form a colored photosensitive resin film; placing a mask on the colored photosensitive resin film, exposing the film to light, developing the film to form a pattern, and then baking the film at a temperature of 150° C. or lower.

12. 3. A method for producing a light-emitting element, comprising: applying the colored photosensitive resin composition according to claim 1 or 2 onto an upper portion of a green light-emitting pixel to form a colored photosensitive resin film; placing a mask on the colored photosensitive resin film, exposing the film to light, developing the film to form a pattern, and then baking the film at a temperature of 150° C. or less.

Images