Photosensitive resin composition, method for producing cured film, substrate with cured film, display device, and sensor

Abstract

To provide a photosensitive resin composition enabling production of a cured film with a low refractive index and also allowing fine patterning, a method for producing a cured film using the composition, a substrate with a cured film produced by the method, and a display device and a sensor each including the substrate with the cured film.SOLUTION: A photosensitive resin composition of the present invention comprises (A) hollow fillers in which the shell-forming material has a refractive index of 1.20 to 1.40, (B) an alkali-soluble resin, and (C) a photopolymerization initiator. The component (B) has a refractive index of 1.50 to 1.70 when formed into a cured film having a thickness of 1 μm.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, a method for producing a cured film, a substrate with a cured film, a display device, and a sensor.

Background Art

[0002] In order to improve the visibility of display devices, touch panels, etc., displays used for these are required to have a reduced reflectance. Therefore, a coating film that reduces the reflectance due to a refractive index difference may be applied to a black matrix or the like that easily reflects light.

[0003] As such a coating layer, a layer having a low refractive index is used. In order to form a layer having a low refractive index, a resin composition added with a low refractive material is known (such as Patent Document 1). Further, since the coating film may be patterned according to the application, an alkali-soluble resin may be added to the composition for forming the coating film to impart alkali developability.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] There is a demand for a photosensitive resin composition that can produce a cured film having a low refractive index and is also capable of fine patterning. However, with the conventional resin compositions described in Patent Document 1 and the like, it has not been possible to achieve both low refractive index of the cured film and fine patterning performance.

[0006] The present invention has been made in view of such a point, and it is possible to produce a cured film having a low refractive index and capable of fine patterning, a method for producing a cured film using the same, a substrate with a cured film produced by the method, and a display device and a sensor having the substrate with the cured film. The purpose is to provide.

Means for Solving the Problems

[0007] In order to solve the above problems, as a result of intensive studies by the present inventors, a hollow filler having a refractive index of 1.20 to 1.40 for the material constituting the shell, and a refractive index of 1.50 to 1.70 when the cured film has a film thickness of 1 μm. It has been found that a cured film obtained by curing a photosensitive resin composition containing an alkali-soluble resin and a photopolymerization initiator is suitable, and the present invention has been completed.

[0008] The cause of this is not necessarily clear, but it is considered as follows. The hollow filler has a cavity inside and can hold a low refractive index medium such as air in the cavity. Therefore, the refractive index of the hollow filler is likely to decrease with respect to the refractive index of the material constituting the shell. By combining a hollow filler having a refractive index of the material constituting such a shell within the above range and an alkali-soluble resin having a refractive index within the above range when used as a cured film, the refractive index of the cured film can be effectively reduced.

[0009] In addition, a hollow filler having a refractive index within the above range is less likely to disperse the light exposed to the photosensitive resin composition applied to the substrate and is more likely to travel straight. In particular, when using hollow magnesium fluoride as the hollow filler, the effect of making the exposed light travel straight as described above can be easily obtained, and the patterning property can be easily enhanced. Further, for example, when forming a coating film having a desired refractive index, using a hollow filler can suppress the addition amount of the inorganic filler, so that the addition amount of a resin component such as an alkali-soluble resin can be increased, and the patterning property can be easily enhanced. Therefore, by using such a hollow filler and an alkali-soluble resin, it is considered that a decrease in the accuracy of the pattern due to the dispersed light and a notch at the pattern end due to insufficient light reaching the bottom of the composition can be suppressed.

[0010] That is, the above problems can be solved by the following configuration.

[0011] [1] (A) A hollow filler, (B) An alkali-soluble resin, (C) A photopolymerization initiator, and the refractive index of the material constituting the shell of the (A) hollow filler is 1.20 to 1.40, the refractive index of the (B) alkali-soluble resin is 1.50 to 1.70 when formed into a cured film with a film thickness of 1 μm, A photosensitive resin composition.

[0012] [2] The average primary particle size of the (A) hollow filler is 150 nm or less The photosensitive resin composition according to [1].

[0013] [3] The porosity of the (A) hollow filler is 5% by volume to 80% by volume The photosensitive resin composition according to [1] or [2].

[0014] [4] The material constituting the shell of the (A) hollow filler is magnesium fluoride, The photosensitive resin composition according to any one of [1] to [3].

[0015] [5] A photosensitive resin composition containing a photosensitive resin composition according to any one of [1] to [4].

[0016] [6] The (D) colorant is a light-shielding material, photosensitive resin composition according to [5].

[0017] [7] The light-shielding material contains carbon black, photosensitive resin composition according to [6].

[0018] [8] A step of applying the photosensitive resin composition according to any one of [1] to [7] onto a substrate, a step of exposing the applied photosensitive resin composition through a photomask, removing the unexposed portion by development, and then performing heat treatment, A method for manufacturing a cured film having the above steps.

[0019] [9] A patterned cured film manufactured by the method for manufacturing a cured film according to [8], having a substrate with a cured film.

[0020]

[10] A display device having the substrate with a cured film according to [9].

[0021]

[11] A sensor having the substrate with a cured film according to [9]. [Advantages of the Invention]

[0022] According to the present invention, there are provided a photosensitive resin composition capable of producing a cured film having a low refractive index and enabling fine patterning, a method for manufacturing a cured film using the same, a substrate with a cured film manufactured by the method, and a display device and a sensor having the substrate with a cured film. [Embodiments for Carrying Out the Invention]

[0023] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. In the present invention, when the content of each component has a first decimal place of 0, the notation after the decimal point may be omitted.

[0024] In addition, in this specification, the numerical range represented by "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value.

[0025] Also, in this specification, "(meth)acrylic acid" is a general term for acrylic acid and methacrylic acid, and means one or both of them. Also, "(meth)acrylate" is a general term for acrylate and methacrylate, and means one or both of them. Also, "(meth)acryloyl group" is a general term for acryloyl group and methacryloyl group, and means one or both of them.

[0026] 1. Photosensitive resin composition The photosensitive resin composition for a light-shielding film according to this embodiment is (A) a hollow filler (hereinafter, also simply referred to as "(A) component"), (B) an alkali-soluble resin (hereinafter, also simply referred to as "(B) component"), (C) a photopolymerization initiator (hereinafter, also simply referred to as "(C) component"), and contains the following. Each component will be described below.

[0027] 1-1. (A) Hollow filler The (A) component is not particularly limited as long as it is a hollow filler having a refractive index of the material constituting the shell of 1.20 to 1.40.

[0028] The hollow filler is a particle having a cavity inside, and the production method (gas-phase reaction, liquid-phase reaction) and shape (spherical, non-spherical) are not particularly limited. Also, metal oxide particles surface-treated with a coupling agent or the like may be used. The cavity inside the hollow filler is also referred to as a cavity part, and the outer shell part is also referred to as a shell.

[0029] Such a hollow filler can lower the refractive index of a cured film formed by curing a photosensitive resin composition. For example, when the photosensitive resin composition contains (D) a colorant, inclusion of such a hollow filler reduces the refractive index of the cured film containing (D) the colorant. Then, reflection caused by the refractive index difference between the formed cured film and an adjacent layer or air is suppressed.

[0030] As the refractive index of the material constituting the shell of the component (A), literature values may be used. For example, a refractive index list published by Filmetrics Inc. (https: / / www.filmetricsinc.jp / refractive-index-database) etc. can be referred to. Further, the refractive index of the material constituting the shell of the component (A) may be measured by the following method. It can be determined from a transparent mixture obtained by mixing the component (A) processed into a powder form with a standard refractive liquid having a known refractive index. In this case, the refractive index of the component (A) is calculated based on the change from the refractive index of the standard refractive liquid in the said mixture. The refractive index of the component (A) may be measured using an Abbe refractometer. From the refractive index of the component (A) thus obtained, the refractive index of the material constituting the shell of the component (A) is calculated by the following formula (1). Formula (1) n シェル =(n A -1.00×porosity / 100) / (1-(porosity / 100)) Here, n シェル represents the refractive index of the material constituting the shell of the component (A), and n A represents the refractive index of the component (A). The porosity represents the ratio (volume %) of the cavity part in the particles, calculated by the measurement method described later. Note that the value of the refractive index of the material constituting the shell of the component (A) and the refractive index of the component (A) in the present application refer to the value of the refractive index with respect to light having a wavelength of 550 nm.

[0031] When the photosensitive resin composition does not contain the light-shielding material described below, the porosity of the hollow filler particles is preferably 5% to 80% by volume, more preferably 5% to 60% by volume, and even more preferably 20% to 60% by volume. When the porosity is 5% by volume or more, a light-shielding film with a low refractive index can be easily obtained. When the porosity is within the range of 20% by volume or more, a cured film with a lower refractive index can be obtained. When the porosity is within the range of 80% by volume or less, excessive scattering of the exposure light is suppressed, and a cured film with good patterning properties and transmittance can be obtained. When the porosity is within the range of 60% by volume or less, a cured film with better patterning properties and transmittance can be obtained.

[0032] When the photosensitive resin composition contains the light-shielding material described below, the porosity of the hollow filler particles is preferably 5% to 80% by volume, and more preferably 20% to 80% by volume. When the porosity is 5% by volume or more, a cured film with a low reflectivity and a low refractive index can be easily obtained. When the porosity is 20% by volume or more, a cured film with a lower reflectivity and a lower refractive index can be easily obtained. When the porosity is 80% by volume or less, a cured film with good patterning properties can be obtained.

[0033] Note that the porosity is the ratio of the cavity part inside the particles to the particles. The porosity can be determined by using a transmission electron microscope. The cavity part of the hollow filler has a low density, and the contrast of the cavity part becomes low in the transmission electron microscope photograph, so the shell and the cavity part of the hollow filler can be confirmed. From the above microscope photograph, first, the longest diameter and the shortest diameter of the hollow filler are measured, and the average value is taken as the particle diameter of the particle, and the volume (V1) assuming the particle shape is a true sphere is obtained. Next, the longest diameter and the shortest diameter of the cavity part of the particle are measured, and the average value is taken as the diameter of the cavity, and the volume (V2) assuming the cavity part shape is a true sphere is obtained. The same measurement is performed on 10 randomly selected particles. The porosity can be calculated for each of the 10 particles as the ratio of the volume (V2) to the volume (V1), and can be represented by their average value.

[0034] Examples of component (A) include sodium hexafluoroaluminate (cryolite), magnesium fluoride, lithium fluoride, etc., which can be used.

[0035] Among these, magnesium fluoride is preferably used as component (A). The reason for this is not necessarily clear, but it is considered as follows. For example, magnesium fluoride not only has a refractive index of 1.38 (the above literature value) at a wavelength of 550 nm of the material constituting the shell, which is sufficiently low, but also has a sufficiently high specific gravity (about 3.2 g / cm 3 ) with respect to the density of general-purpose solvents (about 0.8 to 1.5 g / ml). And such hollow fillers, even if they have a medium with a low specific gravity (such as air) in the cavity, when the photosensitive resin composition is applied to a substrate and before drying is completed, it is difficult to float in the coating film and is likely to be uniformly present in the film thickness direction. Therefore, due to its low refractive index, it is not only difficult to disperse the exposed light and easy to make it travel straight, but also because the hollow fillers are likely to be uniformly present in the film, it is less likely to cause a multiple scattering phenomenon where the light scattered by the hollow fillers is scattered again by another hollow filler, and it is easy to obtain the effect of making the exposed light travel straight, and it is less likely to cause a decrease in the accuracy of the pattern due to the dispersed light. On the other hand, for example, silica has a refractive index of 1.46 (the above literature value) at a wavelength of 550 nm of the material constituting the shell, and because the refractive index is relatively high, it is considered that the exposed light is easily dispersed and the accuracy of the pattern is likely to decrease due to the dispersed light. Also, the specific gravity is lower than that of magnesium fluoride (about 2.2 g / cm 3 ), and hollow silica is likely to float in the coating film when the photosensitive resin composition is applied to a substrate and before drying is completed, and is likely to be unevenly distributed on the air interface side (the side opposite to the substrate). As a result, it is considered that the light scattered by the hollow fillers is likely to be scattered again by another hollow filler, making it difficult to improve the accuracy of the pattern.

[0036] From the perspective of facilitating an increase in pencil hardness, it is preferable to use magnesium fluoride. Since the hollow filler has a cavity inside, when a compressive stress such as a pencil hardness test is applied, the filler itself is likely to crack. And when a large number of hollow filler particles are unevenly distributed on the surface, it is considered that cracks are likely to occur in the hollow filler. As a result, for example, when a large number of hollow filler particles are unevenly distributed on the surface, the cracks in the hollow filler increase the interface between the particles and air, etc., so the scattering component becomes large. Also, when there is a hollow filler on the outermost surface, as a result of the hollow filler falling off, surface irregularities are generated, or scratches are likely to occur due to the microparticles generated by the cracks being dragged on the pencil. Then, the location where the pencil hardness test of the pencil hardness is performed becomes easily visible. As described above, since magnesium fluoride is likely to be uniform in the film thickness direction, it is considered that cracks in the hollow filler are less likely to occur and the pencil hardness is likely to increase.

[0037] Furthermore, from the viewpoint of facilitating an increase in the reflectance obtained by the SCI method of the cured film (hereinafter also referred to as "SCI reflectance") and the lightness obtained by the SCE method (hereinafter also referred to as "SCE lightness"), it is preferable to use magnesium fluoride as the component (A). Here, in the SCE method, specularly reflected light is removed and only diffusely reflected light is measured, and in the SCI method, a measurement value including diffusely reflected light and specularly reflected light is obtained. In particular, in the case of a transparent film that does not contain the (D) colorant described later, since it may be used for the outermost surface layer of a display device, a sensor, etc., it is preferable to reduce the SCI reflectance including reflected light from external light, room lights, etc. In the case of a light-shielding film containing the (D) colorant described later, since it may be used by being laminated with other layers in addition to the outermost surface layer, it is preferable to reduce not only the SCI reflectance but also the SCE lightness from which specularly reflected light is removed. The reason why the use of magnesium fluoride as the component (A) can reduce the SCI reflectance and the SCE reflectance is not necessarily clear, but it is considered as follows. As described above, since magnesium fluoride has a specific gravity higher than that of general-purpose solvents, it is considered to be likely to be uniformly present in the film thickness direction. Then, reagglomeration of magnesium fluoride particles, etc. is difficult to progress, and it becomes easy to suppress diffuse reflection. As a result, the SCI reflectance and the SCE lightness are likely to decrease. On the other hand, for example, as described above, silica has a lower specific gravity than magnesium fluoride (about 2.2 g / cm 3 ), and it is likely to be unevenly distributed on the air interface side (the side opposite to the substrate). As a result, the frequency of silica particles on the air interface side increases, so reagglomeration, etc. is likely to progress, and the particle diameter in the film is likely to increase. As a result, it is considered that the intensity of diffusely reflected light increases.

[0038] From the viewpoint of facilitating the uniform presence of the hollow filler in the coating film as described above, the specific gravity of the material constituting the shell of the component (A) is preferably 2.5 g / cm 3 ~5.0 g / cm 3 and more preferably 3.0 g / cm 3 ~5.0 g / cm 3 and even more preferably 3.2 g / cm 3 ~5.0 g / cm 3It is more preferable that it is so. In addition, as the specific gravity of the material constituting the shell of the component (A), literature values can be used.

[0039] The hollow filler having a refractive index within the above range is less likely to disperse the light exposed to the photosensitive resin composition applied to the substrate in the composition and is more likely to travel straight. Thus, it is considered that it is possible to suppress a decrease in pattern accuracy due to the dispersed light and chipping of the pattern end due to insufficient light reaching the bottom of the composition.

[0040] When the photosensitive resin composition does not contain the light-shielding material described later, the average primary particle size of the component (A) is preferably 150 nm or less, more preferably 10 nm to 150 nm, still more preferably 10 nm to 90 nm, and most preferably 10 nm to 70 nm. When the average primary particle size is 10 nm or more, since the surface energy is not so high, it is difficult to aggregate in the film, and a decrease in pattern accuracy due to the aggregated component (A) diffusing the exposed light hardly occurs. When it is 150 nm or less, since the average primary particle size is moderately small, a decrease in pattern accuracy due to the single particle becoming a diffusion source hardly occurs. Further, when it is 90 nm or less, the patterning property is further enhanced, and when it is 70 nm or less, diffusion by the aggregated component (A) is more suppressed, so the transmittance is further increased.

[0041] When the photosensitive resin composition contains the light-shielding material described later, the average primary particle size of the component (A) is preferably 150 nm or less, more preferably 10 nm to 150 nm. When it is 150 nm or less, since the average primary particle size is moderately small, a decrease in pattern accuracy due to the single particle becoming a diffusion source hardly occurs.

[0042] The average primary particle size of the component (A) is a value obtained by observing the particle size with a transmission electron microscope, randomly selecting 100 particles, measuring the major axis length and minor axis length of the particles, and calculating the sum average thereof. In addition, when the component (A) constitutes an aggregate or an aggregate, the primary particle refers to the particles constituting these.

[0043] As long as the average secondary particle diameter of the component (A) is dispersed with an average secondary particle diameter of 1 to 1000 nm (average particle diameter measured by a laser diffraction / scattering particle size distribution meter or a dynamic light scattering particle size distribution meter), known inorganic fillers can be used without particular limitation. A more preferable average secondary particle diameter is 10 to 300 nm.

[0044] The shell thickness of the component (A) is preferably 3 nm to 25 nm, and more preferably 3 nm to 20 nm. By setting the shell thickness to 3 nm or more, cracking of the shell can be suppressed when dispersing the hollow filler, and by setting the shell thickness to 25 nm or less, the porosity can be easily ensured. The shell thickness is the average value of the shell thicknesses of 10 randomly observed particles by a transmission electron microscope.

[0045] The production method (gas-phase reaction, liquid-phase reaction) and shape (spherical, non-spherical) of the component (A) are not particularly limited.

[0046] The component (A) may be dispersed by a dispersant. As the dispersant, known dispersants can be used, and the component (B) can also be used. The content of the component (A) described later is an amount excluding the dispersant that has little influence on properties such as refractive index.

[0047] When the photosensitive resin composition does not contain the light-shielding material described below, the content of component (A) is preferably 5% by mass to 85% by mass, more preferably 5% by mass to 70% by mass, still more preferably 5% by mass to 55% by mass, and most preferably 15% by mass to 55% by mass, based on the total mass of the solid content. When the content of component (A) is 5% by mass or more, a light-shielding film with a low refractive index can be easily obtained. When the content of component (A) is 85% by mass or less, the diffusion caused by component (A) does not occur too much, so the transmittance increases. Further, when the content of component (A) is 70% by mass or less, the transmittance further increases and the pencil hardness also increases. When the content of component (A) is 55% by mass or less, the transmittance further increases and the patterning property is also good. Also, by setting the content of component (A) to 15% by mass or more, a cured film having excellent pencil hardness can be obtained.

[0048] When the photosensitive resin composition contains the light-shielding material described below, the content of component (A) is preferably 1% by mass to 45% by mass, more preferably 20% by mass to 45% by mass, based on the total mass of the solid content. When the content of component (A) is 1% by mass or more, a light-shielding film with a low reflectance can be easily obtained. When the content of component (A) is 45% by mass or less, the diffusion caused by component (A) does not occur too much, so the pattern accuracy increases. Further, when the content of component (A) is 20% by mass or more, a light-shielding film with a lower reflectance can be obtained.

[0049] 1-2. (B) Alkali-soluble resin Component (B) is not particularly limited as long as it has an acidic group for expressing alkali solubility and the refractive index of the cured film with a film thickness of 1 μm is 1.50 to 1.70.

[0050] In this embodiment, the refractive index of the alkali-soluble resin used as component (B) is set to be 1.50 to 1.70 when it is a cured film with a film thickness of 1 μm. By combining component (A) with such component (B), the refractive index of the cured film can be effectively reduced. From the viewpoint of facilitating the reduction of the refractive index of the cured film, the refractive index of component (B) is preferably 1.50 to 1.60, more preferably 1.50 to 1.55.

[0051] Note that the refractive index of component (B) is a value measured by the following method.

[0052] The resin of component (B) is applied onto a silicon wafer "5-inch P-type wafer 1-100" (manufactured by Advantec Co., Ltd.) with a diameter of 125 mm using a spin coater so that the film thickness after post-baking becomes 1.0 μm. Pre-baking is carried out at 90 °C for 1 minute. Then, post-baking is carried out in an oven at 230 °C for 30 minutes, and the refractive index is measured using a spectroscopic ellipsometer "Alpha-SE" (manufactured by J.A. Woollam Co., Ltd.) with a substrate. Note that when applying component (B), component (B) may be diluted with a solvent such as propylene glycol monomethyl ether acetate so as to be easily applied, or it may be applied by increasing the rotation speed of the spin coater without dilution. Note that the value of the refractive index of component (B) in this application refers to the value of the refractive index with respect to light having a wavelength of 550 nm.

[0053] Component (B) can have a refractive index of 1.50 to 1.70 when it is a cured film with a film thickness of 1 μm by including an alicyclic structure such as dicyclopentane or dicyclopentene, or an aromatic ring structure such as benzene, naphthalene, or fluorene.

[0054] For example, when a photosensitive resin composition is applied to a substrate such as glass to obtain a substrate with a cured film, since the refractive index of the substrate such as glass is about 1.5, by using an alkali-soluble resin having a refractive index of 1.50 to 1.70 when formed into a cured film, the refractive index difference between the cured film and the substrate is sufficiently reduced, and reflection is easily suppressed. When the refractive index of component (B) is 1.50 to 1.60, the refractive index difference between the cured film and the substrate becomes smaller, so reflection is more easily suppressed. When the refractive index of component (B) is 1.50 to 1.55, the refractive index difference between the cured film and the substrate becomes even smaller, so reflection is even more easily suppressed.

[0055] Further, component (B) may contain a plurality of resins of different types (for example, resin (B)-1 and resin (B)-2 described later, etc.). The refractive index of component (B) at this time is measured by forming a coating film as described above in a state where each resin is mixed at a mass ratio contained in the photosensitive resin composition.

[0056] Resin (B)-1 and resin (B)-2 are resins whose refractive index can be 1.50 to 1.70 by themselves, but component (B) may contain an alkali-soluble resin whose refractive index is not 1.50 to 1.70 by itself. At this time, the blending amount of each resin may be adjusted so that the refractive index of the entire alkali-soluble component becomes 1.50 to 1.70.

[0057] The content of component (B) is preferably 5% by mass to 90% by mass, more preferably 25% by mass to 90% by mass, based on the total mass of the solid content. By setting the content of component (B) to 5% by mass or more, the photocurability of the photosensitive resin composition can be enhanced, and the patterning property can be enhanced. By setting the content of component (B) to 90% by mass or less, other components (especially component (A)) can be sufficiently blended, and the effect of reducing the refractive index by component (A) and the like can be sufficiently enhanced. Further, by setting the content of component (B) to 25% by mass or more, the patterning property can be further enhanced.

[0058] 1-2-1. Resin (B)-1 Resin (B)-1 is a polymerizable unsaturated group-containing alkali-soluble resin that contains 5 to 90 mol% of the structure represented by the general formula (1) and 10 to 95 mol% of the structure represented by the general formula (2), has a weight average molecular weight of 3,000 to 50,000, and an acid value of 30 to 200 mg / KOH. For Resin (B)-1, only one kind with a single polymerization ratio may be included in the photosensitive resin composition, or two or more kinds with different polymerization ratios may be included in the photosensitive resin composition.

[0059]

Chemical formula

[0060]

Chemical formula

[0061] In the general formulas (1) and (2), R1, R3, and R4 are each independently a hydrogen atom or a methyl group. R2 is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may contain an ether bond, an ester bond, or a urethane bond therein. However, in the structure represented by the general formula (1), 40 mol% or more of the total number of moles of the structure represented by the general formula (1) has R2 as a dicyclopentanyl group or a dicyclopentenyl group. R5 is a divalent hydrocarbon group having 2 to 10 carbon atoms. p is a number of 0 or 1. X is a hydrogen atom or OC-L-(COOH)k (where L is a divalent or trivalent carboxylic acid residue, and k is a number of 1 to 2). Note that two or more kinds of X are included in one molecule of Resin (B)-1.

[0062] Examples of the hydrocarbon group that R2 can take include saturated linear hydrocarbon groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, and eicosyl group; unsaturated linear hydrocarbon groups such as vinyl group, allyl group, and ethynyl group; cyclic aliphatic hydrocarbon groups such as cyclopropyl group, cyclopentyl group, cyclohexyl group, 2-methylcyclohexyl group, 4-methylcyclohexyl group, dicyclopentanyl group, dicyclopentenyl group, dicyclohexyl group, norbornyl group, isobornyl group, adamantyl group, and a substituent represented by the following general formula (3) (* indicates the bonding part with the ester site of the structure represented by the general formula (1)); hydrocarbon groups having an aromatic ring such as phenyl group, tolyl group, mesityl group, naphthyl group, anthryl group, phenanthryl group, benzyl group, 2-phenylethyl group, 2-phenylvinyl group, and decahydronaphthyl group; aliphatic ethers such as methoxyethyl group, 2-(methoxyethoxy)ethyl group, and isoamyl group; and aliphatic urethanes such as 2-(ethoxycarbonylamino)ethyl group. However, 40 mol% or more of R2 with respect to the total number of moles of the structure represented by the general formula (1) is a dicyclopentanyl group or a dicyclopentenyl group. The structure represented by the general formula (1) may include a plurality of structures with different R2s. From the viewpoint of heat resistance, it is preferable that 50 mol% or more of R2 is a dicyclopentanyl group or a dicyclopentenyl group.

[0063]

Chemical formula

[0064] Examples of hydrocarbon groups that R5 can take include an ethylene group, a 1,2-propylene group, a 1,4-butylene group, and a 1,6-hexamethylene group. Among these, an ethylene group, a 1,2-propylene group, and a 1,4-butylene group are preferred. The structure represented by the general formula (2) may contain a plurality of structures with different R5s.

[0065] X is -OC-L-(COOH) k (However, L represents a divalent or trivalent carboxylic acid residue, and k represents a number from 1 to 2.) The structure is formed by reacting a divalent carboxylic acid, a trivalent carboxylic acid, or an acid anhydride thereof with a hydroxyl group in the copolymer. Examples of the divalent or trivalent carboxylic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, chlorendic acid, and trimellitic acid. Among these, tetrahydrophthalic anhydride, succinic anhydride, and trimellitic anhydride are more preferred.

[0066] When the total of the structure represented by the general formula (1) and the structure represented by the general formula (2) is 100 mol%, the ratio of the structure represented by the general formula (1) is 5 mol% to 90 mol%, preferably 20 mol% to 70 mol%. Also, the structure represented by the general formula (2) is 10 mol% to 95 mol%, preferably 30 mol% to 80 mol%.

[0067] Resin (B)-1 may contain other structures other than the structure represented by the general formula (1) and the structure represented by the general formula (2). Examples of the other structures include structures derived from unsaturated group-containing carboxylic acids represented by the general formula (8) described later, styrene which may have a substituent on the phenyl group, and monomer maleimide. Examples of substituents that styrene can have on the phenyl group include alkyl groups having 1 to 10 carbon atoms. Examples of monomer maleimide include N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, and N-(4-hydroxyphenyl)maleimide. Among these, unsubstituted styrene and N-phenylmaleimide are preferred.

[0068] When the total structural units of Resin (B)-1 are 100 mol%, the ratio of the other structure can be 20 mol% to 50 mol%.

[0069] Resin (B)-1 can be synthesized by a known method. For example, after radical copolymerization of (meth)acrylate esters having the functional groups described above as R2 and glycidyl (meth)acrylate in a solvent to obtain a copolymer, unsaturated group-containing carboxylic acids such as (meth)acrylic acid (including those modified with alkylene oxide) are reacted with the glycidyl groups in the copolymer, and subsequently, a dicarboxylic acid compound, a tricarboxylic acid compound, or an acid anhydride thereof is reacted with the hydroxyl groups formed by the reaction of the glycidyl groups and the unsaturated group-containing carboxylic acids to synthesize Resin (B)-1.

[0070] Examples of the (meth)acrylate esters having the functional groups described above as R2 used in the synthesis method include dicyclopentanyl (meth)acrylate (Formula (4)), dicyclopentenyl (meth)acrylate (Formula (5)), ethylene glycol-modified dicyclopentanyl (meth)acrylate (Formula (6)), ethylene glycol-modified dicyclopentenyl (meth)acrylate (Formula (7)), and the like. These (meth)acrylate esters having a dicyclopentanyl group or a dicyclopentenyl group may be used in combination of two or more.

[0071]

Chemical formula

[0072]

Chemical formula

[0073]

Chemical formula

[0074]

Chemical formula

[0075] In general formulas (4) to (7), R1 represents a hydrogen atom or a methyl group, similar to R1 in general formula (1). Further, general formulas (6) and (7) illustrate compounds having only one ethylene oxide group in the molecule, but they may have a plurality of ethylene oxide groups in the molecule, or may have other alkylene oxide groups such as a propylene oxide group.

[0076] When radically copolymerizing (meth)acrylate esters having the functional groups described above as R2 and glycidyl (meth)acrylate, other (meth)acrylate esters having the structure represented by general formula (1) may be copolymerized. Examples of the other (meth)acrylate esters include (meth)acrylate esters having a hydrocarbon group with 1 to 20 carbon atoms such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, dicyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, anthracenyl (meth)acrylate, benzyl (meth)acrylate, phenethyl (meth)acrylate, cresyl (meth)acrylate, triphenylmethyl (meth)acrylate, and cumyl (meth)acrylate. These (meth)acrylate esters may be used in combination of two or more.

[0077] In addition, the blending amount of other (meth)acrylic acid esters is adjusted so that the amount of the (meth)acrylic acid esters having a dicyclopentanyl group or a dicyclopentenyl group is 40 mol% or more with respect to the total of the (meth)acrylic acid esters having a dicyclopentanyl group or a dicyclopentenyl group and other (meth)acrylic acid esters.

[0078] Further, the blending ratio of the (meth)acrylic acid esters having the structure represented by the general formula (1) and glycidyl (meth)acrylate may be adjusted so that the blending amount of the (meth)acrylic acid esters having the structure represented by the general formula (1) is 5 mol% to 90 mol% and the blending amount of glycidyl (meth)acrylate is 10 mol% to 95 mol%.

[0079] For the radical polymerization, known radical polymerization initiators such as azo compounds and peroxides may be used, and the degree of polymerization may be controlled by using known chain transfer agents, polymerization inhibitors, etc. The reaction temperature may be appropriately set in consideration of the half-life temperature of the radical polymerization initiator used.

[0080] Next, unsaturated group-containing carboxylic acids such as (meth)acrylic acid are reacted with the glycidyl groups in the copolymer obtained by the copolymerization to open the ring of the glycidyl groups. At this time, the amount of the unsaturated group-containing carboxylic acids to be reacted is preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 100 mol% with respect to the glycidyl groups. By increasing the amount of the unsaturated group-containing carboxylic acids used, the introduction of unsaturated groups and groups corresponding to X into the resin (B)-1 can be increased, and the photocurability and alkali solubility can be enhanced.

[0081] Examples of the unsaturated group-containing carboxylic acids to be reacted with the glycidyl groups include compounds represented by the following formula (8). R4, R5, and p are the same as those described for the general formula (2).

[0082]

Chemical formula

[0083] The divalent hydrocarbon group having 2 to 10 carbon atoms as R5 is preferably a divalent alkylene group having 2 to 10 carbon atoms or a divalent alkylarylene group having 2 to 10 carbon atoms. These alkylene groups and alkylarylene groups may be linear, branched, or cyclic. Among these, R5 is preferably an ethylene group, a 1,2-propylene group, or a 1,4-butylene group. The unsaturated group-containing carboxylic acids may be a plurality of compounds having different R5s. The unsaturated group-containing carboxylic acids are preferably (meth)acrylic acid with p = 0.

[0084] The addition reaction of the unsaturated group-containing carboxylic acids can be carried out by heating and stirring at 90 to 120 °C while blowing air in the presence of catalysts such as triethylbenzylammonium chloride, 2,6-isobutylphenol, and tris(dimethylaminomethyl)phenol.

[0085] Examples of the dicarboxylic acid compound, tricarboxylic acid compound, or their acid anhydrides that react with the hydroxyl group generated by the reaction of the glycidyl group and the unsaturated group-containing carboxylic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, chlorendic acid, trimellitic acid, and their acid anhydrides. These compounds may be used in combination of two or more. Among these, tetrahydrophthalic anhydride, succinic anhydride, and trimellitic anhydride are preferred.

[0086] The reaction can be carried out by heating and stirring at 90 to 130 °C in the presence of catalysts such as triethylamine, tetraethylammonium bromide, and triphenylphosphine.

[0087] Note that the synthesis method of Resin (B)-1 is not limited to this. For example, the above (meth)acrylate esters and (meth)acrylic acid may be subjected to radical copolymerization in a solvent, and then a (meth)acrylate compound having a glycidyl group such as glycidyl (meth)acrylate is reacted with the carboxyl group in the copolymer, and then the above dicarboxylic acid compound, tricarboxylic acid compound or their acid anhydrides are reacted with the generated hydroxyl group.

[0088] When Resin (B)-1 has other structures such as styrene and monomer maleimide described above, in any method, styrene, monomer maleimide, etc. may be copolymerized during the first radical polymerization.

[0089] The weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) measurement of Resin (B)-1 is preferably from 3,000 to 50,000, more preferably from 4,000 to 20,000, and still more preferably from 4,000 to 9,000. When the weight average molecular weight is 3,000 or more, the adhesion of the pattern during alkali development is improved, and when the weight average molecular weight is 50,000 or less, the developability is improved.

[0090] For the weight average molecular weight of Resin (B)-1, the sampled solution is dissolved in tetrahydrofuran, and the molecular weight distribution is measured with HLC-8220GPC manufactured by Tosoh Corporation, and the value obtained by calculating the weight average molecular weight in terms of standard polystyrene is used. Also, for the acid value, the sampled solution is dissolved in dioxane and neutralized and titrated with a 0.1N aqueous potassium hydroxide solution, and the value obtained by calculating the acid value in terms of the solid content of the sample solution from the equivalence point is used.

[0091] The acid value of Resin (B)-1 is preferably from 30 mgKOH / g to 200 mgKOH / g, more preferably from 50 mgKOH / g to 150 mgKOH / g. When the acid value is 30 mgKOH / g or more, it is difficult for residues to remain during alkali development, and when it is 200 mgKOH / g or less, the penetration rate of the alkali developer can be appropriately adjusted to make it difficult to cause peeling development.

[0092] 1-2-2. Resin (B)-2 Resin (B)-2 is an epoxy (meth) acrylate acid adduct obtained by reacting an epoxy compound having two glycidyl ether groups derived from bisphenols with (meth) acrylic acid and then reacting the resulting compound having a hydroxy group with a polybasic carboxylic acid or its anhydride. The epoxy compound derived from bisphenols means an epoxy compound obtained by reacting bisphenols with epihalohydrin or an equivalent thereof.

[0093] Resin (B)-2 is preferably a bisphenol type alkali-soluble resin having a fluorene structure represented by the following general formula (9).

[0094]

Chemical formula

[0095] In the general formula (9), Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a part of the hydrogen atoms constituting Ar may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an arylalkyl group, a cycloalkyl group having 3 to 10 carbon atoms or a cycloalkylalkyl group, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. R6 is independently an alkylene group having 2 to 4 carbon atoms. l is independently a number from 0 to 3. G is independently a (meth) acryloyl group or a substituent represented by the following general formula (10) or the following general formula (11). Y is a tetravalent carboxylic acid residue. Z is independently a hydrogen atom or a substituent represented by the following general formula (12), and at least one of Z is a substituent represented by the following general formula (12). q is a number having an average value of 1 to 20.

[0096]

Chemical formula

[0097]

Chemical formula

[0098] In general formulas (10) and (11), R7 is a hydrogen atom or a methyl group, R8 is an alkylene group or an alkylarylene group having 2 to 10 carbon atoms, R9 is a saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and m is a number from 0 to 10. * indicates the bonding site with the compound represented by general formula (9).

[0099]

Chemical formula

[0100] In general formula (12), W is a divalent or trivalent carboxylic acid residue, and n is a number of 1 or 2. * indicates the bonding site with the compound represented by general formula (9).

[0101] The resin represented by general formula (9) can be synthesized by the following method.

[0102] First, an epoxy compound (a) having a bisarylfluorene skeleton which may have several alkylene oxide-modified groups in one molecule and is represented by the following general formula (13) (hereinafter, also simply referred to as "epoxy compound (a)") is reacted with at least one of (meth)acrylic acid, a (meth)acrylic acid derivative represented by the following general formula (14), and a (meth)acrylic acid derivative represented by the following general formula (15) to obtain a diol compound which is epoxy (meth)acrylate. The bisarylfluorene skeleton is preferably a bisnaphtholfluorene skeleton or a bisphenolfluorene skeleton.

[0103]

Chemical formula

[0104] In the general formula (13), each Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a part of the hydrogen atoms constituting Ar may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. R6 is independently an alkylene group having 2 to 4 carbon atoms. l is independently a number from 0 to 3.

[0105]

Chemical formula

[0106]

Chemical formula

[0107] In the general formulas (14) and (15), R7 is a hydrogen atom or a methyl group, R8 is an alkylene group or alkylarylene group having 2 to 10 carbon atoms, R9 is a saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and m is a number from 0 to 10.

[0108] For the reaction of the epoxy compound (a) with (meth)acrylic acid or its derivative, a known method can be used. For example, Japanese Patent Laid-Open No. 4-355450 describes that by using about 2 moles of (meth)acrylic acid with respect to 1 mole of an epoxy compound having two epoxy groups, a diol compound containing a polymerizable unsaturated group can be obtained. In the present embodiment, the compound obtained by the reaction is a diol (d) containing a polymerizable unsaturated group represented by the following general formula (16) (hereinafter, also simply referred to as "diol (d)").

[0109]

Chemical formula

[0110] In general formula (16), each Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a part of the hydrogen atoms constituting Ar may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. Each G is independently a (meth)acryloyl group or a substituent represented by general formula (17) or general formula (18), and R6 is independently an alkylene group having 2 to 4 carbon atoms. l is independently a number from 0 to 3.

[0111]

Chemical formula

[0112]

Chemical formula

[0113] In general formula (17) and general formula (18), R7 is a hydrogen atom or a methyl group, R8 is an alkylene group or alkylarylene group having 2 to 10 carbon atoms, R9 is a saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and m is a number from 0 to 10. * indicates the bonding site with the compound represented by general formula (16).

[0114] Next, the obtained diol (d) is reacted with a dicarboxylic acid, tricarboxylic acid or acid anhydride thereof (b) and a tetracarboxylic acid or acid dianhydride thereof (c) to obtain an unsaturated group-containing curable resin having a carboxy group and a polymerizable unsaturated group in one molecule represented by general formula (9).

[0115] The acid component is a polyvalent acid component capable of reacting with the hydroxyl groups in the diol (d) molecule. In order to obtain the resin represented by the general formula (9), it is necessary to use a dicarboxylic acid or tricarboxylic acid or their acid anhydrides (b) and a tetracarboxylic acid or its dianhydride (c) in combination. The carboxylic acid residue of the acid component may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. Further, these carboxylic acid residues may contain a bond containing a hetero element such as -O-, -S-, or a carbonyl group.

[0116] Examples of the dicarboxylic acid or tricarboxylic acid or their acid anhydrides (b) include chain hydrocarbon dicarboxylic acids or tricarboxylic acids, alicyclic hydrocarbon dicarboxylic acids or tricarboxylic acids, aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids, and their acid anhydrides.

[0117] Examples of the chain hydrocarbon dicarboxylic acid or tricarboxylic acid include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid, etc., and these dicarboxylic acids or tricarboxylic acids with any substituent introduced, etc. are included.

[0118] Examples of the alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid include cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, hexahydrotrimellitic acid, and norbornanedicarboxylic acid, etc., and these dicarboxylic acids or tricarboxylic acids with any substituent introduced, etc. are included.

[0119] Examples of the aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid include phthalic acid, isophthalic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and trimellitic acid, etc., and these dicarboxylic acids or tricarboxylic acids with any substituent introduced are included.

[0120] Among these, the dicarboxylic acid or tricarboxylic acid is preferably succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, or trimellitic acid, and more preferably succinic acid, itaconic acid, or tetrahydrophthalic acid.

[0121] It is preferable to use the monoanhydride of the dicarboxylic acid or tricarboxylic acid.

[0122] Examples of the tetracarboxylic acid or its dianhydride (c) include chain hydrocarbon tetracarboxylic acids, alicyclic hydrocarbon tetracarboxylic acids, aromatic hydrocarbon tetracarboxylic acids, and their dianhydrides.

[0123] Examples of the chain hydrocarbon tetracarboxylic acid include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, and these chain hydrocarbon tetracarboxylic acids with substituents such as alicyclic hydrocarbon groups and unsaturated hydrocarbon groups introduced.

[0124] Examples of the alicyclic hydrocarbon tetracarboxylic acid include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, and norbornanetetracarboxylic acid, and these alicyclic tetracarboxylic acids with substituents such as chain hydrocarbon groups and unsaturated hydrocarbon groups introduced.

[0125] Examples of the aromatic hydrocarbon tetracarboxylic acid include pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, and naphthalene-2,3,6,7-tetracarboxylic acid.

[0126] Among these, the tetracarboxylic acid is preferably biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, or diphenyl ether tetracarboxylic acid, and more preferably biphenyltetracarboxylic acid and diphenyl ether tetracarboxylic acid.

[0127] It is preferable to use the acid dianhydride of the tetracarboxylic acid.

[0128] Also, instead of the tetracarboxylic acid or its acid dianhydride (c), aryl esters of bisanhydride trimellitic acid can also be used. Aryl esters of bisanhydride trimellitic acid are compounds produced, for example, by the method described in International Publication No. 2010 / 074065, and structurally are acid dianhydrides in which two hydroxyl groups of aromatic diols (such as naphthalenediol, biphenol, and terphenyl diol) and carboxy groups of two molecules of trimellitic anhydride are each reacted to form an ester bond.

[0129] The reaction method of the diol (d) with the acid components (b) and (c) is not particularly limited, and a known method can be adopted. For example, Japanese Patent Application Laid-Open No. 9-325494 describes a method of reacting an epoxy (meth) acrylate with a tetracarboxylic dianhydride at a reaction temperature of 90 to 140°C.

[0130] At this time, the molar ratio of epoxy (meth) acrylate (diol (d)), dicarboxylic acid or tricarboxylic acid or their acid monohydrides (b), and tetracarboxylic dianhydride (c) is preferably (d):(b):(c)=1.0:0.01 to 1.0:0.2 to 1.0 so that the terminal of the compound becomes a carboxy group.

[0131] For example, when using acid monoanhydride (b) and acid dianhydride (c), it is preferable to react them such that the molar ratio of the amount of acid component [(b) / 2 + (c)] to diol (d) [((b) / 2 + (c)) / (d)] is greater than 0.5 and not more than 1.0. When the molar ratio is not more than 1.0, the terminal of the unsaturated group-containing curable resin represented by the general formula (1) will not become an acid anhydride, so an increase in the content of unreacted acid dianhydride can be suppressed, and the stability over time of each composition can be enhanced. Also, when the molar ratio is greater than 0.5, an increase in the remaining amount of unreacted components among the diols (d) containing polymerizable unsaturated groups can be suppressed, and the stability over time of each composition can be enhanced. Note that for the purpose of adjusting the acid value and molecular weight of the unsaturated group-containing curable resin represented by the general formula (3), the molar ratios of the respective components (b), (c), and (d) can be arbitrarily changed within the above-described range.

[0132] Note that the synthesis of diol (d) and the subsequent reaction with the polyvalent carboxylic acid or its anhydride are usually carried out in a solvent using a catalyst as necessary.

[0133] Examples of the solvent include cellosolve solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, high-boiling ether-based or ester-based solvents such as diglyme, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate, and ketone-based solvents such as cyclohexanone and diisobutyl ketone. Note that the reaction conditions regarding the solvent, catalyst, etc. are not particularly limited, but for example, it is preferable to use a solvent that does not have a hydroxyl group and has a boiling point higher than the reaction temperature as the reaction solvent.

[0134] Also, the reaction between an epoxy group and a carboxy group or a hydroxyl group is preferably carried out using a catalyst. As the catalyst, Japanese Patent Application Laid-Open No. 9-325494 describes ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, and phosphines such as triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine.

[0135] Resin (B)-2 preferably has an acid value of 50 mgKOH / g to 200 mgKOH / g, more preferably 60 mgKOH / g to 150 mgKOH / g. When the acid value is 50 mgKOH / g or more, residues are less likely to remain during alkali development. When the acid value is 200 mgKOH / g or less, the penetration rate of the alkali developer can be appropriately adjusted to make peeling development less likely to occur. The acid value can be determined by titration with 1 / 10N-KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0136] The weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) measurement of Resin (B)-2 is preferably 1000 to 40000, more preferably 1500 to 30000, and even more preferably 2000 to 15000. When the weight average molecular weight (Mw) is 1000 or more, the adhesion of the pattern during alkali development is improved. When the weight average molecular weight (Mw) is 40000 or less, the developability is improved.

[0137] The acid value and the polymerization average molecular weight (Mw) of Resin (B)-2 can be measured in the same manner as Resin (B)-1.

[0138] When Resin (B)-2 is used in combination with Resin (B)-1, the content of Resin (B)-2 is preferably 0.1% by mass or more and less than 10% by mass based on the total amount of Resin (B)-1 and Resin (B)-2.

[0139] 1-3. (C) Photoinitiator The component (C) is not particularly limited as long as it is a compound that can initiate the polymerization of a compound having a polymerizable unsaturated bond and capable of addition polymerization by the stimulation of light.

[0140] Examples of component (C) include photoinitiators such as acetophenone compounds, triazine compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, imidazole compounds, and acyloxime compounds. In this specification, component (C) is used in the sense of including a sensitizer. From the viewpoint of easily generating active radicals with high efficiency by light stimulation, component (C) is preferably an acyloxime compound.

[0141] Examples of acetophenone compounds include acetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, and oligomers of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one.

[0142] Examples of triazine compounds include 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthio-styryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(piperonyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, and the like.

[0143] Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin - tert - butyl ether, and the like.

[0144] Examples of benzophenone compounds include benzophenone, methyl o - benzoylbenzoate, 4 - phenylbenzophenone, 4 - benzoyl - 4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert - butylperoxycarbonyl)benzophenone, 2,4,6 - trimethylbenzophenone, 4,4‘-bis(N,N - diethylamino)benzophenone, and the like.

[0145] Examples of thioxanthone compounds include thioxanthone, 2 - chlorothioxanthone, 2 - methylthioxanthone, 2 - isopropylthioxanthone, 4 - isopropylthioxanthone, 2,4 - diethylthioxanthone, 2,4 - dichlorothioxanthone, 1 - chloro - 4 - propoxythioxanthone, and the like.

[0146] Examples of imidazole compounds include 2-(o - chlorophenyl)-4,5 - diphenylimidazole dimer, 2-(o - chlorophenyl)-4,5 - di(m - methoxyphenyl)imidazole dimer, 2-(o - fluorophenyl)-4,5 - diphenylimidazole dimer, 2-(o - methoxyphenyl)-4,5 - diphenylimidazole dimer, 2,4,5 - triaryl imidazole dimer, and the like.

[0147] Examples of acyloxime compounds include 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-bicycloheptyl-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-adamantylmethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-adamantylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-tetrahydrofuranylmethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-tetrahydrofuranylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-thiophenylmethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-thiophenylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-morphonylmethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-morphonylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-bicycloheptanecarboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-tricyclodecane carboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-adamantanecarboxylate, 1-[4-(phenylsulfanyl)phenyl]octane-1,2-dione = 2-o-benzoyloxime, 1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethanone-o-acetyl oxime, (2-methylphenyl)(7-nitro-9,9-dipropyl-9H-fluoren-2-yl)-acetyl oxime, ethanone,1-[7-(2-Methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]-1-(O-acetyloxime), ethanone, 1-(-9,9-dibutyl-7-nitro-9H-fluoren-2-yl)-1-o-acetyloxime, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), 1,2-octadiene, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)]-, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), 1-(4-phenylsulfanylphenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylsulfanylphenyl)butane-1,2-dione-2-oxime-O-acetate, 1-(4-methylsulfanylphenyl)butan-1-one oxime-O-acetate, 4-ethoxy-2-methylphenyl-9-ethyl-6-nitro-9H-carbazol-3-yl-O-acetyloxime, 5-(4-isopropylphenylthio)-1,2-indanedione, 2-(O-acetyloxime) and the like are included. Examples of commercially available acyl oxime compounds include Irgacure OXE01 (manufactured by BASF Japan Ltd.), Adeka Arcles NCI-831E (manufactured by Adeka Corporation), etc. The photoinitiator may be used alone as only one type, or two or more types may be used in combination.,

[0148] Other examples of acyl oxime-based photoinitiators include O-acyl oxime-based photoinitiators represented by general formula (19) or general formula (20).

[0149]

Chemical formula

[0150] In formula (19), R 10 , R 11 each independently represents an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 4 to 12 carbon atoms, and R 12represents an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. Here, the alkyl group and the aryl group may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkanoyl group having 1 to 10 carbon atoms, or a halogen, and the alkylene moiety may contain an unsaturated bond, an ether bond, a thioether bond, or an ester bond. Further, the alkyl group may be any of a linear, branched, or cyclic alkyl group.

[0151]

Chemical formula

[0152] In formula (20), R 13 and R 14 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a cycloalkylalkyl group or an alkylcycloalkyl group, or a phenyl group optionally substituted with an alkyl group having 1 to 6 carbon atoms. R 15 are each independently a linear or branched alkyl group or alkenyl group having 2 to 10 carbon atoms, and a part of the -CH2- groups in the alkyl group or alkenyl group may be substituted with an -O- group. Further, a part of the hydrogen atoms in these R 13 ~R 15 groups may be substituted with halogen atoms.

[0153] Further, the component (D) preferably has a molar extinction coefficient at 365 nm of 10000 L / (mol·cm) or more. Since such a photoinitiator has high sensitivity, sufficient photosensitivity can be ensured even in a photosensitive resin composition containing the component (C) having a relatively large acrylic equivalent, and the developability (resolution) of the photosensitive resin composition can be sufficiently enhanced. Examples of such photoinitiators include Omnirad 1312 (manufactured by IGM Resins B.V., "Omnirad" is a registered trademark of the company), and Adeka Arcles NCI-831E (manufactured by Adeka Corporation, "Adeka Arcles" is a registered trademark of the company), and the like.

[0154] In this specification, the molar extinction coefficient of the photopolymerization initiator can be determined as the value obtained by measuring the absorbance of a 0.001 wt% acetonitrile solution using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Technologies Corporation) in a 1 cm optical path length quartz cell.

[0155] Note that as the component (C), an active radical generator or an acid generator may be used.

[0156] Examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds, and the like.

[0157] Examples of the acid generator include onium salts such as 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl·methyl·benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylates, benzoin tosylates, and the like.

[0158] Examples of sensitizers include triethylamine, triethanolamine, methyldiethanolamine, triisopropanolamine, benzophenone, 4,4'-bis(dimethylamino)benzophenone (Michler's ketone), 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4,4'-diethylaminobenzophenone, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butylacetophenone and other acetophenones; benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether and other benzoin ethers; 2-dimethylaminoethyl benzoate, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, (n-butoxy)ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 3,3'-dimethyl-4-methoxybenzophenone and other benzophenone-based, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone and other thioxanthone-based; 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone and other aminobenzophenone-based; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and camphorquinone and the like are included.

[0159] The content of component (C) is preferably 1% by mass to 30% by mass, more preferably 2% by mass to 25% by mass, and even more preferably 3% by mass to 10% by mass, based on the total mass of component (B) and component (E). When the content of component (C) is 1% by mass or more, it has an appropriate photopolymerization rate, so sufficient sensitivity can be ensured. Also, when the content of component (C) is 30% by mass or less, a faithful line width can be reproduced with respect to the mask and the pattern edge can be sharpened.

[0160] The content of the sensitizer is preferably 0.5% by mass to 400% by mass, more preferably 1% by mass to 300% by mass, based on the total mass of component (C). When the content of the sensitizer is 0.5% by mass or more, the sensitivity of the polymerization initiator can be improved and the polymerization rate can be increased. Also, when the content of the sensitizer is 400% by mass or less, an excessive increase in sensitivity can be suppressed, and burning, peeling chips, etc. are less likely to occur during polymerization (especially during photopolymerization).

[0161] 1-4. (D) Colorant (D) The colorant (hereinafter, also simply referred to as “component (D)”) is not particularly limited as long as it can impart a desired color tone according to the use of the cured film.

[0162] (D) Component is not particularly limited as long as it is a known colorant, but is preferably an organic pigment or an inorganic pigment. In particular, when the photosensitive resin composition according to the present embodiment is used for forming a light-shielding film (black matrix), component (D) preferably contains a light-shielding material. In the present application, the light-shielding material refers to at least one pigment selected from the group consisting of organic black pigments, inorganic black pigments, and mixed-color organic pigments.

[0163] Examples of organic black pigments include perylene black, cyanine black, aniline black, lactam black, etc.

[0164] Examples of inorganic black pigments include carbon black, chromium oxide, iron oxide, titanium black, etc.

[0165] Examples of the mixed organic pigments include those obtained by mixing two or more pigments selected from red, blue, green, purple, yellow, cyanine, magenta, etc. to simulate blackening.

[0166] Examples of the mixed organic pigments include pigments obtained by mixing at least two colors selected from organic pigments such as azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, threne pigments, perylene pigments, perinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, thioindigo pigments, etc.

[0167] In addition, examples of the organic pigments that can be used when using the mixed organic pigment as the component (D) include those with the following numbers in the Color Index name. Pigment Red 2, 3, 4, 5, 9, 12, 14, 22, 23, 31, 38, 112, 122, 144, 146, 147, 149, 166, 168, 170, 175, 176, 177, 178, 179, 184, 185, 187, 188, 202, 207, 208, 209, 210, 213, 214, 220, 221, 242, 247, 253, 254, 255, 256, 257, 262, 264, 266, 272, 279, etc. Pigment Orange 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81, etc. Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 55, 73, 74, 81, 83, 93, 95, 97, 109, 110, 111, 117, 120, 126, 127, 128, 129, 130, 136, 138, 139, 150, 151, 153, 154, 155, 173, 174, 175, 176, 180, 181, 183, 185, 191, 194, 199, 213, 214, etc. Pigment Green 7, 36, 58, etc. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, 80, etc. Pigment Violet 19, 23, 37, etc.

[0168] Among these, from the viewpoints of light-shielding property, surface smoothness, dispersion stability, and fine-line patterning property, an inorganic black pigment is preferable, and carbon black is more preferable.

[0169] The average primary particle diameter of the carbon black is preferably 5 nm to 60 nm, more preferably 10 nm to 50 nm, and even more preferably 20 nm to 45 nm. In this specification, the particle diameter or average primary particle diameter of the light-shielding material means the additive average value of 1500 light-shielding materials, which is the average value of the major axis and minor axis obtained by observing the particles or primary particles of the light-shielding material with an electron microscope. The larger the average primary particle diameter of the carbon black, the easier it is to disperse at a high concentration. By making the average primary particle diameter of the carbon black not overly large, it is possible to suppress the shape defect of the osmotic particles and the decrease in surface roughness.

[0170] Also, the DBP oil absorption amount of the carbon black is preferably 100 ml / 100 g or less. The DBP oil absorption amount means the volume of dibutyl phthalate (DBP) absorbed by 100 g of carbon black (JIS K 6217-4 (2017)). When the DBP oil absorption amount of the carbon black is within the above range, the resistance value and blackness degree of the cured film can be made higher, and the decrease in coatability due to the increase in the viscosity of the photosensitive resin composition can be suppressed.

[0171] Also, the pH of the carbon black is preferably 2 to 10, more preferably 5 to 9, and even more preferably 4 to 8. The pH value means the value measured with a glass electrode pH meter for a mixed solution of carbon black and distilled water. The higher the pH of the carbon black, the higher the stability of the carbon black. By making the pH of the carbon black within a non-excessive range, the adhesion of the cured film to the substrate can be further enhanced.

[0172] Also, the ash content of the carbon black is preferably 1.0% or less. When the ash content is 1.0% or less, the resistance value of the cured film can be made higher.

[0173] Also, the carbon black preferably has a specific surface area of 20 m 2 / g to 300 m 2 / g. When the specific surface area is 20 m 2 / g or more, the shape of the cured film is likely to be stable. When the specific surface area is 300 m 2 / g or less, the required amounts of dispersants, dyes, etc. can be reduced, so the cost can be further suppressed.

[0174] Also, the carbon black preferably has acidic functional groups on the surface by oxidation treatment. In particular, it is preferable to have two or more types of acidic functional groups on the surface by multiple types of oxidation treatment. The above acidic functional groups can enhance the dispersibility of the carbon black. Examples of the above oxidation treatment include treatments using ozone gas, nitric acid, sodium hypochlorite, hydrogen peroxide, nitric oxide gas, nitrogen dioxide gas, sulfuric anhydride, fluorine gas, concentrated sulfuric acid, nitric acid, and various peroxides. Examples of the above acidic functional groups include hydroxyl group, oxo group, hydroperoxy group, carbonyl group, carboxyl group, peroxycarboxylic acid group, aldehyde group, ketone group, nitro group, nitroso group, amide group, imide group, sulfonic acid group, sulfinic acid group, sulfenic acid group, thiocarboxylic acid group, chlorosyl group, chloric group, perchloric group, iodoxysyl group, and iodyl group.

[0175] Also, the component (D) may be surface-treated with the surface being coated with a dye. In particular, carbon black with the surface coated with a dye can enhance the developability of the photosensitive resin composition, and can also enhance the adhesion to the substrate, fine line reproducibility, and light-shielding property of the cured film formed by curing this, and can increase the resistance value of the cured film.

[0176] The above-mentioned dye only needs to be able to adsorb on the surface of the light-shielding material, and basic dyes, acid dyes, direct dyes, reactive dyes, etc. can be used. At this time, when an acidic functional group (oxidation treatment) is imparted to the surface of the light-shielding material (especially carbon black) to enhance its dispersibility, an acid dye that easily interacts with the acidic functional group (especially an acid dye having a sulfonic acid group or a carboxyl group) is preferred. Further, from the viewpoint of suppressing the reaction with the acidic group of the component (A), an acid dye or a non-ionic dye is preferred as compared with a dye having an amino group or the like. Further, from the viewpoint of further enhancing the light-shielding property of the cured film, a dark-colored dye is preferred.

[0177] Specific examples of the above dyes include food coloring dyes such as Food Black No.1, Food Black No.2, Food Red No.40, Food Blue No.1, Food Yellow No.7, acid dyes of various colors such as Bernacid Red 2BMN, Basacid Black X34 (BASF X-34) (manufactured by BASF), Kayanol Red 3BL (manufactured by Nippon Kayaku Company), Dermacarbon 2GT (manufactured by Sandoz), Telon Fast Yellow 4GL-175, BASF Basacid Black SE 0228, Basacid Black X34 (BASF X-34) (manufactured by BASF), Basacid Blue 750 (manufactured by BASF), Bernacid Red (manufactured by Bemcolors, Poughkeepsie, N.Y.), BASF Basacid Black SE 0228 (manufactured by BASF), Pontamine Brilliant Bond Blue and other Pontamine Brilliant Bond Blue and other Pontamine (registered trademark) dyes (manufactured by Bayer Chemicals Corporation, Pittsburgh, PA), Cartasol Yellow GTF Presscake (manufactured by Sandoz, Inc); Cartasol Yellow GTF Liquid Special 110 (manufactured by Sandoz, Inc.); Yellow Shade 16948 (manufactured by Tricon), Direct Brilliant Pink B (manufactured by Crompton & Knowles), Carta Black 2GT (manufactured by Sandoz, Inc.), Sirius Supra Yellow GD 167, Cartasol Brilliant Yellow 4GF (manufactured by Sandoz);, Pergasol Yellow CGP (manufactured by Ciba-Geigy), Pyrazol Black BG (manufactured by JCI), Diazol Black RN Quad (manufactured by JCJ), Pontamine Brilliant Bond Blue; Berncolor A.Y.Direct dyes of various colors such as 34, Cibacron Brilliant Red 3B-A (Reactive Red 4) (manufactured by Aldrich Chemical, Milwaukee, WI), Drimarene Brilliant Red X-2B (Reactive Red 56) (manufactured by Pylam Products, Inc., Tempe, AZ), Levafix Brilliant Red E-4B, Levafix Brilliant Red F-6BA, and similar Levafix® dyes manufactured by Dystar L.P. (Charlotte, NC), Procion Red H8B (Reactive Red 31) (manufactured by JCI America), and other reactive dyes of various colors, Neozapon Red 492 (manufactured by BASF), Orasol Red G (manufactured by Ciba-Geigy), Aizen Spilon Red C-BH (manufactured by Hodogaya Chemical Company), Spirit Fast Yellow 3G, Aizen Spilon Yellow C-GNH (manufactured by Hodogaya Chemical Company), Orasol Black RL (manufactured by Ciba-Geigy), Orasol Black RLP (manufactured by Ciba-Geigy), Savinyl Black RLS (manufactured by Sandoz), Orasol Blue GN (manufactured by Ciba-Geigy), Luxol Blue MBSN (manufactured by Morton-Thiokol), Morfast Black Concentrate A (manufactured by Morton-Thiokol), and other oil-soluble dyes are included. These may be used alone or in combination of two or more.

[0178] The content of the above dyes is preferably 0.5% by mass to 10% by mass, more preferably 1% by mass to 7% by mass, based on the total mass of the component (D). The larger the amount of the dye, the higher the resistance value of the cured film can be increased. By ensuring that the amount of the dye does not become excessive, it is possible to suppress the thickening of the photosensitive resin composition due to the excess dye and the occurrence of aggregation caused by the excess dye inhibiting the dispersibility of other components.

[0179] Further, the above dye may be lakeized with a metal or a metal salt. By lakeizing the dye, the dye can be fixed to the surface of the light-shielding material via the above metal or metal salt, and reduction of the above effect due to detachment of the dye from the surface of the light-shielding material can be suppressed. Examples of the above metal include aluminum, magnesium, calcium, strontium, barium, manganese, and the like. Examples of the above metal salt include hydrochlorides and sulfates of these metals. The content of the above metal or metal salt is preferably 0.3 times mole or more, more preferably 0.5 times mole, and even more preferably 0.8 times mole with respect to the dye.

[0180] Also, when the photosensitive resin composition according to the present embodiment is used for forming a light-shielding film (black matrix), the ratio (m D ) of the total mass (m A ) of the component (hollow filler) (A) to the total mass (m A / m D ) of the light-shielding material is preferably 0.01 to 0.75, more preferably 0.10 to 0.75, and even more preferably 0.20 to 0.75. When m A / m D is 0.01 or more, a low reflectance can be achieved. When m A / m D is 0.10 or more, the reflectance further decreases. When m A / m D is 0.20 or more, the reflectance further decreases. When m A / m D is 0.75 or less, the patterning property becomes good.

[0181] Component (D) is usually mixed with other compounding components as a dispersion of a light-shielding material dispersed in a solvent. In this case, as other compounding components, a dispersant for promoting the dispersion of component (D) or stabilizing the dispersibility can be added. As the dispersant used for the dispersion of component (D), known compounds (compounds commercially available under names such as dispersants, dispersion wetting agents, dispersion accelerators, etc.) used for pigment (light-shielding material) dispersion can be used without particular limitation.

[0182] Examples of the dispersant used for the dispersion of component (D) include cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, and pigment derivative type dispersants (dispersion aids). In particular, as the above dispersant, a cationic polymer dispersant having a cationic functional group such as an imidazolyl group, a pyrrolyl group, a pyridyl group, a primary, secondary or tertiary amino group as an adsorption point to the colorant is preferable. Further, the above cationic polymer dispersant preferably has an amine value of 1 mgKOH / g to 100 mgKOH / g. Also, the cationic polymer dispersant preferably has a number average molecular weight (Mn) of 1000 to 100000. The blending amount of the dispersant is preferably 1% by mass to 35% by mass, more preferably 2% by mass to 25% by mass, based on the total mass of the light-shielding material.

[0183] When the photosensitive resin composition according to this embodiment is used for forming a light-shielding film (black matrix), the content of the light-shielding material is arbitrarily determined by the desired light-shielding degree. Among them, the content of the light-shielding material is preferably 10% by mass to 60% by mass, more preferably 10% by mass to 50% by mass, based on the total mass of the solid content in the photosensitive resin composition. By setting the content of the light-shielding material to 10% by mass or more, sufficient light-shielding property can be obtained. Also, by setting the content of the light-shielding material to 60% by mass or less, the radiation exposed for photocuring is not overly shielded, so that the patterning property becomes good. By setting the content of the light-shielding material to 60% by mass or less, the patterning property becomes better.

[0184] In addition, the content of component (D) in this specification is the amount based on component (D) after surface treatment when component (D) is surface-treated with a dye or the like that coats the surface. On the other hand, the content of component (D) is the amount excluding the other compounding components (such as dispersants) that have little influence on light-shielding properties.

[0185] 1-5. (E) Photopolymerizable compound The (E) photopolymerizable compound (hereinafter also simply referred to as “component (E)”) is not particularly limited as long as it is a compound having a polymerizable unsaturated bond and capable of addition polymerization. By adding component (E), the exposure sensitivity is increased and the developability (resolution, for example, the linearity of the pattern) of the coating film or cured film is increased.

[0186] Component (E) is preferably a polymerizable compound having an ethylenic unsaturated bond.

[0187] Examples of the polymerizable compound having an ethylenically unsaturated bond include (meth)acrylic acid esters having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, glycerol (meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, or dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide-modified hexa(meth)acrylate of phosphazene, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and (meth)acrylic acid esters, and dendritic polymers having a (meth)acrylic group as a compound having an ethylenic double bond. These photopolymerizable monomers may be used alone or in combination of two or more thereof.

[0188] Examples of the dendritic polymers include dendrimer acrylates which are spherical macromolecules formed by radially assembling dendritic molecules having acrylic groups, hyperbranched acrylic polymers, hyperbranched acrylic oligomers, and dendritic polymers obtained by adding a polyvalent mercapto compound to a part of the carbon-carbon double bonds in the (meth)acryloyl groups of polyfunctional (meth)acrylates. Specifically, dendritic polymers obtained by reacting a (meth)acryloyl group of a polyfunctional (meth)acrylate represented by the following general formula (E1) with a polyvalent mercapto compound represented by the following general formula (E2) are included. From the viewpoints of high functionality, easy enhancement of reactivity, and easy reduction of curing shrinkage during curing for high molecular weight substances, it is preferable to use such dendritic polymers.

[0189]

Chemical formula

[0190] In formula (E1), R 21 is a hydrogen atom or a methyl group, and R 22 is the remaining part obtained by donating r hydroxy groups out of k hydroxy groups of R 23 (OH) k to the ester bonds in the formula. Preferred R 23 (OH) k is a polyhydric alcohol based on a non-aromatic linear or branched hydrocarbon skeleton having 2 to 8 carbon atoms, a polyhydric alcohol ether formed by linking a plurality of molecules of the polyhydric alcohol via an ether bond by dehydration condensation of the alcohol, or an ester of these polyhydric alcohols or polyhydric alcohol ethers and hydroxy acids. k and r independently represent integers of 2 to 20, provided that k ≥ r.

[0191]

Chemical formula

[0192] In formula (E2), R 24 is a single bond or a hydrocarbon group having 1 to 6 carbon atoms with a valence of 2 to 6, and s is R24 is 2 when it is a single bond, and R 24 is the same as the valence of R when it is a group with a valence of 2 to 6. 24 is the same as the valence of R.

[0193] Examples of the polyfunctional (meth)acrylate represented by the general formula (E1) include (meth)acrylic acid esters such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and caprolactone-modified pentaerythritol tri(meth)acrylate.

[0194] Examples of the polyvalent mercapto compound represented by the general formula (E2) include trimethylolpropane tri(mercaptoacetate), trimethylolpropane tri(mercapto propionate), pentaerythritol tetra(mercaptoacetate), pentaerythritol tri(mercaptoacetate), pentaerythritol tetra(mercapto propionate), dipentaerythritol hexa(mercaptoacetate), dipentaerythritol hexa(mercapto propionate), and the like.

[0195] The polymerizable compound having an ethylenically unsaturated bond may be used alone with only one of these polymerizable compounds, or two or more thereof may be used in combination. Further, when the component (B) has an ethylenically unsaturated bond, it can play a role of crosslinking the polymerizable compound having an ethylenically unsaturated bond and the component (B). In order to exhibit this function, it preferably has three or more unsaturated bonds. By containing three or more unsaturated bonds, the alkali resistance is enhanced and the developability becomes good. Further, for the component (C), the acrylic equivalent obtained by dividing the molecular weight by the number of (meth)acrylic groups in one molecule is preferably 50 g / eq to 300 g / eq, and more preferably 80 g / eq to 200 g / eq. When the acrylic equivalent is 300 g / eq or less, the crosslinking density increases, so the alkali resistance increases and the developability becomes good. When the acrylic equivalent is 200 g / eq or less, the alkali resistance can be further enhanced. When the acrylic equivalent is 50 g / eq or more, it can be appropriately photocured within a range where the crosslinking density does not become too high.

[0196] (E) component content is preferably 0% by mass to 30% by mass, more preferably 1% by mass to 30% by mass, and still more preferably 10% by mass to 30% by mass with respect to the total mass of the solid content. By setting the content of the component (E) to 1% by mass or more, the photocurability of the photosensitive resin composition can be enhanced and the patterning property can be enhanced. By setting the content of the component (E) to 10% by mass or more, the patterning property can be further enhanced. By setting the content of the component (E) to 30% by mass or less, other components (especially the component (B)) can be sufficiently blended, and the effects such as alkali solubility (developability) by the component (B) can be sufficiently enhanced.

[0197] (B) component and (E) component are preferably in a blending ratio of 30 / 70 to 100 / 0 in terms of weight ratio (B) / (E), and more preferably 65 / 35 to 82.5 / 17.5. When the blending ratio of the (B) component is 30 / 70 or more, the cured product after photocuring is less likely to become brittle, and in the unexposed part, the acid value of the coating film is less likely to decrease, so that a decrease in solubility in an alkaline developer can be suppressed. Therefore, problems such as jagged pattern edges and lack of sharpness are less likely to occur. When the blending ratio of the (B) component is 65 / 35 or more, problems during patterning are less likely to occur. Further, when the blending ratio of the (B) component is 82.5 / 17.5 or less, since the ratio of the photoreactive functional group in the resin is sufficient, a desired crosslinked structure can be formed. Also, since the acid value in the resin component is not too high, the solubility in the alkaline developer in the exposed part is less likely to increase, so that the formed pattern can be prevented from becoming thinner than the target line width and pattern dropout can be suppressed.

[0198] 1-6. (F) Solvent (F) Solvent (hereinafter, also simply referred to as “(F) component”) is not particularly limited as long as it adjusts the viscosity of the photosensitive resin composition and improves coatability.

[0199] (F) As the component, known solvents can be used. Examples of the (F) component include terpenes such as α- or β-terpineol, ester solvents such as butyl acetate, cyclohexyl acetate, 3-methoxybutyl acetate, 3-methoxy-3-methylbutyl acetate, and 1,3-butylene glycol diacetate, ketone solvents such as acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone, methyl isobutyl ketone, and cyclohexanone, ether solvents having an ethylene glycol skeleton such as diethylene glycol ethyl methyl ether methyl cellosolve, ethyl cellosolve, methyl carbitol, dimethyl carbitol, ethyl carbitol, and butyl carbitol, ester and ether solvents having a propylene glycol skeleton such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol diacetate, acetate ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, and butyl carbitol acetate, alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxybutanol, and ethylene glycol mono-t-butyl ether, aromatic solvents such as toluene, xylene, and tetramethylbenzene, aliphatic solvents, amine solvents, and amide solvents. From the viewpoint of safety, ester and ether solvents having a propylene glycol skeleton and acetate ester solvents are preferred, and ester and ether solvents having a propylene glycol skeleton are more preferred. These solvents may be used in combination of two or more kinds.

[0200] (F) The content of the component is preferably 60% by mass to 98% by mass, more preferably 70% by mass to 98% by mass, and even more preferably 75% by mass to 95% by mass based on the total mass of the photosensitive resin composition. When the content of the (F) component is 60% by mass or more, the coatability of the photosensitive resin composition can be sufficiently enhanced. When the content of the (F) component is 98% by mass or less, it is easier to form a cured film with a thicker film thickness.

[0201] 1-7. Other additives The photosensitive resin composition according to this embodiment may contain, if necessary, an epoxy compound and its curing agent and curing accelerator, an inorganic filler other than the (A) component, a coupling agent, a surfactant, a resin other than the alkali-soluble resin, a thermal polymerization inhibitor and an antioxidant, a plasticizer, a filler, a leveling agent, an antifoaming agent, an ultraviolet absorber and other components.

[0202] 1-7-1. Epoxy compound Examples of epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, bisnaphthol fluorene type epoxy compounds, diphenylfluorene type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, phenol aralkyl type epoxy compounds, phenol novolac compounds containing a naphthalene skeleton (e.g., NC-7000L: manufactured by Nippon Kayaku Co., Ltd.), naphthol aralkyl type epoxy compounds, trisphenol methane type epoxy compounds (e.g., EPPN-501H: manufactured by Nippon Kayaku Co., Ltd.), epoxy compounds having an aromatic structure such as tetrakisphenol ethane type epoxy compounds, glycidyl ethers of polyhydric alcohols, glycidyl esters of polyvalent carboxylic acids, copolymers of monomers having a (meth)acryloyl group containing glycidyl (meth)acrylate as a unit typified by a copolymer of methacrylic acid and glycidyl methacrylate, epoxy compounds having a glycidyl group such as hydrogenated bisphenol A diglycidyl ether (e.g., Epiclon HBE-100: manufactured by Shin-Nippon Rika Co., Ltd., "Epiclon" is a registered trademark of the company), 1,4-cyclohexanedimethanol-bis 3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5,1-spiro(3,4-epoxy)cyclohexyl-m-dioxane (e.g., Araldite CY175: manufactured by Huntsman Corporation, "Araldite" is a registered trademark of the company), bis(3,4-epoxycyclohexylmethyl) adipate (e.g., CYRACURE UVR-6128: manufactured by Dow Chemical Company), 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (e.g., Celoxide 2021P: manufactured by Daicel Corporation, "Celoxide" is a registered trademark of the company), butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone (e.g., Epolide GT401: manufactured by Daicel Corporation, "Epolide" is a registered trademark of the company), epoxy compounds having an epoxycyclohexyl group (e.g., HiREM-1: manufactured by Shikoku Kasei Kogyo Co., Ltd.), polyfunctional epoxy compounds having a dicyclopentadiene skeleton (e.g., HP7200 series: manufactured by DIC Corporation), 2,Alicyclic epoxy compounds such as 1,2-epoxy-4-(2-oxiranyl) cyclohexane adducts of 2-bis(hydroxymethyl)-1-butanol (e.g., EHPE3150: manufactured by Daicel Corporation), epoxy polybutadiene (e.g., NISSO-PB·JP-100: manufactured by Nippon Soda Co., Ltd., "NISSO-PB" is a registered trademark of the company), epoxy compounds having a silicone skeleton, etc. are included. Among these, from the viewpoint of enhancing the flatness and low gas evolution property of the cured film, the epoxy compound having the above-mentioned aromatic structure is preferable.,

[0203] Examples of the curing agent include amine compounds, polyvalent carboxylic acid compounds or their anhydrides, thermally decomposable esters of polyvalent carboxylic acids, phenolic resins, amino resins, dicyandiamide, Lewis acid complex compounds, etc. that contribute to the curing of the epoxy resin. Among these, it is preferably selected from the group consisting of polyvalent carboxylic acids or their anhydrides, and thermally decomposable esters of polyvalent carboxylic acids.

[0204] Examples of the curing accelerator include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, tertiary amines such as 2-(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)undecene-7, 1,5-diazabicyclo[4.3.0]nona-5-ene, phosphines such as triphenylphosphine, tricyclohexylphosphine, triphenylphosphine triphenylborane, metal compounds such as tin octylate, etc. Among these, 1,8-diazabicyclo[5.4.0]undec-7-ene or 1,5-diazabicyclo[4.3.0]nona-5-ene or their salts are preferable.

[0205] 1-7-2. Other Compounds Examples of inorganic fillers other than the component (A) include talc, mica, glass fiber, carbon fiber, silica, calcium silicate, magnesium carbonate particles, calcium carbonate particles, calcium sulfate particles, barium sulfate particles, alumina particles, titanium oxide particles.

[0206] Examples of coupling agents include silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane, titanium-based coupling agents, and aluminum-based coupling agents. Among these, 3-glycidoxypropyltrimethoxysilane, which is a silane coupling agent, is preferred.

[0207] Examples of surfactants include fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, anionic surfactants, cationic surfactants, betaine-based surfactants, and the like.

[0208] Examples of resins other than alkali-soluble resins include vinyl resins, polyester resins, polyamide resins, polyimide resins, polyurethane resins, polyether resins, melamine resins, and the like.

[0209] Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenol-based compounds, and the like.

[0210] Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like. Examples of fillers include glass fiber, silica, mica, alumina, and the like.

[0211] Examples of defoaming agents and leveling agents include silicone-based, fluorine-based, and acrylic-based compounds.

[0212] Examples of ultraviolet absorbers include benzotriazole compounds, benzophenone compounds, triazine compounds, and the like.

[0213] 2. Method for producing the photosensitive resin composition The photosensitive resin composition according to this embodiment can be obtained by mixing the above components.

[0214] 3. Method for manufacturing a cured film The cured film according to this embodiment may be manufactured, for example, through the steps of: i) applying a photosensitive resin composition onto a substrate to form a coating film; ii) selectively exposing the coating film to radiation to cure it, and developing the coating film cured by the exposure to form a pattern (exposure and development steps); and iii) heat-treating (main curing) the coating film on which the pattern has been formed (heat treatment step).

[0215] The cured film according to this embodiment may be a cured film with a pattern formed thereon or a cured film without a pattern formed thereon. When manufacturing a cured film without a pattern formed thereon, the cured film may be manufactured through only the step of forming the coating film in the above step i).

[0216] 3-1. Step of forming a coating film The application of the photosensitive resin composition can be performed by a known coating method. Examples of the coating method include known solution immersion methods, spray methods, methods using a roller coater, a land coater, a slit coater, a spinner, etc. By these methods, the photosensitive resin composition can be applied to a desired thickness.

[0217] The coating film thus formed is preferably dried before exposure. The drying of the coating film can be performed by a known drying method. Examples of the drying method include heating by an oven, a hot air blower, a hot plate, an infrared heater, etc., vacuum drying, and combinations thereof. The heating temperature and heating time during drying can be appropriately selected according to the solvent used, and for example, it is preferably performed at 60 to 110°C for 1 to 5 minutes.

[0218] 3-2. Exposure and development steps Exposure can be performed by a method of irradiating radiation through a photomask onto a part of the above coating film. By this exposure, the part corresponding to the pattern of the coating film is photocured.

[0219] A known photomask can be used. Examples of photomasks include multi-tone masks such as halftone masks and grayscale masks. In a grayscale mask, a light-shielding portion and a diffraction grating are formed on a light-transmissive substrate. The diffraction grating has an interval between light-transmitting regions such as slits, dots, and meshes that is equal to or less than the resolution limit of the light used for exposure, and this configuration controls the light transmittance. In a halftone mask, a light-shielding portion and a semi-transmissive portion are formed on a light-transmissive substrate. The semi-transmissive portion controls the light transmittance of the light used for exposure.

[0220] The exposure apparatus used for exposure and its exposure irradiation conditions can be appropriately selected. Examples of the radiation to be irradiated include visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays. Among these radiations, ultraviolet light is preferably used. Also, known exposure apparatuses (such as ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, far ultraviolet lamps, etc.) can be used as the apparatus for irradiating the radiation. Further, the wavelength of the irradiated radiation is preferably 250 nm to 450 nm. The exposure dose of the radiation is preferably 25 mJ / cm2 to 3000 mJ / cm2.

[0221] After exposure, the coating film irradiated with the radiation is developed with an alkali to remove the coating film in the unexposed portion.

[0222] Examples of the developing method of the coating film include shower developing method, spray developing method, dip (immersion) developing method, and paddle (liquid bath) developing method. Note that the development can be performed using a commercially available developing machine, an ultrasonic cleaner, or the like.

[0223] Examples of the developer suitable for development include aqueous solutions of carbonates of alkali metals and alkaline earth metals, aqueous solutions of hydroxides of alkali metals, etc. Among these, it is preferable to perform the development at a temperature of 23 to 28 °C using a weakly alkaline aqueous solution containing 0.05 to 3 mass% of carbonates such as sodium carbonate, potassium carbonate, and lithium carbonate. Note that in the development process, a commercially available developing machine, an ultrasonic cleaner, or the like can be used.

[0224] 3-3. Heat Treatment Step The exposed part (coating film) after development is heat-treated for full curing (post-baking).

[0225] The method of heating the exposed part (coating film) after development can be carried out by a known method (heating by an oven, a hot air blower, a hot plate, an infrared heater, etc., vacuum drying, or a combination thereof). The heating temperature is not particularly limited as long as the coating film is fully cured (post-baked). The heating temperature is preferably carried out at a temperature of 60 to 250 °C for 20 to 60 minutes.

[0226] After heat curing, the coating film (cured film) may be washed with short-wavelength radiation to remove organic contaminants on the surface of the coating film.

[0227] The washing can be carried out, for example, by irradiating ultraviolet rays with wavelengths of 184.9 nm and 253.7 nm using a low-pressure mercury lamp. The irradiation amount at this time can be 1000 mJ.

[0228] 4. Substrate with a cured film The substrate with a cured film according to this embodiment is not particularly limited as long as it includes the cured film manufactured by the above manufacturing method and a substrate.

[0229] The substrate with a cured film according to this embodiment may be a substrate with a cured film using the substrate used in the step of forming the coating film as it is, or a substrate with a cured film obtained by transferring the cured film obtained by the manufacturing method to a different substrate.

[0230] Examples of the substrate include a semiconductor wafer, a semiconductor chip, a light-emitting element, an optical system glass wafer, a metal foil, a polishing pad, a resin coating film, a wiring layer, etc.

[0231] The substrate may be a flexible substrate or a non-flexible substrate. A flexible substrate is a substrate that can repeatedly bend and deform back to its original shape (a flat, non-bent shape). The ability to deform back to the original shape here means that there are no creases even after repeated bending. Examples of flexible substrates include resin films such as polyimide, flexible glass such as Corning's Willow glass and AGC's Dragontrail. Note that a transparent electrode such as ITO or gold may be vapor-deposited or patterned on the surface of the flexible substrate.

[0232] 5. Display device The display device according to this embodiment can use the substrate with the cured film as various functional layers such as a black matrix, a color filter, a light-shielding film, a protective film, and a wavelength conversion layer.

[0233] The light source of the display device may be a known light source such as an organic electroluminescence (EL) light source and a laser diode (LED) light source. Also, the display device may have a configuration in which a wavelength conversion layer containing quantum dots or a phosphor compound is disposed between the light source and the substrate with the cured film. The substrate with the cured film has particularly good flexibility resistance even when it is a thick film with a film thickness of 2 μm or 3 μm or more. Therefore, it is useful as a light-shielding film or the like that is disposed laterally with respect to the LED light source in an LED display having such a film thickness to suppress lateral light leakage.

[0234] 6. Sensor The sensor according to this embodiment can use the substrate with the cured film for the light-receiving element of the sensor or the like.

[0235] The sensor according to this embodiment is suitably used for components that require precise light-receiving sensitivity, such as sensors for detecting and ranging with light (laser) for in-vehicle use in autonomous driving (LiDAR) and encoder light-receiving elements.

Examples

[0236] Hereinafter, embodiments of the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited thereto.

[0237] Regarding various measuring instruments, when the same model is used, the name of the instrument manufacturer is omitted from the second place. Also, all the glass substrates used in the examples are used after the same treatment. Also, regarding the content of each component, when the first digit after the decimal point is 0, the notation after the decimal point may be omitted.

[0238] [Measurement method of physical properties] (Solid content concentration) The solid content concentration was determined from the following formula using the weight [W1 (g)] of 1 g of the resin solution obtained in the synthesis example impregnated in a glass filter [weight: W0 (g)] and the weight [W2 (g)] after heating at 160 ° C for 2 hours. Solid content concentration (wt%) = 100×(W2 - W0) / (W1 - W0)

[0239] (Acid value) The acid value was determined by dissolving the resin solution in dioxane and titrating with a 1 / 10N - KOH aqueous solution using a potentiometric titrator "COM - 1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0240] (Molecular weight) The molecular weight was measured by gel permeation chromatography (GPC) "HLC - 8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgel Super H - 2000 (2 pieces) + TSKgel Super H - 3000 (1 piece) + TSKgel Super H - 4000 (1 piece) + TSKgel Super H - 5000 (1 piece) (manufactured by Tosoh Corporation), temperature: 40 ° C, speed: 0.6 ml / min), and the weight average molecular weight (Mw) was determined as a value in terms of standard polystyrene (manufactured by Tosoh Corporation, PS - oligomer kit).

[0241] (Average primary particle size, shell thickness, porosity) The particle-containing solution was diluted with a solvent to a particle concentration of about 0.1 wt%, and the resulting dispersion was dropped onto a metallic mesh with a carbon support film to prepare a measurement sample. The average value of the particle diameters obtained by randomly observing 100 particles with a transmission electron microscope (TEM; JEOL Ltd., JEM-2000EX) was defined as the average primary particle diameter, and the average value of the shell thickness obtained by randomly observing 10 particles was defined as the shell thickness. Also, for the porosity, the longest and shortest diameters of the hollow filler were measured, and the average value was taken as the particle diameter of the particle, assuming the particle shape to be a true sphere to obtain the volume (V1). Next, the longest and shortest diameters of the cavity part of the particle were measured, and the average value was taken as the diameter of the cavity, assuming the cavity part shape to be a true sphere to obtain the volume (V2). The same measurement was performed on 10 randomly selected particles and expressed as the average value of the ratio of the volume (V2) to the volume (V1).

[0242] (Refractive index of component (B)) (The refractive index of component (B) was measured by the following method.)

[0243] (B) component was diluted with propylene glycol monomethyl ether acetate so that the solid content concentration became 20 mass%, and spin-coated on a silicon wafer with a diameter of 125 mm, "5-inch P-type wafer 1-100" (manufactured by Advantec Co., Ltd.) using a spin coater so that the film thickness after post-baking became 1.0 μm. Pre-baking was carried out at 90 °C for 1 minute. Then, post-baking was carried out at 230 °C for 30 minutes in an oven. Using the substrate, the refractive index with respect to light with a wavelength of 550 nm was measured with a spectroscopic ellipsometer "Alpha-SE" (manufactured by J.A. Woollam Co., Ltd.). -ter acetate so that the solid content concentration became 20 mass%, and spin-coated on a silicon wafer with a diameter of 125 mm, "5-inch P-type wafer 1-100" (manufactured by Advantec Co., Ltd.) using a spin coater so that the film thickness after post-baking became 1.0 μm. Pre-baking was carried out at 90 °C for 1 minute. Then, post-baking was carried out at 230 °C for 30 minutes in an oven. Using the substrate, the refractive index with respect to light with a wavelength of 550 nm was measured with a spectroscopic ellipsometer "Alpha-SE" (manufactured by J.A. Woollam Co., Ltd.). Advantec Co., Ltd.) so that the film thickness after post-baking became 1.0 μm. Pre-baking was carried out at 90 °C for 1 minute. Then, post-baking was carried out at 230 °C for 30 minutes in an oven. Using the substrate, the refractive index with respect to light with a wavelength of 550 nm was measured with a spectroscopic ellipsometer "Alpha-SE" (manufactured by J.A. Woollam Co., Ltd.). -ter acetate so that the solid content concentration became 20 mass%, and spin-coated on a silicon wafer with a diameter of 125 mm, "5-inch P-type wafer 1-100" (manufactured by Advantec Co., Ltd.) using a spin coater so that the film thickness after post-baking became 1.0 μm. Pre-baking was carried out at 90 °C for 1 minute. Then, post-baking was carried out at 230 °C for 30 minutes in an oven. Using the substrate, the refractive index with respect to light with a wavelength of 550 nm was measured with a spectroscopic ellipsometer "Alpha-SE" (manufactured by J.A. Woollam Co., Ltd.). -ter acetate so that the solid content concentration became 20 mass%, and spin-coated on a silicon wafer with a diameter of 125 mm, "5-inch P-type wafer 1-100" (manufactured by Advantec Co., Ltd.) using a spin coater so that the film thickness after post-baking became 1.0 μm. Pre-baking was carried out at 90 °C for 1 minute. Then, post-baking was carried out at 230 °C for 30 minutes in an oven. Using the substrate, the refractive index with respect to light with a wavelength of 550 nm was measured with a spectroscopic ellipsometer "Alpha-SE" (manufactured by J.A. Woollam Co., Ltd.).

[0244] [Preparation example of component (A)] [Preparation of hollow magnesium fluoride] With reference to Japanese Patent No. 5943754 and Korean Patent Publication No. 102510057, hollow magnesium fluoride particles with the average primary particle size, shell thickness, and porosity described below were prepared, respectively, and hollow magnesium fluoride dispersions (A)-1 to (A)-8 were prepared with 20% by mass of hollow magnesium fluoride particles, 2% by mass of a polymer dispersant, and 78% by mass of PGMEA.

[0245] <Production of Hollow Silica and Solid Magnesium Fluoride> In the production of the above-described hollow magnesium fluoride dispersion, in the same manner except that the hollow magnesium fluoride particles were changed to silica particles and solid magnesium fluoride particles, hollow silica dispersions and solid magnesium fluoride dispersions having the average primary particle size, shell thickness, and porosity described below were prepared.

[0246] [Synthesis Examples of Component (B) and Component (C)] The abbreviations used in the synthesis examples are as follows. DCPMA: Dicyclopentanyl methacrylate GMA: Glycidyl methacrylate St: Styrene AA: Acrylic acid AIBN: Azobisisobutyronitrile TDMAMP: Tris(dimethylaminomethyl)phenol HQ: Hydroquinone TEA: Triethylamine BPFE: Bisphenol fluorene type epoxy resin TEAB: Tetraethylammonium bromide BPDA: 3,3’,4,4’-Biphenyltetracarboxylic dianhydride THPA: Tetrahydrophthalic anhydride PGMEA: Propylene glycol monomethyl ether acetate

[0247] (Synthesis Example 1) Into a 1 L four-necked flask equipped with a reflux condenser, PGMEA (300.0 g) was placed, and after purging the inside of the flask system with nitrogen, the temperature was raised to 120 °C. A monomer mixture (a mixture in which 10 g of AIBN was dissolved in DCPMA (66.1 g, 0.30 mol), GMA (85.3 g, 0.60 mol), and St (10.4 g, 0.10 mol)) was added dropwise from a dropping funnel over 2 hours into this flask, and it was further stirred at 120 °C for 2 hours to obtain a copolymer solution.

[0248] Next, after purging the inside of the flask system with air, AA (43.2 g, 0.60 mol), TDMAMP (0.8 g), and HQ (0.15 g) were added to the obtained copolymer solution, and it was stirred under heating at 120 °C for 6 hours to obtain a copolymer solution containing polymerizable unsaturated groups.

[0249] Furthermore, THPA (59.3 g, 0.39 mol) and TEA (0.5 g) were added to the obtained copolymer solution containing polymerizable unsaturated groups, and it was reacted at 120 °C for 4 hours to obtain a polymerizable unsaturated group-containing alkali-soluble copolymer resin solution (B)-1. The solid content concentration of the resin solution was 48% by mass, the acid value (in terms of solid content) was 79 mg KOH / g, Mw by GPC analysis was 8500, and the refractive index was 1.52.

[0250] (Synthesis Example 2) BPFE (114.4 g, 0.23 mol), AA (33.2 g, 0.46 mol), PGMEA (157 g), and TEAB (0.48 g) were charged into a 500 ml four-necked flask equipped with a reflux condenser, and it was stirred and reacted at 100 to 105 °C for 20 hours. Next, BPDA (35.3 g, 0.12 mol) and THPA (18.3 g, 0.12 mol) were charged into the flask, and it was stirred at 120 to 125 °C for 6 hours to obtain an alkali-soluble resin (B)-2. The solid content concentration of the obtained resin solution was 56.1% by mass, the acid value (in terms of solid content) was 103 mg KOH / g, Mw by GPC analysis was 3600, and the refractive index was 1.62.

[0251] (Synthesis Example 3) Into a 1 L four-necked flask, PTMA (20 g, 0.19 mol of mercapto groups), DPHA (212 g, 2.12 mol of acrylic groups), PGMEA (58 g), HQ (0.1 g), and BzDMA (0.01 g) were added and reacted at 60 °C for 12 hours to obtain a dendritic polymer solution. The solid content concentration of the dendritic polymer solution was 80% by mass, and Mw by GPC analysis was 10,000. For the obtained dendritic polymer, disappearance of mercapto groups was confirmed by the iodometry method.

[0252] [Preparation of Photosensitive Resin Composition] A photosensitive resin composition was prepared using the following components.

[0253] [(A) Hollow Filler] (A)-1: Hollow magnesium fluoride, average primary particle size 56 nm, shell thickness 10 nm, porosity 27% (A)-2: Hollow magnesium fluoride, average primary particle size 56 nm, shell thickness 15 nm, porosity 10% (A)-3: Hollow magnesium fluoride, average primary particle size 56 nm, shell thickness 7 nm, porosity 45% (A)-4: Hollow magnesium fluoride, average primary particle size 56 nm, shell thickness 5 nm, porosity 63% (A)-5: Hollow magnesium fluoride, average primary particle size 56 nm, shell thickness 4 nm, porosity 75% (A)-6: Hollow magnesium fluoride, average primary particle size 40 nm, shell thickness 7 nm, porosity 28% (A)-7: Hollow magnesium fluoride, average primary particle size 80 nm, shell thickness 14 nm, porosity 27% (A)-8: Hollow magnesium fluoride, average primary particle size 100 nm, shell thickness 18 nm, porosity 26% (A)-9: Hollow magnesium fluoride, average primary particle size 130 nm, shell thickness 23 nm, porosity 26% (A)’-10: Solid magnesium fluoride, average primary particle size 56 nm (A)'-11: Hollow silica, average primary particle size 56 nm, shell thickness 10 nm, porosity 27% Note that the refractive index of the material constituting the shell of component (A) was taken as the value described in the refractive index list (https: / / www.filmetricsinc.jp / refractive-index-database) published by Filmetrics. The refractive index of the light with a wavelength of 550 nm of the materials constituting the shells of (A)-1 to (A)-9 and (A)'-10 was 1.38, and the refractive index of the light with a wavelength of 550 nm of the material constituting (A)'-11 was 1.46.

[0254] ((B) Alkali-soluble resin) (B)-1: Alkali-soluble resin synthesized in Synthesis Example 1 (B)-2: Alkali-soluble resin synthesized in Synthesis Example 2

[0255] ((C) Photoinitiator) (C)-1: Irgacure OXE01 (manufactured by BASF Japan Ltd.) (C)-2: Adeka Arcles NCI-831E (manufactured by Adeka Corporation)

[0256] ((D) Colorant) (D)-1: Carbon black dispersion (Carbon black: 25% by mass, polymer dispersant: 3% by mass, PGMEA: 72% by mass)

[0257] ((E) Photopolymerizable compound) (E)-1: Mixture of dipentaerythritol penta and hexaacrylate (M-405, manufactured by Toagosei Co., Ltd.) (E)-2: Mixture of pentaerythritol tri and tetraacrylate (M-450, manufactured by Toagosei Co., Ltd.) (E)-3: Dendritic polymer obtained in the above Synthesis Example 3

[0258] ((F) Solvent) (F)-1: PGMEA (propylene glycol monomethyl ether acetate) (F)-1: Butyl Acetate

[0259] (Surfactant) EFS-131: Active ingredient 20% by mass, Solvent: Butyl Acetate, Nonionic type EFS-321: Active ingredient 20% by mass, Solvent: PGMEA, Nonionic type EFS-521: Active ingredient 20% by mass, Solvent: PGMEA, Nonionic type EFS-801: Active ingredient 100% by mass, Nonionic type DOWSIL TM SH 3775 M Fluid: Active ingredient 100% by mass, Silicone type (hereinafter also referred to as "SH 3775 M") In addition, MEGAFACE (R) The EFS series is an environmentally considerate PFAS-free surfactant manufactured by DIC Corporation.

[0260] The above-mentioned respective components were mixed at the compounding ratios shown in Tables 1 to 6 below to prepare the photosensitive resin compositions of Examples 1 to 97 and Comparative Examples 1 to 6. Note that the numerical values other than the (F) component shown in Tables 1 to 6 are the masses of only the solid content, and the values shown in the columns of the (A) component and the (D) component indicate the addition amounts of the added inorganic particles or carbon black, and the polymer dispersants used for these are described in separate columns. Also, the solvents contained in the (A) component, the (D) component, and the surfactant are described as being totaled in (F)-1 or (F)-2 respectively.

[0261] Note that the refractive indices of Resin B-1 and Resin B-2 with respect to light of a wavelength of 550 nm measured by the above method were 1.53 and 1.60 respectively.

[0262]

Table 1

[0263]

Table 2

[0264]

Table 3

[0265]

Table 4

[0266]

Table 5

[0267]

Table 6

[0268] [Evaluation] <Refractive Index of Hardened Film> (Evaluation Method) The above photosensitive resin composition was applied onto a glass substrate "#1737" (manufactured by Corning Inc.) with a size of 125 mm × 125 mm using a spin coater so that the film thickness after post-baking would be 1 μm for cases other than Examples 18 and 41, and 0.1 μm for Examples 18 and 41. Pre-baking was carried out at 90°C for 1 minute. Subsequently, post-baking was carried out at 230°C for 30 minutes using an oven to obtain a substrate for refractive index evaluation.

[0269] Using the obtained evaluation substrates for refractive index of Examples 1 to 97 and Comparative Examples 1 to 6, the refractive index of the hardened film after post-baking was measured using spectroscopic ellipsometry "Alpha-SE" (manufactured by J.A.Woollam Co., Inc.), and the refractive index results at 550 nm are shown in Tables 7 to 12.

[0270] <Evaluation of Transmittance> (Evaluation Method) Using the evaluation substrates for refractive index of Examples 1 to 47 and Comparative Examples 1 to 2 and 5, the transmittance in the visible light region of 380 nm to 780 nm was measured using an ultraviolet-visible-near-infrared spectrophotometer "UH4150". The results are shown in Tables 7 to 9. Note that values of Δ or above were considered qualified.

[0271] (Evaluation Criteria) ◎: Transmittance is 95% or more ○: Transmittance is 90% or more and less than 95% △: Transmittance is 85% or more and less than 90% ×: Transmittance is less than 85%

[0272] (Measurement of Pencil Hardness) Using the refractive index evaluation substrates of Examples 1 to 47 and Comparative Examples 1 to 2, 5, in accordance with the JIS-K5400 test method, when applying a load of 500 g using a pencil hardness tester, the highest pencil hardness without scratching the coating film was taken as the measured value. The pencil used was "Mitsubishi Hi-Uni". The results are described in Tables 7 to 9. Note that △ or above was considered qualified.

[0273] (Evaluation Criteria) ○: Pencil hardness is 3H or more △: Pencil hardness is F, H, 2H ×: Pencil hardness is HB or less

[0274] (Reflectance of Transparent Film) Using the refractive index evaluation substrates of Examples 1 to 47 and Comparative Examples 1 to 2, 5, the SCI reflectance (film surface reflectance) R% on the cured film side was measured under the conditions of C light source, incident angle of 2°, and wavelength range of 380 to 780 nm using a spectrocolorimeter "SD7000" (manufactured by Nippon Denshoku Industries Co., Ltd.). The results are described in Tables 7 to 9. Note that △ or above was considered qualified.

[0275] (Evaluation Criteria) 〇: R% ≦ 6.6% △: 6.6% < R% ≦ 7.0% ×: 7.0% < R%

[0276] (Evaluation of OD / μm) Using the refractive index evaluation substrates of Examples 48 to 97 and Comparative Examples 3 to 4, 6, the OD value of the substrate was evaluated using a transmission densitometer. Also, the film thickness of the formed light-shielding film was measured, and the value obtained by dividing the OD value by the film thickness was defined as OD / μm. The results are described in Tables 10 to 12. (Reflectance of Light-Shielding Film) Using the substrates for refractive index evaluation of Examples 48 to 97 and Comparative Examples 3 to 4 and 6, the SCI reflectance (film surface reflectance) R% on the cured film side was measured under the conditions of a C light source, an incident angle of 2°, and a wavelength range of 380 to 780 nm using a spectrocolorimeter "SD7000" (manufactured by Nippon Denshoku Industries Co., Ltd.). The results are shown in Tables 10 to 12.

[0277] (Brightness in SCE mode) Using the substrates for refractive index evaluation of Examples 48 to 97 and Comparative Examples 3 to 4 and 6, the SCE brightness on the cured film side was measured under the conditions of a C light source, an incident angle of 2°, and a wavelength range of 380 to 780 nm using a spectrocolorimeter "SD7000" (manufactured by Nippon Denshoku Industries Co., Ltd.). The results are shown in Tables 10 to 12. Those with a value of ○ or more were considered qualified.

[0278] (Evaluation criteria for brightness in SCE mode) ○: Brightness in SCE mode is less than 6.0 ×: Brightness in SCE mode is 6.0 or more

[0279] (Patternability) The photosensitive resin compositions of Examples 1 to 97 and Comparative Examples 1 to 6 above were applied onto a glass substrate "#1737" (manufactured by Corning) measuring 125 mm × 125 mm using a spin coater so that the film thickness after post-baking would be 1 μm for those other than Examples 18 and 41, and 0.1 μm for Examples 18 and 41. Pre-baking was carried out at 90°C for 1 minute. Thereafter, a negative photomask having a line pattern with an opening width of 1 to 20 μm was brought into close contact with the dried coating film, and ultraviolet light of 40 mJ / cm2 was irradiated using an ultra-high pressure mercury lamp with an i-line illuminance of 30 mW / cm2 to effect the photocuring reaction of the photosensitive portion.

[0280] Next, this exposed coated plate was placed in an aqueous solution of 0.04% potassium hydroxide at 23°C and developed under a shower developing pressure of 1 kgf / cm2. Starting from the developing time when the pattern began to appear (break time = BT), after developing for +20 seconds, spray water washing was performed at a pressure of 5 kgf / cm2 to remove the unexposed part of the coating film and form a line pattern on the glass substrate. Then, after heat post-baking at 85°C for 60 minutes using a hot air dryer, the minimum resolution line width was defined as the minimum opening line in the resulting line pattern where no pattern peeling occurred. In addition, Examples 1 to 47, Comparative Examples 1 to 2, 5, and Examples 48 to 97, Comparative Examples 3 to 4, 6 were evaluated according to the following evaluation criteria. The results are shown in Tables 7 to 12. Note that a result of △ or better was considered qualified. (Evaluation Criteria for Patterning Properties) <Examples 1 to 47, Comparative Examples 1 to 2, 5> 〇: Less than 20 μm △: Greater than 20 μm and 30 μm or less ×: Greater than 30 μm <Examples 48 to 97, Comparative Examples 3 to 4, 6> 〇: Less than 5 μm △: Greater than 5 μm and 10 μm or less ×: Greater than 10 μm

[0281]

Table 7

[0282]

Table 8

[0283]

Table 9

[0284]

Table 10

[0285]

Table 11

[0286]

Table 12

[0287] From the results of Table 7 and Table 12, it can be seen that by using (A) a hollow filler with a refractive index of the material constituting the shell being 1.20 to 1.40 and (B) an alkali-soluble resin with a refractive index of 1.50 to 1.70 when the cured film has a film thickness of 1 μm, a cured film with a low refractive index can be obtained, and the patterning property is also improved.

[0288] Comparing Examples 25 to 47 with Comparative Example 1, it can be seen that adding (A) a hollow filler with a refractive index of the material constituting the shell being 1.20 to 1.40 reduces the refractive index. In particular, comparing Example 31 with Comparative Example 1, it can be seen that not only is the refractive index further reduced, but the pencil hardness is also improved.

[0289] Comparing Example 4 with Comparative Example 5, for Comparative Example 5 using a hollow filler with a shell refractive index exceeding 1.40, Example 4 using a hollow filler with a shell refractive index of 1.20 to 1.40 shows a decrease in refractive index, and an improvement in transmittance, patterning property, and film surface reflectance. Also, in Example 4, since magnesium fluoride with a sufficiently high specific gravity is used with respect to the density of a general-purpose solvent, component (A) is more likely to be uniformly present in the film thickness direction compared to Comparative Example 5 using silica with a lower density than magnesium fluoride, and it can be seen that the pencil hardness is improved.

[0290]

[0291] ​When comparing Examples 78 to 97 and Comparative Example 3, which contain the same amount of component (D), it can be seen that by adding a hollow filler with a refractive index of the material constituting the (A) shell of 1.20 to 1.40, the refractive index decreases and the reflectance is significantly improved.

[0292] When comparing Example 48 and Comparative Example 6, it can be seen that even in the system containing component (D), Example 48 using a hollow filler with a refractive index of the shell of 1.20 to 1.40 has improved refractive index, film surface reflectance, patterning property, and SCE brightness compared to Comparative Example 6 using a hollow filler with a refractive index of the shell of more than 1.40.

[0293] When comparing Example 50 and Comparative Example 4, which contain the same amount of component (D), it can be seen that Example 50 using a hollow filler has a lower refractive index, significantly improved reflectance, and good patterning property compared to Comparative Example 4 using solid particles.

Industrial Applicability

[0294] According to the photosensitive resin composition of the present invention, a cured film with a low refractive index can be obtained, and the patterning property is also good.

Claims

1. (A) a hollow filler; (B) an alkali-soluble resin; (C) a photopolymerization initiator; and Including, The refractive index of the material constituting the shell of the hollow filler (A) is 1.20 to 1.40, The (B) alkali-soluble resin has a refractive index of 1.50 to 1.70 when cured into a film having a thickness of 1 μm. Photosensitive resin composition.

2. The hollow filler (A) has an average primary particle size of 150 nm or less. The photosensitive resin composition according to claim 1 .

3. The porosity of the hollow filler (A) is 5% by volume to 80% by volume. The photosensitive resin composition according to claim 1 .

4. The material constituting the shell of the hollow filler (A) is magnesium fluoride. The photosensitive resin composition according to claim 1 .

5. (D) a colorant; The photosensitive resin composition according to claim 1 .

6. The (D) colorant is a light-shielding material. The photosensitive resin composition according to claim 5 .

7. The light blocking material includes carbon black. The photosensitive resin composition according to claim 6.

8. A step of applying the photosensitive resin composition according to any one of claims 1 to 7 onto a substrate; a step of exposing the applied photosensitive resin composition through a photomask, removing the unexposed area by development, and then performing a heat treatment; The method for producing a cured film comprising the steps of:

9. A patterned cured film produced by the method for producing a cured film according to claim 8. Substrate with cured film.

10. A display device comprising the substrate with the cured film according to claim 9.

11. A sensor comprising a substrate with the cured film according to claim 9.

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