Photosensitive resin composition, light-shielding film, and display device

Abstract

To provide a photosensitive resin composition and light-shielding film that achieve both high light-shielding properties and reduced reflectivity on both the glass substrate side and the film side, while also being environmentally friendly by using extremely low amounts of fluorine and meeting requirements such as PFAS regulations. [Solution] A photosensitive resin composition characterized by containing components (A) to (F) and satisfying both (i) and (ii) below. (i) When a cured film of the composition is deposited on a glass substrate with an average film thickness in the range of 0.5 to 4.0 μm, and the surface of the film is measured by XPS, the peak area A of SiO2 in the peak fit analysis of the Si2p3 / 2 peak is... SiO2 And, peak area A SiO The ratio (A SiO2 / A SiO The value must be between 0.10 and 10.0. (ii) The ratio of the amount of element F to the total amount of elements Si, C, O, and F present on the surface of the film [F / (Si+C+O+F)] is 5.0% or less.

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition, a light-shielding film made of a cured product obtained by curing the resin composition, and a display device equipped with the light-shielding film. [Background technology]

[0002] In recent years, with the development of mobile devices, there has been an increase in display devices with touch panels or liquid crystal panels used outdoors or in vehicles. In these display devices, a light-shielding film is provided on the outer frame of the touch panel to block light leakage from the area around the liquid crystal panel on the back, and a light-shielding film (black matrix) is provided on the liquid crystal panel to suppress light leakage from the screen when displaying black and to suppress color mixing between adjacent color resists.

[0003] Black matrices are required to have both high light-shielding properties and low reflectivity. For example, Patent Document 1 proposes a technology that achieves both high light-shielding properties, reduced reflectivity of the light-shielding film, and good patterning performance (developability) during alkaline development when manufacturing the light-shielding film. This is achieved by particularly incorporating silica particles into a photosensitive resin composition and examining the atomic ratio of Si elements near the surface of the film when elemental analysis is performed on a cross-section of the film made from the cured product of the photosensitive resin composition using energy-dispersive X-ray spectroscopy with STEM-EDS. In Patent Document 1, when evaluating reflectivity, the reflectivity from the surface side of the glass substrate coated with and cured with the photosensitive resin composition is measured.

[0004] Incidentally, in light-shielding films for sensors such as various display devices and solid-state image sensors, depending on the design of the device configuration, there are not only cases where it is necessary to reduce the reflectance of the light-shielding film applied to a transparent substrate such as glass on the transparent substrate side, but also cases where it is necessary to reduce the reflectance of the side opposite to the surface in contact with the transparent substrate (hereinafter sometimes referred to as the "film surface (side)").

[0005] For example, Patent Document 2 proposes a technique to obtain a colored cured film for an image display device containing silica particles, in which the Si element content is 7.0 atm% or more as determined by surface elemental composition analysis by X-ray photoelectron spectroscopy (XPS). This technique involves using particles with a relatively small primary particle size and a relatively high concentration to lower the reflectance on the surface side of the colored cured film. However, in Patent Document 2, when evaluating the reflectance, the reflectance is only measured from the colored cured film side (not the glass substrate side) of the substrate with the colored cured film. Furthermore, the colored cured film in Patent Document 2 uses fluorine-based compounds, which are not necessarily environmentally friendly and do not meet the requirements of recent regulations on perfluorinated compounds (PFAS).

[0006] Furthermore, Patent Document 3 proposes a technique for reducing the reflectivity of both the cured film (light-shielding film) and the substrate (glass substrate) by incorporating silica particles in a photosensitive resin composition, and by using hollow particles as the silica particles, focusing on the high dispersibility and low refractive index of the hollow particles.

[0007] Furthermore, Patent Document 4 proposes a technique for reducing the reflectivity on both the substrate (glass substrate) side and the film surface side by focusing on suppressing the aggregation of silica particles and improving dispersibility (mobility) by specifying both the acid value and amine value of the dispersant, specifying the total mass of the dispersant relative to the total mass of the silica particles, and further including a first solvent and a second solvent as the solvent. However, even with the technologies proposed in Patent Documents 3 and 4, while it is possible to relatively increase the light-shielding component when achieving a reduction in reflectivity due to silica segregation on the film surface side, along with high light-shielding properties, the inventors of the present invention have found that this results in the generation of aggregated foreign matter, making it impossible to meet the quality requirements. Therefore, there was still room for improvement in achieving both high light-shielding properties and a reduction in reflectivity on both the glass substrate surface and the film surface. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Application Laid-Open No. 2022-52426 [Patent Document 2] Japanese Patent No. 6845469 [Patent Document 3] Japanese Patent Application Laid-Open No. 2020-166156 [Patent Document 4] Japanese Patent Application Laid-Open No. 2024-68130 [Summary of the Invention] [Problems to be Solved by the Invention]

[0009] Therefore, as a result of intensive studies based on the prior art as described above, the inventors have found that, as a technical matter that has not been focused on in the prior art, the peak area A of SiO2 in the peak fitting analysis of the Si2p3 / 2 peak measured by X-ray photoelectron spectroscopy (XPS) on the surface of the light-shielding film ,

[0010] , SiO , , SiO , , SiO , , , , , SiO2 ,

[0009] , SiO2 , , SiO2 , , , and the peak area A of SiO SiO and the ratio (A SiO2 / A SiO ) is defined within a predetermined range, it is possible to achieve both high light-shielding properties and reduction of reflectance on both the glass substrate surface side and the film surface side, and by minimizing the amount of fluorine used, it was found that a light-shielding film that can meet the requirements for PFAS regulations and the like and is environmentally considerate can be obtained, and the present invention was completed.

[0010] Therefore, an object of the present invention is to provide a photosensitive resin composition that achieves both high light-shielding properties and reduction of reflectance on both the glass substrate surface side and the film surface side, and moreover, has an extremely small amount of fluorine used and can meet the requirements for PFAS regulations and the like and is environmentally considerate, a light-shielding film composed of a cured product of the composition, and a display device including the light-shielding film. In addition, in the development of a light-shielding film composed of a photosensitive resin composition using silica particles and its cured product, the ratio of the peak areas A SiO2 / A SiOThrough the study, it is also an object of the present invention to provide a method for evaluating the degree of reflectance of the film surface (i.e., the degree of segregation of silica particles described later).

Means for Solving the Problems

[0011] That is, the gist of the present invention is as follows. [1] A photosensitive resin composition for forming a light-shielding film, comprising the following components (A) to (F): (A) An alkali-soluble resin, (B) A photopolymerizable compound having at least one ethylenically unsaturated bond, (C) A photopolymerization initiator, (D) A light-shielding agent, (E) Silica particles, (F) A silane coupling agent and satisfying both of the following (i) and (ii). A photosensitive resin composition characterized by (i) On a glass substrate, a film composed of a cured product of the photosensitive resin composition is formed with an average film thickness in the range of 0.5 to 4.0 μm, and in the peak fitting analysis of the Si2p3 / 2 peak measured by X-ray photoelectron spectroscopy (XPS) with respect to the surface of the film, the peak area A of SiO2 of 103.9 to 104.2 eV SiO2 and the peak area A of SiO of 101.8 to 102.3 eV SiO and the ratio (A SiO2 / A SiO ) is 0.10 to 10.0. (ii) The ratio of the amount of F element to the total amount of Si, C, O and F elements present in the surface of the film [F / (Si + C + O + F)] is 5.0% or less. [2] The photosensitive resin composition according to [1], wherein the component (A) is a polymerizable unsaturated group-containing alkali-soluble resin represented by the following general formula (II).

Chemical formula

[10] [9]. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a photosensitive resin composition that achieves both high light-shielding properties and a reduction in reflectivity on both the glass substrate side and the film side, and moreover, uses an extremely small amount of fluorine, thus meeting requirements such as PFAS regulations and being environmentally friendly, as well as a light-shielding film made of a cured product thereof, and a display device equipped with the light-shielding film. [Brief explanation of the drawing]

[0013] [Figure 1] Figure 1 shows the peaks of SiO2 and SiO measured by XPS for the film according to Example 28. [Modes for carrying out the invention]

[0014] Embodiments of the present invention will be described below.

[0015] 1. Photosensitive resin composition The photosensitive resin composition for forming a light-shielding film of the present invention (hereinafter sometimes referred to as "photosensitive resin composition") comprises (A) an alkali-soluble resin, (B) a photopolymerizable compound having at least one ethylenically unsaturated bond, (C) a photopolymerization initiator, (D) a light-shielding agent, (E) silica particles, and (F) a silane coupling agent. The photosensitive resin composition of the present invention may also preferably further contain compound (G) described below. Furthermore, the photosensitive resin composition of the present invention may also preferably contain (H) a solvent. Hereafter, for example, (A) alkali-soluble resin may be referred to as "component (A)," and the same applies to other components.

[0016] Furthermore, the photosensitive resin composition of the present invention satisfies both of the following conditions (i) and (ii). (i) A film made of the cured product of the photosensitive resin composition is deposited on a glass substrate with an average film thickness in the range of 0.5 to 4.0 μm, and the peak area A of the Si2p3 / 2 peak in the peak fit analysis of the Si2p3 / 2 peak measured by X-ray photoelectron spectroscopy (XPS) on the surface of the film is calculated to be SiO2 at 103.9 to 104.2 eV. SiO2 And the peak area A of SiO at 101.8~102.3 eV SiO The ratio (A SiO2 / A SiO The value must be between 0.10 and 10.0. (ii) The ratio of the amount of element F to the total amount of elements Si, C, O, and F present on the surface of the film [F / (Si+C+O+F)] is 5.0% or less.

[0017] First, let's explain (i) above. As shown in (i) above, the photosensitive resin composition of the present invention is used when a film made of a cured product of the photosensitive resin composition is formed on a glass substrate with an average film thickness in the range of 0.5 to 4.0 μm, and when the surface of the film is measured by X-ray photoelectron spectroscopy (XPS), the ratio of the peak areas is A. SiO2 / A SiO The characteristic is that the ratio A of the peak area is between 0.10 and 10.0. SiO2 / A SiO As this range allows for a reduction in reflectivity on both the glass substrate side and the film side, as will be confirmed in the embodiments described later. For example, a preferred range for the ratio of the peak areas is 0.25 to 10.0.

[0018] The reason for setting the average film thickness within the aforementioned range during XPS measurement is that if the average film thickness is below the lower limit, sufficient light shielding cannot be achieved, and the film tends to become transparent. On the other hand, if it exceeds the upper limit, patternability decreases, and it may affect the state of the silica particles. In other words, considering these points, if the measurement is not performed within the aforementioned range of average film thickness, it may not be suitable for the purpose of XPS measurement in this invention. The preferred average film thickness is 0.5 to 3.5 μm, and more preferably 0.5 to 3.0 μm. The average film thickness can be the value measured using a stylus-type step shape measuring device. The film deposition method will be described later.

[0019] Regarding the reduction of the reflectivity of the film (cured film, light-shielding film), as shown in the prior art, by incorporating silica particles, the refractive index of the cured film (light-shielding film) can be lowered. As a result, reflection caused by the difference in refractive index between the glass substrate and the film on the glass substrate side, or by the difference in refractive index between air and the film on the film side, can be suppressed, thereby reducing the reflectivity of the film. Furthermore, it is thought that the effect of reducing reflectivity can be obtained more effectively by making the silica particles present in greater quantity (higher density) near the surface of the film (glass substrate side and the film side opposite to it). For example, as examined in the aforementioned Patent Documents 3 and 4, it is thought that a sufficient amount of silica particles can be unevenly distributed near the surface of the film (glass substrate side and the film side opposite to it) by improving the dispersibility of silica particles in the photosensitive resin composition and making it less likely for the movement of silica particles to be restricted due to aggregation in the composition.

[0020] However, regarding the degree of segregation of silica particles, for example, Patent Document 1 involves surface elemental composition analysis of the film surface by XPS, and Patent Document 2 involves energy-dispersive X-ray analysis of the film cross-section using STEM-EDS to investigate the Si element content. However, since both methods focus only on the Si element, they are not accurate measurement methods that reflect whether silica particles are segregated near the surface of the film when other components containing Si that are not due to silica particles are used in combination.

[0021] Furthermore, our own investigations revealed that simply increasing the silica content can sometimes increase the difference in refractive index between the air layer and the film surface, meaning that low reflectivity on the film surface is not always achieved. We also found that high silica content can lead to aggregation, or, when cured, silica particles may be exposed to the outside from the film surface, resulting in increased surface irregularities. Therefore, it is necessary to use an appropriate silica content ratio, as this can negatively affect the quality. Therefore, after careful consideration, we found that not only is it possible to increase the amount (concentration) of silica near the surface of the film by adjusting the silica content, but in particular, by using components having SiO bonds (structure (X)), such as compound (G) described later, in combination with silica particles, the peak A originating from SiO2 in the silica particles can be improved. SiO2 And, the SiO-derived peak A present in compound (G), etc. SiO By focusing on the ratio, we found a range of the ratio that can achieve a reduction in reflectivity on both the glass substrate side and the film side, taking into account the effect of segregation of silica particles as well as the impact on leveling properties (surface smoothness, wettability to the underlying substrate) and quality. In other words, in the present invention, as described above, when measured by XPS, the ratio of the peak areas is A. SiO2 / A SiOThe technical significance lies in the discovery of a new technical aspect: by setting the value to 0.10-10.0, it becomes possible to determine that a large amount of silica particles are segregated on the film surface, and it also becomes possible to determine the amount (proportion) of SiO (the amount of components such as compound (G) described later) while considering the impact on leveling properties and quality, as mentioned above.

[0022] The reason for using the Si2p3 / 2 peak in the XPS measurement of this invention is that the bonding state of Si measured by XPS is generally analyzed using the Si2p3 / 2 peak, and there is a large amount of past analysis data available for reference, such as in the software's database and literature. Peak fitting analysis, also known as peak fitting processing, is performed for purposes such as separating overlapping peaks and estimating peak positions. The peak fitting procedure is usually performed in the following order: (1) background removal and correction, (2) selection of a fitting function, (3) optimization using nonlinear least squares method, (4) determination of fitting function parameters, and (5) evaluation and examination using a database. The procedure is not limited, as it can be determined appropriately taking into account known methods, but in this invention, the procedure and conditions used in the embodiments described later can be adopted.

[0023] In this invention, by measuring using XPS, especially when a component having an SiO bond (structure (X)), such as compound (G) described later, is used in combination with silica particles, the peak derived from SiO2 in the silica particles and the peak derived from SiO in compound (G) can be separated, and the ratio of the respective peak areas obtained therefrom, A SiO2 / A SiOThis was achieved based on the discovery that the reflectance of the film surface (glass substrate side and film surface side and the opposite side) correlates well with this. In other words, the degree of silica segregated near the surface of a film made from a cured product of a photosensitive resin composition cannot be accurately reflected by conventional methods of measuring the degree of Si content, and it has been difficult to predict the reflectance of the surface of the obtained film in relation to the composition's components and their amounts. However, in the photosensitive resin composition of the present invention, even if the components or structure are changed, the ratio of the peak areas, A SiO2 / A SiO The fact that this can be achieved by adjusting it to fall within a predetermined range also has technical significance.

[0024] Each peak obtained by this method is shown, for example, in Figure 1. The solid line peaks in Figure 1 represent the measured values ​​obtained by the method described later in <XPS Analysis of Film Surface>, and these are referred to later in <Ratio of Peak Area A of Film Surface>. SiO2 / A SiO By separating the peaks using the method described in "Calculation of", the peaks can be separated into the SiO2 peak shown by the dotted line and the SiO peak shown by the dashed line. Furthermore, by integrating each of these peaks, the area of ​​each peak can be calculated. Then, the calculated peak area A SiO2 , A SiO Based on this, A is the ratio of the peak areas. SiO2 / A SiO It is possible to calculate this.

[0025] Next, we will explain (ii). As described in (ii), the photosensitive resin composition of the present invention is characterized in that the ratio of the amount of element F to the total amount of elements Si, C, O, and F present on the surface of the film formed in (i) [F / (Si+C+O+F)] is 5.0% or less. This ratio is preferably 1.0% or less, more preferably 0.1% or less, even more preferably 0.01% or less, even more preferably 0.001% or less, and most preferably contains no F.

[0026] In other words, in the present invention, by minimizing the use of components containing element F in the photosensitive resin composition, or by using components with a relatively low amount of element F, it is possible to meet requirements such as PFAS regulations, be environmentally conscious, and obtain a film that has the characteristics of (i) above and has reduced reflectivity on the film surface.

[0027] The method for measuring the amount of each element is not limited, but as shown in the examples below, it can be measured by quantitative analysis of each element by scanning the energy range in which the specific element appears with high resolution using narrow-scan analysis in XPS measurement, similar to (i), as described below. The analytical conditions are preferably as described in the examples, and the content (atomic concentration (atom%)) can be measured by correcting the peak area with a relative sensitivity factor using the relative sensitivity factor method based on the peak intensity in the narrow spectrum of the detected element (Si, C, O, F), and then calculating the ratio (%) of the content of element F to the total content of elements Si, C, O, and F. In (i) and (ii) above, the measurement range and depth can be set as appropriate according to the measuring device, etc., and are not limited. However, the measurement range (planar range) should generally follow the X-ray irradiation range, and it is usually preferable to measure a circular area of ​​about 1 mm to 10 mm. The measurement depth is 2 to 8 nm, and is usually preferably 2 to 4 nm. In other words, the depth range for the aforementioned "film surface," etc., is determined from the range of the measurement depth.

[0028] The specific components of the photosensitive resin composition of the present invention that possesses the above-mentioned (i) and (ii) will be described below.

[0029] <(A) Alkali-soluble resin> The alkali-soluble resin is more preferably an unsaturated group-containing alkali-soluble resin that has an acid value for imparting alkali developability and possesses appropriate photocurability when combined with the photopolymerizable compound of component (B) described later. While any known unsaturated group-containing alkali-soluble resin can be used without limitation, those described below are even more preferable because they offer high heat resistance and enable the formation of highly detailed patterns.

[0030] A first example of an unsaturated group-containing alkali-soluble resin that is preferably applicable as an alkali-soluble resin is an epoxy (meth)acrylate adduct obtained by reacting a compound having two or more epoxy groups with (meth)acrylic acid (meaning acrylic acid and / or methacrylic acid), and then reacting the resulting epoxy (meth)acrylate compound having a hydroxyl group with (a) a dicarboxylic acid or tricarboxylic acid or its monoanhydride, and / or (b) a tetracarboxylic acid or its dianhydride. Examples of compounds having two or more epoxy groups that lead to an epoxy (meth)acrylate adduct include bisphenol-type epoxy compounds and novolac-type epoxy compounds. Specifically, a bisphenol-type epoxy compound represented by the following general formula (I) can be preferably cited.

[0031] [ka]

[0032] In general formula (I), R1, R2, R3, and R4 each independently represent a hydrogen atom, a C1-C5 alkyl group, a halogen atom, or a phenyl group, and A represents -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a fluorene-9,9-diyl group, or a direct bond. l is an integer from 0 to 10. Preferred R1, R2, R3, and R4 are hydrogen atoms, and preferred A is a fluorene-9,9-diyl group. Also, since l usually has multiple values, the average value is 0 to 10 (not necessarily an integer), but the preferred average value of l is 0 to 3. From here on, the explanation will use the case where l=0 in general formula (I).

[0033] Bisphenol-type epoxy compounds are epoxy compounds having two glycidyl ether groups obtained by reacting bisphenols with epichlorohydrin. This reaction generally involves oligomerization of the diglycidyl ether compound, and therefore includes epoxy compounds containing two or more bisphenol skeletons.

[0034] The bisphenols used in this reaction include bis(4-hydroxyphenyl)ketone, bis(4-hydroxy-3,5-dimethylphenyl)ketone, bis(4-hydroxy-3,5-dichlorophenyl)ketone, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxy-3,5-dimethylphenyl)sulfone, bis(4-hydroxy-3,5-dichlorophenyl)sulfone, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxyphenyl) Nyl)dimethylsilane, bis(4-hydroxy-3,5-dimethylphenyl)dimethylsilane, bis(4-hydroxy-3,5-dichlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3- Chlorophenyl)propane, bis(4-hydroxyphenyl) ether, bis(4-hydroxy-3,5-dimethylphenyl) ether, bis(4-hydroxy-3,5-dichlorophenyl) ether, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene, 9, 9-Bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-Bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-Bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-Bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-Bis(4-hydroxy-3,5-dichlorophenyl)fluorene, 9,9-Bis(4-hydroxy-3,5-dibromophenyl)fluorene, 9,9-Bis[4-(2-hydroxyethoxy)phenyl]fluorene, 4,4'-Biphenol, 3,Examples include 3'-biphenols. Among these, bisphenols having a fluorene-9,9-diyl group are particularly preferred.

[0035] Furthermore, the (a) dicarboxylic acid or tricarboxylic acid acid monoanhydride to be reacted with the epoxy (meth)acrylate obtained by reacting such an epoxy compound with (meth)acrylic acid can be a chain-type hydrocarbon dicarboxylic acid or tricarboxylic acid acid monoanhydride, an alicyclic dicarboxylic acid or tricarboxylic acid acid monoanhydride, or an aromatic dicarboxylic acid or tricarboxylic acid acid monoanhydride. Here, examples of chain-type hydrocarbon dicarboxylic acid or tricarboxylic acid acid monoanhydrides 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, and may also be a dicarboxylic acid or tricarboxylic acid acid monoanhydride to which any substituent has been introduced. Furthermore, examples of alicyclic dicarboxylic acid or tricarboxylic acid acid monoanhydrides include cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chloridenic acid, hexahydrotrimellitic acid, norbornanedicarboxylic acid, and may also be acid monoanhydrides of dicarboxylic acid or tricarboxylic acid to which any substituent has been introduced. Furthermore, examples of aromatic dicarboxylic acid or tricarboxylic acid acid monoanhydrides include phthalic acid, isophthalic acid, trimellitic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and may also be acid monoanhydrides of dicarboxylic acid or tricarboxylic acid to which any substituent has been introduced.

[0036] Furthermore, as the (b) tetracarboxylic acid dianhydride to be reacted with epoxy (meth)acrylate, a dianhydride of a chain-type hydrocarbon tetracarboxylic acid, a dianhydride of an alicyclic tetracarboxylic acid, or a dianhydride of an aromatic tetracarboxylic acid can be used. Here, as the dianhydride of a chain-type hydrocarbon tetracarboxylic acid, for example, there are dianhydrides of butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, etc., and furthermore, dianhydrides of tetracarboxylic acids to which any substituent has been introduced may also be used. As the dianhydride of an alicyclic tetracarboxylic acid, for example, there are dianhydrides of cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid, etc., and furthermore, dianhydrides of tetracarboxylic acids to which any substituent has been introduced may also be used. Furthermore, examples of acidic dianhydrides of aromatic tetracarboxylic acids include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, naphthalene-2,3,6,7-tetracarboxylic acid, and other acidic dianhydrides of tetracarboxylic acids to which any substituent has been introduced may also be used.

[0037] The molar ratio (a) / (b) of (a) a dicarboxylic acid or tricarboxylic acid monoanhydride and (b) a tetracarboxylic acid dianhydride reacted with epoxy (meth)acrylate is preferably 0.01 to 10.0, and more preferably 0.02 to less than 3.0. A molar ratio (a) / (b) within the above range is preferable because it is easier to obtain the optimal molecular weight for a photosensitive resin composition with good photopatternability, and alkali solubility is not impaired.

[0038] The reaction between the epoxy compound and (meth)acrylic acid, and the reaction method between the epoxy (meth)acrylate obtained in this reaction and the aforementioned polybasic carboxylic acid or its acid anhydride, are not particularly limited and known methods can be employed. For example, it can be produced by the method described in Japanese Patent Publication No. 8-278629 and Japanese Patent Publication No. 2008-9401, etc. First, as a method for reacting the epoxy compound with (meth)acrylic acid, for example, one method is to add an equimolar amount of (meth)acrylic acid to the epoxy group of the epoxy compound into a solvent, and in the presence of a catalyst (triethylbenzylammonium chloride, 2,6-diisobutylphenol, etc.), heat and stir at 90-120°C while blowing in air to carry out the reaction. Next, as a method for reacting the hydroxyl group of the reaction product, the epoxy acrylate compound, with an acid anhydride, predetermined amounts of the epoxy acrylate compound, acid dianhydride, and acid monoanhydride are added to a solvent, and the reaction is carried out by heating and stirring at 90-130°C in the presence of a catalyst (tetraethylammonium bromide, triphenylphosphine, etc.). The epoxy acrylate acid adduct obtained by this method has the skeleton of general formula (II).

[0039] [ka]

[0040] In formula (II), R1, R2, R3, and R4 each independently represent a hydrogen atom, a C1-C5 alkyl group, a halogen atom, or a phenyl group; A represents -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a fluorene-9,9-diyl group, or a direct bond; X represents a tetravalent carboxylic acid residue; Y1 and Y2 each independently represent a hydrogen atom or -OC-Z-(COOH)m (where Z represents a divalent or trivalent carboxylic acid residue, and m represents a number from 1 to 2); and n represents an integer from 1 to 20. R5 represents a hydrogen atom or a methyl group.

[0041] Next, a second example of an unsaturated group-containing alkali-soluble resin that is preferably applicable to alkali-soluble resins includes copolymers of (meth)acrylic acid, (meth)acrylic acid esters, etc., which have (meth)acryloyl groups and carboxyl groups. Examples of such resins include an unsaturated group-containing alkali-soluble resin obtained by copolymerizing (meth)acrylic acid esters containing glycidyl (meth)acrylate in a solvent, reacting the copolymer with (meth)acrylic acid, and finally reacting it with an anhydride of a dicarboxylic acid or tricarboxylic acid. The copolymer can be based on the copolymer described in Japanese Patent Publication No. 2014-111722, which consists of 20-90 mol% repeating units derived from diester glycerol with hydroxyl groups at both ends esterified with (meth)acrylic acid, and 10-80 mol% repeating units derived from one or more polymerizable unsaturated compounds copolymerizable thereto, with a number average molecular weight (Mn) of 2000-20000 and an acid value of 35-120 mgKOH / g, and the unsaturated group-containing alkali-soluble resin described in Japanese Patent Publication No. 2018-141968, which is a polymer with a weight average molecular weight (Mw) of 3000-50000 and an acid value of 30-200 mg / KOH, containing units derived from (meth)acrylic acid ester compounds and units having (meth)acryloyl groups and di or tricarboxylic acid residues.

[0042] Furthermore, the weight-average molecular weight (Mw) of the alkali-soluble resin is preferably between 2,000 and 10,000, and more preferably between 3,000 and 8,000. If the weight-average molecular weight (Mw) is less than 2,000, the adhesion of the pattern during development cannot be maintained, and pattern peeling is likely to occur. If the weight-average molecular weight (Mw) exceeds 10,000, development residue and residual film in unexposed areas are likely to remain. In addition, the alkali-soluble resin is preferably in the range of 30 to 200 mgKOH / g. If this value is less than 30 mgKOH / g, alkaline development may not be successful, or special development conditions such as strong alkali may be required. If it exceeds 200 mgKOH / g, the penetration of the alkaline developer solution becomes too fast, and peeling development is likely to occur.

[0043] The alkali-soluble resin content is preferably 5 to 70% by mass, more preferably 5 to 60% by mass, and even more preferably 10 to 55% by mass, based on the total solid content of the photosensitive resin composition. The alkali-soluble resin content can be adjusted together with the photopolymerizable compound of component (B) described later.

[0044] <(B) Photopolymerizable compounds having at least one ethylenically unsaturated bond> The (B) component includes, for example, hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxyhexyl (meth)acrylate, as well as 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, tetramethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra Examples of (meth)acrylic acid esters such as la(meth)acrylate, dipentaerythritol tetra(meth)acrylate, glycerol(meth)acrylate, glycerol di(meth)acrylate, glycerol tri(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, dendritic polymers having (meth)acroyl groups, etc., can be used, and one or more of these can be used. Examples of dendritic polymers having (meth)acroyl groups include known dendritic polymers obtained by adding thiol groups from a polyvalent mercapto compound to some of the carbon-carbon double bonds in the (meth)acroyl group of a polyfunctional (meth)acrylate compound.

[0045] The component (B) can crosslink molecules of alkali-soluble resins, and to achieve this function, it is preferable to use a component having two or more ethylenically unsaturated bonds. Furthermore, the acrylic equivalent obtained by dividing the molecular weight of the monomer by the number of (meth)acroyl groups in one molecule should be between 50 and 300.

[0046] Regarding the amount of component (B), the mixing ratio with component (A) is 50 / 50 to 90 / 10 by mass ratio (A) / (B), preferably 60 / 40 to 80 / 20. If the mixing ratio of component (A) is less than 50 / 50, the cured product after photocuring will become brittle, and the acid value of the coating film in the unexposed areas will be low, reducing its solubility in alkaline developer and potentially resulting in jagged and less sharp pattern edges. Furthermore, if the mixing ratio of component (A) is greater than 90 / 10, the proportion of photoreactive functional groups in the resin will be low, resulting in insufficient cross-linking structure formation. Additionally, the acid value of the resin component may be too high, potentially increasing solubility in alkaline developer in the exposed areas. This can lead to problems such as the formed pattern becoming thinner than the target line width or the pattern being prone to gaps.

[0047] <(C) Photopolymerization initiator> The (C) component includes, for example, acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, and benzyldimethylketal; benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone, 4,4'-bisdimethylaminobenzophenone (Michler ketone), 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, and hydroxybenzophenone. Benzophenones such as benzophenone and 4,4'-diethylaminobenzophenone; benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; 2-(o-chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5-diphenylbiimidazole, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, 2,4,5-triarylbi Biimidazole compounds such as imidazole and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2-biimidazole; halomethyldiazole compounds such as 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, and 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole; 2,4,6-tris(trichloromethyl)-1,3,5-triazine, and 2-methyl-4,6-bis(trichloro Methyl)-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,Halomethyl-s-triazine compounds such as 6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime), 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)butane-1-oneoxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-bicycloheptyl-1-oneoxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-adamantilmethane-1-oneoxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole- 3-yl]-adamantilmethane-1-oneoxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-tetrahydrofuranylmethane-1-oneoxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-tetrahydrofuranylmethane-1-oneoxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-thiophenylmethane-1-one Oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-thiophenylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-molofonylmethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-molofonylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2 -methylbenzoyl)-9H-carbazol-3-yl]-ethane-1-onoxime-O-bicycloheptane carboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethane-1-onoxime-O-tricyclodecane carboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethane-1-onoxime-O-adamantane carboxylate, 1-[4-(phenylsulfanyl)phenyl]octane-1,2-Dione=2-O-benzoyl oxime, 1-[9-ethyl-6-(2-methylbenzoyl)carbazole-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-acetyl oxime), ethanone,1-(-9,9-dibutyl-7-nitro-9H-fluoren-2-yl)-1-O-acetyl oxime O-acyloxime compounds such as ethyloxime, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyloxime); sulfur compounds such as thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone; 2-ethyl Anthraquinones such as ruanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone; organic peroxides such as azobisisobutylnitrile, benzoyl peroxide, and cumene peroxide; 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, β-mercaptopropionic acid, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3- Mercaptopropionate, stearyl-3-mercaptopropionate, trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), 3,Examples include thiol compounds such as 3'-thiodipropionic acid, dithiodipropionic acid, and laurylthiopropionic acid. Among these, O-acyloxime compounds are preferred from the viewpoint of easily obtaining a highly sensitive photosensitive resin composition for light-shielding films. Furthermore, two or more of these photopolymerization initiators can also be used. In this invention, the term "photopolymerization initiator" includes sensitizers.

[0048] Examples of O-acyloxime compounds that can be preferably used include O-acyloxime photopolymerization initiators represented by the following general formulas (6) and (7). Among these compounds, when using a high concentration of light-shielding components, it is preferable to use an O-acyloxime photopolymerization initiator having a molar extinction coefficient of 10,000 or more at 365 nm.

[0049] [ka]

[0050] In general formula (6), R9, R 10 Each of these 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, R 11 represents 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 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 portion may contain unsaturated bonds, ether bonds, thioether bonds, or ester bonds. Furthermore, the alkyl group may be linear, branched, or cyclic alkyl groups.

[0051] [ka]

[0052] In general formula (7), R 12 and R13 Each of these is independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, a cycloalkylalkyl group, or an alkylcycloalkyl group having 4 to 10 carbon atoms, or a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms. 14 Each of these R is independently a linear or branched alkyl or alkenyl group having 2 to 10 carbon atoms, and some of the -CH2- groups in the alkyl or alkenyl group may be substituted with -O- groups. Furthermore, these R 12 ~R 14 Some of the hydrogen atoms in the base may be substituted with halogen atoms.

[0053] Furthermore, compounds that do not act as photoinitiators or sensitizers on their own but can increase the photoinitiator or sensitizer capacity when used in combination with the above-mentioned compounds may be added. Examples of such compounds include amine compounds that are effective when used in combination with benzophenone. Examples of the above-mentioned amine compounds include triethylamine, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone.

[0054] The amount of component (C) is preferably 2 to 40 parts by mass, and more preferably 3 to 30 parts by mass, per 100 parts by mass of the total of components (A) and (B).

[0055] <(D) Light-blocking agent> The component (D) is not particularly limited, but is preferably an inorganic or organic black pigment, and more preferably consists of at least one light-shielding component selected from the group consisting of organic black pigments, inorganic black pigments, and mixed pseudo-black pigments. Examples of such organic black pigments include perylene black, aniline black, cyanine black, and lactam black. Examples of inorganic black pigments include carbon black, chromium oxide, iron oxide, and titanium black. Examples of mixed pseudo-black pigments include those obtained by mixing two or more pigments from red, blue, green, purple, yellow, cyanine, magenta, etc., to produce a pseudo-black color. As such a light-shielding agent, one of the above light-shielding components may be used alone, or two or more may be used in combination. Furthermore, as such a light-shielding agent, carbon black is particularly preferred from the viewpoint of good light-shielding properties, surface smoothness, dispersion stability, and compatibility with resins.

[0056] The light-shielding agent is preferably a light-shielding component (particularly preferably carbon black) with an average particle size of 50 to 250 nm, and more preferably 80 to 200 nm. If the average particle size of such a light-shielding component (particularly preferably carbon black) falls below the lower limit, the light-shielding performance of the resulting light-shielding film tends to decrease. In addition, an increase in surface area leads to more reaction sites and makes aggregation more likely. If the average particle size exceeds the upper limit, the smoothness of the light-shielding film decreases. The average particle size of the light-shielding component can be determined by particle size distribution measurement using dynamic light scattering or the like.

[0057] Furthermore, the light-shielding agent is preferably dispersed in the (H) solvent described below together with a dispersant to form a light-shielding dispersion, which is then incorporated into the photosensitive resin composition. Here, the solvent used for dispersion becomes part of the (H) component described below, so any of the solvents listed in the (H) component can be used, but for example, propylene glycol monomethyl ether acetate, cyclohexanone, etc., are preferably used. The blending ratio of the (D) component that forms the light-shielding dispersion is preferably in the range of 20 to 70% by mass relative to the total solid content of the photosensitive resin composition of the present invention, more preferably in the range of 25 to 60% by mass, even more preferably in the range of 35 to 60% by mass, and particularly preferably in the range of 40 to 60% by mass. When the light-shielding dispersion contains the dispersant, the content here refers to the content including the dispersant.

[0058] Furthermore, known dispersants such as various polymer dispersants can be used as the dispersant. Examples of dispersants include known compounds conventionally used for pigment dispersion (compounds commercially available under names such as dispersants, dispersion wetting agents, and dispersion accelerators), which can be used without particular limitation. Examples include cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, and pigment derivative type dispersants (dispersion aids). In particular, cationic polymer dispersants having cationic functional groups such as imidazolyl groups, pyrrolyl groups, pyridyl groups, and primary, secondary, or tertiary amino groups as adsorption sites to pigments, with an amine value of 1 to 100 mg KOH / g and a number average molecular weight in the range of 1,000 to 100,000 are preferred. The amount of this dispersant is preferably 1 to 35% by mass in component (D).

[0059] <(E) Silica particles> The silica particles of component (E) are not particularly limited in terms of their manufacturing method (such as gas-phase reaction or liquid-phase reaction) or shape (spherical or non-spherical). Furthermore, the type of silica particles is not particularly limited; solid silica or hollow silica particles may be used. "Hollow silica particles" refers to silica particles that have a cavity inside.

[0060] Component (E) can lower the refractive index of a film (light-shielding film, cured film) made from a cured product of a photosensitive resin composition. As a result, it can suppress reflection caused by the difference in refractive index between the glass substrate and the film on the glass substrate side, or by the difference in refractive index between air and the film on the film side, thereby lowering the reflectivity of the film surface.

[0061] The average particle size of component (E) is preferably in the range of 50 to 180 nm, and more preferably in the range of 50 to 130 nm. Compared with silica particles with a small particle size of several nm, silica particles within the above range are less likely to aggregate. Therefore, when the particle size of component (E) is within the above range, the dispersion stability is improved to an appropriate degree, allowing component (E) to segregate near the surface. Furthermore, the movement of component (E) due to aggregation within the film is less likely to be restricted, and a sufficient amount of component (E) can be segregated to the surface side of the film. As a result, the reflectivity can be reduced on both the glass substrate side and the film surface side of the film. In addition, by setting the average particle size of component (E) within the above range, in addition to the segregation effect mentioned above, it is possible to suppress the decrease in linearity and surface smoothness of the film due to component (E) segregated to the surface side of the film.

[0062] The average particle size of component (E) can be measured by the cumulant method using, for example, a dynamic light scattering particle size analyzer "Particle Size Analyzer FPAR-1000" (manufactured by Otsuka Electronics Co., Ltd.).

[0063] In the present invention, it is preferable that the surface of the silica particles is surface-treated in order to moderately improve the dispersion stability described above and to reduce the restriction of the movement of component (E) due to aggregation within the film, so that a sufficient amount of component (E) can be segregated to the surface side of the film. While there are no limitations on known surface treatments for silica particles, it is particularly preferable to use silica particles surface-modified with a hydrophobic functional group in order to improve compatibility with the solvent (H) described later and to improve the dispersion stability described above. Among these, it is preferable that the hydrophobic functional group is a group containing an aryl group or alkyl group having 1 to 8 carbon atoms, such as a phenyl group, vinyl group, styryl group, epoxy group, or cyclohexyl group, and more preferably a group containing a phenyl group and / or a vinyl group.

[0064] For the silica particles with the aforementioned surface treatment, commercially available silica particles with the aforementioned functional groups can be used, or they can be obtained by surface treating untreated silica particles. The surface treatment method is not limited as long as it can introduce the aforementioned functional groups to the surface of the silica particles, and methods using known surface treatment agents can be used, but from the viewpoint of reactivity with silica particles and ease of handling, a surface treatment method using a silane coupling agent having the aforementioned functional groups is preferred. For the surface treatment method of silica particles using a silane coupling agent, known methods can be appropriately adopted, but for example, it can be carried out by a method using a silane coupling agent shown in the following chemical formula. [ka] (However, each R6 independently represents the aforementioned aryl group or alkyl group having 1 to 8 carbon atoms, each R7 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, each R8 independently represents an alkyl group having 1 to 4 carbon atoms, and q is 1 to 3.)

[0065] There are no restrictions on the amount of silane coupling agent applied to the silica particles, but it is preferably 0.5 to 5% by mass relative to the mass of the silica particles, and more preferably 1 to 4% by mass.

[0066] Here, the refractive index of component (E) is preferably between 1.10 and 1.47. While ordinary silica particles with a refractive index of 1.45 to 1.47 can be used, using hollow silica particles with a lower refractive index can also lower the refractive index of the light-shielding film compared to a light-shielding film containing only ordinary silica particles. The refractive index can be determined from a transparent mixture obtained by mixing powdered silica particles with a standard refractive index solution of known refractive index. The refractive index of the silica particles can be measured using an Abbe refractometer.

[0067] The shape of component (E) may be spherical or elliptical. Of these, spherical is preferred. The sphericity is preferably between 1.0 and 1.5. If the sphericity of the silica particles is within this range, the particle shape will be close to a perfect sphere. As a result, it becomes possible to uniformly fill the thin film in the in-plane direction (the direction horizontal to the glass substrate surface), and the silica particles can be prevented from being exposed to the outside from the surface of the film while maintaining the smoothness of the film surface. As a result, a light-shielding film with a low refractive index and sufficient strength can be obtained. The sphericity of component (E) can be determined from the ratio of the longest diameter to the shortest diameter of the particles (the average value of any 100 silica particles). Here, the longest diameter and shortest diameter are values ​​obtained by photographing component (E) with a transmission electron microscope and measuring the longest and shortest diameters from the resulting microscope image.

[0068] Component (E) can be mixed with other components as a dispersion in solvent (H), which will be described later. Alternatively, known dispersants can be used to form a dispersion of silica particles.

[0069] The amount of component (E) is preferably in the range of 2 to 20% by mass, and more preferably in the range of 2.5 to 15% by mass, relative to the total solid content of the photosensitive resin composition. If the solvent (H) described later is included, it is preferably 0.1 to 5% by mass, and more preferably 0.1 to 2% by mass, relative to the total mass of the photosensitive resin composition containing the solvent. When the amount of silica particles is within the above range, good light patterning properties and high light shielding can be achieved while achieving low reflectivity. If the dispersant is contained in the dispersion of silica particles, the content here shall also represent the content including the dispersant, as in the case of component (D) above. The amount of this dispersant is preferably 1 to 40% by mass in component (E).

[0070] <(F) Silane coupling agent> Examples of silane coupling agents for component (F) include epoxy compounds such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; (meth)acrylate compounds such as 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyltriethoxysilane; vinyl compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, and p-styryltrimethoxysilane; isocyanates such as 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane; and ureido compounds such as 3-ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane. By using a silane coupling agent, adhesion to the glass substrate can be improved.

[0071] The amount of silane coupling agent used is preferably 0.05 to 10% by mass, and more preferably 0.1 to 5% by mass, relative to the total solid content of the photosensitive resin composition.

[0072] <Compound (G)> In the present invention, it is preferable to further include a compound (G) having a dimethylsiloxane unit represented by the following structure (X) and an ethylene glycol repeating unit represented by the following structure (Y-1) and / or a propylene glycol repeating unit represented by the following structure (Y-2), wherein the ratio of the number of units in one molecule, (X) / [(Y-1)+(Y-2)], is 0.1 to 100. By further including such a compound (G), the ratio of the peak areas A is obtained. SiO2 / A SiO A film satisfying the above conditions can be obtained. That is, although the exact mechanism of action is not necessarily clear, it is presumed that by further using a compound (G) which contains such structure (X) and structure (Y-1) and / or structure (Y-2) in a predetermined ratio and has a structure in which hydrophobic groups and hydrophilic groups are clearly separated, it is possible to improve the interaction with silica particles in the photosensitive resin composition while also improving their movement to the surface side of the film. As a result, it is thought that silica particles can be segregated by being present in greater numbers (more densely) near the surface of the film (the glass substrate side and the film surface side and the opposite side), thereby reducing the reflectivity of the film surface.

[0073] [ka]

[0074] In structure (X), a is 15 or greater. By using compound (G) having structure (X) with a repeating number a of 15 or greater, it is possible to maintain good hydrophobicity and expect a balanced interaction effect with silica particles. Preferably, a is 20 or greater. Although there is no upper limit to a, it is preferable that a is 150 or less because excessive hydrophobicity tends to lead to stronger interactions with other materials than with silica particles, and it may become impossible to have a large (high concentration) amount of silica particles on the film surface side.

[0075] [ka]

[0076] [ka]

[0077] For such a compound (G), the ratio of the number of units (X) / [(Y-1)+(Y-2)] is more preferably 1.0 to 100, even more preferably 1.0 to 50, and even more preferably 1.0 to 40.

[0078] Here, any compound (G) can be used as such, as long as it has the aforementioned structure (X) and structure (Y-1) and / or structure (Y-2) in a predetermined ratio of units. For example, examples include copolymers of polydimethylsiloxane with polyethylene glycol and / or polypropylene glycol, copolymers of polydimethylsiloxane with propylmethylsiloxane having a polyethylene glycol and / or polypropylene glycol structure, copolymers of polydimethylsiloxane having a propyl group in part of its side chain with polyethylene glycol and / or polypropylene glycol, copolymers of polydimethylsiloxane having a hydrosilyl group in part of its side chain with polyethylene glycol and / or polypropylene glycol, copolymers of polydimethylsiloxane with poly(ethylene glycol / propylene glycol), copolymers in which polyethylene glycol and / or propylene glycol are introduced into the side chains of polydimethylsiloxane, copolymers of a structure in which (meth)acrylic groups are introduced into the side chains and / or terminals of polydimethylsiloxane with polyethylene glycol mono(meth)acrylate and / or polypropylene glycol mono(meth)acrylate, and copolymers of a structure in which (meth)acrylic groups are introduced into the side chains and / or terminals of polydimethylsiloxane with poly(ethylene glycol) di(meth)acrylate. Among these, a more preferred embodiment is the use of a copolymer of polydimethylsiloxane and polyethylene glycol and / or polypropylene glycol, a copolymer of polydimethylsiloxane having a propyl group in part of its side chain and polyethylene glycol and / or polypropylene glycol, or a copolymer of a structure in which (meth)acrylic groups are introduced to the side chain and / or terminal of polydimethylsiloxane and / or polyethylene glycol mono(meth)acrylate and / or polypropylene glycol mono(meth)acrylate. Note that "poly(ethylene glycol / propylene glycol)" above refers to a random copolymer of ethylene glycol and propylene glycol. The copolymer may be a random copolymer or a block copolymer.

[0079] The number of units in structure (X) and structure (Y-1) and / or structure (Y-2) can be determined using known methods. For example, it can be calculated from the charging ratio of each component, including the structure of each unit, when producing each copolymer, or it can be calculated from nuclear magnetic resonance (NMR) spectroscopy measurements. As a method of calculation from NMR spectroscopy measurements, for example, the poly(dimethylsiloxane)-graft-poly(ethylene oxide) described in the "Supporting information," which is an electronic supplement to Colloid Polym Sci, vol.285, 673-680 (2007) 1 Molecular structure analysis using H-NMR and other methods can be used as references.

[0080] The amount of compound (G) used is preferably in the range of 0.005 to 10% by mass relative to the total solid content of the photosensitive resin composition. If the solvent (H) described later is included, it is preferably 0.001 to 1.0% by mass relative to the total mass of the photosensitive resin composition containing the solvent. It is even more preferably 0.001 to 0.5% by mass relative to the total mass.

[0081] <(H) Solvent> In addition to the components (A) to (G) above, it is preferable to use a solvent, which is component (H), in the photosensitive resin composition of the present invention. Examples of solvents include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-2-butanone, and diacetone alcohol; terpenes such as α- or β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, and propylene glycol Examples include glycol ethers such as glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; and esters such as ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxypropionate, 3-ethoxypropionate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Organic solvents may be used individually or in mixtures of two or more.

[0082] <Other ingredients> The photosensitive resin composition may optionally contain other resin components besides component (A), such as epoxy resin, as well as additives such as curing agents, curing accelerators, thermal polymerization inhibitors and antioxidants, plasticizers, fillers other than silica, and defoamers.

[0083] Other examples of resin components include vinyl resin, polyester resin, polyamide resin, polyimide resin, polyurethane resin, polyether resin, melamine resin, epoxy resin, and the like.

[0084] Examples of curing agents include, for example, amine compounds, polycarboxylic acid compounds, phenolic resins, amino resins, dicyandiamides, Lewis acid complex compounds, etc., which contribute to the curing of epoxy resins. Examples of curing accelerators include, for example, tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, borate esters, Lewis acids, organometallic compounds, imidazoles, etc., which contribute to accelerating the curing of epoxy resins.

[0085] Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, and hindered phenol compounds. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of fillers include glass fiber, mica, and alumina. Examples of defoamers include acrylic compounds.

[0086] <Solid content> The photosensitive resin composition of the present invention mainly contains components (A) to (F) and, if necessary, compound (G) and solvent (H). The solid content (including monomers that become solid after curing) excluding the solvent of component (H) preferably contains a total of 70% by mass of (A) to (F) and, if necessary, compound (G), more preferably 80% by mass or more, and even more preferably 90% by mass or more. The amount of solvent (H) varies depending on the target viscosity, but it is preferable that it be included in the photosensitive resin composition of the present invention in the range of 60 to 90% by mass.

[0087] 2. Light-shielding film The light-shielding film of the present invention is a film made from a cured product of the above-mentioned photosensitive resin composition. Furthermore, as described above, it is preferably characterized by having an average film thickness of 0.5 μm to 4.0 μm.

[0088] Furthermore, the light-shielding film of the present invention is preferably a film made of a photocured product of a photosensitive resin composition. The term "photocured product" as used herein refers to any product that has been cured by light at any stage during the curing of the photosensitive resin composition, and includes products that have been cured by heat (post-bake) after photocuring. That is, the photocured product referred to herein may be a cured product cured solely by photocuring, or a cured product that has been heat-cured after photocuring. Thus, the light-shielding film of the present invention is obtained by curing the above-mentioned photosensitive resin composition of the present invention with light (and, if necessary, further curing by heat after photocuring). While there are no particular limitations on the methods that can be used to form a light-shielding film having a specific pattern, for example, a suitable method is to use a photosensitive resin composition in solution (containing the above-mentioned (H) component), apply the solution-like photosensitive resin composition to a substrate, then perform a heat treatment (pre-bake) to remove the (H) component, then perform an exposure treatment using a mask for forming a desired light-shielding film pattern to photo-cure the photosensitive (photocurable) resin in the photosensitive (exposed) portion, and then perform a development treatment to remove the photosensitive resin composition in the unexposed portion, thereby forming a light-shielding film (light-shielding film pattern) by further heat treatment (post-bake) as needed. Below, we will briefly describe a method that can be suitably used to form such a light-shielding film.

[0089] In this method for forming a light-shielding film, first, the solution-type photosensitive resin composition is applied to a substrate. Methods for applying such a solution-type photosensitive resin composition to a substrate include, for example, known methods such as immersion in solution, spraying, and methods using a roller coater, land coater, slit coater, or spin coater. The substrate can be any substrate for which a light-shielding film needs to be formed; a known transparent substrate for a display device (e.g., a glass substrate) is a suitable example.

[0090] Furthermore, in this method for forming a light-shielding film, after applying the solution-like photosensitive resin composition onto a substrate, a heat treatment (pre-bake) is performed to remove the solvent in the composition. The heating temperature and heating time in this pre-bake can be appropriately set according to the type of solvent used, etc. For example, the heating temperature can be set to 60 to 110°C (set so as not to exceed the heat resistance temperature of the transparent substrate), and the heating time can be set to 1 to 5 minutes. A dried coating film of the photosensitive resin composition can be obtained by such a heat treatment.

[0091] Furthermore, in this method for forming a light-shielding film, the pre-baked coating (a dried coating of the photosensitive resin composition) is subjected to exposure treatment using a mask for forming a desired light-shielding film pattern, and the resin in the photosensitive portion (the portion irradiated with light) of the coating is photocured. The conditions used in this exposure treatment are not particularly limited, and known exposure conditions used when forming a light-shielding film using a photosensitive resin can be used as appropriate, and appropriate conditions can be appropriately adopted depending on the types of components (A), (B), and (C) used.

[0092] Furthermore, in this method for forming a light-shielding film, the coating film after exposure is subjected to a developing treatment to remove the photosensitive resin composition from the unexposed portions of the coating film. The method of this developing treatment is not particularly limited, and known developing methods can be appropriately adopted. Since the photosensitive resin composition uses an alkali-soluble resin as component (A), it is preferable to perform the developing treatment (alkaline developing treatment) using an alkaline developer. As such an alkaline developer, known alkaline developers such as aqueous solutions of alkali metal or alkaline earth metal carbonates or hydroxides can be used. In this way, by performing the developing treatment and removing the resin composition from the unexposed portions, a patterned light-shielding film (light-shielding film pattern: pixel pattern) can be formed. In order to sufficiently harden the obtained light-shielding film or to sufficiently remove the developer, the light-shielding film (light-shielding film pattern) may be further subjected to a heat treatment (post-bake).

[0093] Post-baking can be carried out by known methods (heating using an oven, hot air blower, hot plate, infrared heater, etc., vacuum drying, or a combination thereof). The heating temperature is not particularly limited as long as it is the temperature at which the coating film fully hardens (post-bake) and takes into account the heat resistance of the substrate. Preferably, the heating is carried out at a temperature of 80 to 250°C for 20 to 120 minutes.

[0094] In this way, a light-shielding film made from a photocured product of a photosensitive resin composition can be formed. However, the method for forming such a light-shielding film is not limited to the method described above. In addition to forming a fine pattern by exposure, development, and other operations as described above, other methods, such as forming a desired pattern by screen printing, can also be appropriately employed.

[0095] The light-shielding film of the present invention formed in this manner preferably has an OD value of 3.5 / μm or more per 1 μm of film thickness, and more preferably 3.7 / μm or more. Furthermore, as shown in the examples described later, the reflectance is preferably measured by the SCI method and the SCE method on both the glass substrate side and the film side. On the glass substrate side, the SCI method value is preferably 5.2% or less, and the SCE method value is preferably 0.45% or less. A more preferable reflectance is 4.9% or less for the SCI method and 0.4% or less for the SCE method. On the other hand, on the film side, the SCI method value is preferably less than 7.1%, and the SCE method value is preferably 0.45% or less. A more preferable reflectance is 6.1% or less for the SCI method and 0.45% or less for the SCE method. A still more preferable reflectance is 4.7% or less for the SCI method and 0.40% or less for the SCE method.

[0096] 3.Display device The display device of the present invention is characterized by comprising the light-shielding film of the present invention. The type of such display device is not particularly limited, and examples include liquid crystal display devices, organic electroluminescent devices represented by organic EL elements, touch panels, etc. Furthermore, as long as such a display device of the present invention comprises the light-shielding film, other configurations are not particularly limited. In addition, as such a display device of the present invention, it is preferable that the light-shielding film of the present invention is provided on the back surface of the transparent substrate on the display surface side of the display device (a device comprising a transparent substrate with a light-shielding film arranged so that the light-shielding film is viewed through the transparent substrate). With the display device of the present invention, it is possible to sufficiently reduce reflection on both the glass substrate surface side and the film surface side by the light-shielding film, thereby improving visibility and other aspects. [Examples]

[0097] The embodiments of the present invention will be specifically described below based on examples and comparative examples, but the present invention is not limited thereto. Unless otherwise specified, "parts" refers to parts by mass.

[0098] First, we will show an example of the synthesis of an alkali-soluble resin of component (A) of the present invention (resin synthesis example). The resin in the resin synthesis example was evaluated as follows.

[0099] [Solid content concentration] The weight [W1(g)] after impregnating 1g of the resin solution obtained in the resin synthesis example with a glass filter [weight: W0(g)] and the weight [W2(g)] after heating at 160°C for 2 hours were used to determine the following formula. Solid content concentration (weight%) = 100 × (W2-W0) / (W1-W0)

[0100] [Acid value] The resin solution was dissolved in dioxane and titrated with a 1 / 10N-KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) to determine the result.

[0101] [Molecular weight] The molecular weight was measured using gel permulation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, columns: TSKgelSuper H-2000 (2) + TSKgelSuper H-3000 (1) + TSKgelSuper H-4000 (1) + TSKgelSuper H-5000 (1) (manufactured by Tosoh Corporation), temperature: 40℃, rate: 0.6 ml / min), and the weight-average molecular weight (Mw) was determined as a value converted to standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit).

[0102] The abbreviations used in the resin synthesis examples are as follows: AA: Acrylic acid BPFE: Bisphenol fluorene type epoxy compound [A reaction product of 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyloxirane. In compounds of general formula (I), A is a fluorene-9,9-diyl group and R1-R4 are hydrogen atoms.] BPDA: 3,3',4,4'-biphenyltetracarboxylic acid dianhydride THPA:1,2,3,6-tetrahydrophthalic anhydride PGMEA: Propylene glycol monomethyl ether acetate TEAB: Tetraethylammonium bromide

[0103] [Examples of resin synthesis] In a four-necked flask (capacity 500 ml) equipped with a reflux condenser, BPFE (114.4 g (0.23 mol)), AA (33.2 g (0.46 mol)), PGMEA (157 g) and TEAB (0.48 g) were charged and reacted by stirring at 100-105°C for 20 hours. Next, BPDA (35.3 g (0.12 mol)) and THPA (18.3 g (0.12 mol)) were added to the reaction product in the flask and stirred at 120-125°C for 6 hours to obtain a resin solution containing a polymerizable unsaturated group-containing alkali-soluble resin. In the obtained resin solution, the solid content concentration was 56.1% by mass, the acid value (based on solid content) was 103 mg KOH / g, and the Mw value determined by GPC analysis was 3600.

[0104] Furthermore, synthesis examples 1 to 11 and comparative synthesis examples 1 to 3 of silica particles of component (E) of the present invention are shown. The average particle size of components (D) and (E) was evaluated as follows.

[0105] [Average particle size] The average particle diameters of (D) the light-shielding agent and (E) the silica particles were measured as follows. First, a dispersion was prepared as a measurement sample by dispersing the particles to be measured in propylene glycol monomethyl ether acetate (PGMEA) as a solvent so that the particle concentration was 0.1 to 0.5 mass%. Then, the particle size distribution of the particles in the obtained dispersion (measurement sample) was measured by dynamic light scattering using a particle size analyzer (Particle Size Analyzer FPAR-1000, manufactured by Otsuka Electronics Co., Ltd.), and the average particle diameter was determined by analyzing the obtained particle size distribution using the cumulant method. The value obtained in this way was adopted as the average particle diameter of the particles to be measured (light-shielding agent and silica particles).

[0106] [Synthesis Example 1] Under atmospheric conditions, a mixture of 400 parts t-butanol, 200 parts Nissan Chemical's Snowtex ST-YL (40% solids aqueous solution), and 1 part phenyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-103) was heated under reflux for 5 minutes and allowed to cool to room temperature. Next, under reduced pressure, propylene glycol monomethyl ether acetate was added, and water and t-butanol were removed by azeotropic distillation. Further addition of propylene glycol monomethyl ether acetate was prepared to prepare a silica particle-containing dispersion that was a 30 wt% solids PGMEA solution. The average particle size of the silica particles was 62 nm.

[0107] [Synthesis Example 2] A silica particle-containing dispersion was prepared using the same procedure as in Synthesis Example 1, except that the amount of phenyltrimethoxysilane was changed from 1 part to 2.7 parts. The average particle size of the silica particles was 64 nm.

[0108] [Synthesis Example 3] A silica particle-containing dispersion was prepared using the same procedure as in Synthesis Example 1, except that 1 part of phenyltrimethoxysilane in Synthesis Example 1 was replaced with 0.8 parts of diphenyldimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-202S). The average particle size of the silica particles was 62 nm. Ta.

[0109] [Synthesis Example 4] A silica particle-containing dispersion was prepared using the same procedure as in Synthesis Example 1, except that 1 part of phenyltrimethoxysilane in Synthesis Example 1 was replaced with 20 parts of phenyltriethoxysilane (Shin-Etsu Chemical Co., Ltd., KBE-103). The average particle size of the silica particles was 63 nm.

[0110] [Synthesis Example 5] A silica particle-containing dispersion was prepared using the same procedure as in Synthesis Example 1, except that 1 part of phenyltrimethoxysilane in Synthesis Example 1 was replaced with 10 parts of phenyltriethoxysilane and 0.5 parts of vinyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-1003). The average particle size of the silica particles was 67 nm.

[0111] [Synthesis Example 6] A silica particle-containing dispersion was prepared using the same procedure as in Synthesis Example 1, except that 1 part of phenyltrimethoxysilane was replaced with 2 parts of p-styryltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-1403). The average particle size of the silica particles was 68 nm.

[0112] [Synthesis Example 7] In Synthesis Example 1, 200 parts of Snowtex ST-YL were replaced with 200 parts of a silica particle dispersion prepared by Corefront Co., Ltd. using silica particles (43-00-701) to a 40% solids aqueous solution, and 1 part of phenyltrimethoxysilane was replaced with 1.5 parts. Otherwise, the silica particle-containing dispersion was prepared using the same procedure as in Synthesis Example 1. The average particle size of the silica particles was 70 nm.

[0113] [Synthesis Example 8] A silica particle-containing dispersion was prepared using the same procedure as in Synthesis Example 7, except that 1.5 parts of phenyltrimethoxysilane were changed to 3 parts. The average particle size of the silica particles was 70 nm.

[0114] [Synthesis Example 9] A silica particle-containing dispersion was prepared using the same procedure as in Synthesis Example 1, except that 200 parts of Snowtex ST-YL in Synthesis Example 1 were replaced with 200 parts of Nissan Chemical's Snowtex ST-ZL (40% solids content), and 1 part of phenyltrimethoxysilane was replaced with 0.8 parts of diphenyldimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-202S). The average particle size of the silica particles was 83 nm.

[0115] [Synthesis Example 10] A silica particle-containing dispersion was prepared using the same procedure as in Synthesis Example 1, except that 200 parts of Snowtex ST-YL in Synthesis Example 1 were replaced with Nissan Chemical's Snowtex MP-1040 (40% solids content), and 1 part of phenyltrimethoxysilane was replaced with 1.8 parts of p-styryltrimethoxysilane. The average particle size of the silica particles was 105 m.

[0116] [Synthesis Example 11] A silica particle-containing dispersion was prepared using the same procedure as in Synthesis Example 1, except that 1 part of phenyltrimethoxysilane was changed to 6 parts. The average particle size of the silica particles was 65 nm.

[0117] [Comparative Synthesis Example 1] Under atmospheric conditions, 400 parts of t-butanol and 200 parts of Nissan Chemical's Snowtex ST-YL (40% solids aqueous solution) were heated under reflux for 5 minutes and allowed to cool to room temperature. Next, under reduced pressure, propylene glycol monomethyl ether acetate was added, and water and t-butanol were removed by azeotropic reaction. Further addition of propylene glycol monomethyl ether acetate was prepared to create a silica particle-containing dispersion that was a 30 wt% solids PGMEA solution.

[0118] [Comparative Synthesis Example 2] A silica particle-containing dispersion was prepared using the same procedure as in Synthesis Example 2, except that 200 parts of Snowtex ST-YL were replaced with Nissan Chemical's MP-2040, and 1 part of phenyltrimethoxysilane was changed to 2 parts. The average particle size of the silica particles was 200 nm.

[0119] [Comparative Synthesis Example 3] A silica particle-containing dispersion was prepared using the same procedure as in Synthesis Example 2, except that one part of the phenyltrimethoxysilane in Synthesis Example 2 was replaced with 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-503). The average particle size of the silica particles was 63 nm.

[0120] The components and abbreviations used in the photosensitive resin compositions of Examples 1 to 59 and Comparative Examples 1 to 6 described below are as follows:

[0121] (A) Component (alkali-soluble resin): An alkali-soluble resin solution containing unsaturated groups obtained in the resin synthesis example.

[0122] (B) Component (photopolymerizable compound): A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (product name "DPHA" manufactured by Nippon Kayaku Co., Ltd.).

[0123] (C) Ingredient (photopolymerization initiator): ADEKA Arclus NCI-831, manufactured by ADEKA Corporation. ("ADEKA Arclus" is a registered trademark of the company.)

[0124] (D) Ingredients (light-blocking agent): <D-1、D-2> Carbon black-A or B was used as the light-shielding component, and D-1 (CB dispersion (I)) or D-2 (CB dispersion (II)) below was used to introduce it. • D-1 (CB dispersion (I)): PGMEA dispersion with a concentration of 25% by mass of carbon black-A (CB-A) and 3% by mass of polymer dispersant (average particle size of 110 nm by cumulant method in CB-A dispersion). • D-2 (CB Dispersion (II)): PGMEA dispersion with a concentration of 25% by mass of carbon black-B (CB-B) and 3% by mass of polymer dispersant (average particle size of 130 nm by cumulant method in CB-B dispersion). <d-3> Lactam Black (BASF's Irgaphor® Black S 0100 CF) was used as the light-blocking component, and D-3 (Lactam Black Dispersion (III)) described below was used for its introduction. • D-3 (Lactam Black Dispersion (III)): PGMEA dispersion with a lactam black concentration of 20% by mass and a polymer dispersant of 3% by mass (average particle size of 220 nm in the dispersion, measured by the cumulant method).

[0125] (E) Component (silica particles): The following E-1 to E-17 were used. • E-1: Silica particle-containing dispersion prepared in Synthesis Example 1 • E-2: Silica particle-containing dispersion prepared in Synthesis Example 2 • E-3: Silica particle-containing dispersion prepared in Synthesis Example 3 • E-4: Silica particle-containing dispersion prepared in Synthesis Example 4 • E-5: Silica particle-containing dispersion prepared in Synthesis Example 5 • E-6: Silica particle-containing dispersion prepared in Synthesis Example 6 • E-7: Silica particle-containing dispersion prepared in Synthesis Example 7 • E-8: Silica particle-containing dispersion prepared in Synthesis Example 8 • E-9: Silica particle-containing dispersion prepared in Synthesis Example 9 • E-10: Silica particle-containing dispersion prepared in Synthesis Example 10 • E-11: Admatec Admanano YA050C series (PGMEA dispersion of 30% by mass silica particles surface-treated with vinyl groups, average particle size 50 nm) • E-12: MSD-71 manufactured by Sakai Chemical Co., Ltd. (PGMEA dispersion containing 30% by mass of silica particles surface-treated with phenyl groups, with an average particle size of 101 nm) • E-13: Silica manufactured by CIK Nanotech (30% by mass PGMEA dispersion, average particle size 130 nm) • E-14: Silica particle-containing dispersion prepared in Synthesis Example 11 • E-15: Silica particle-containing dispersion prepared in Comparative Synthesis Example 1 • E-16: Silica particle-containing dispersion prepared in Comparative Synthesis Example 2 • E-17: Silica particle-containing dispersion prepared in Comparative Synthesis Example 3

[0126] (F) Component (F-1: Silane coupling agent): Uleidopropyltriethoxysilane (methanol solution diluted, solids content 50%) (Product name: KBE-585A, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0127] Compound (G): The following W-1 to W-6 and Z-1 to Z-2 were used. W-1: A compound in which structure (X) has a=75, possesses structure (Y-1), and (X) / (Y-1)=38. W-2: A compound in which structure (X) has a=90, possesses structure (Y-1), and (X) / (Y-1)=30. W-3: A compound with structure (X) where a=115, structure (Y-1), and (X) / (Y-1)=23. W-4: A compound with structure (X) where a=20, structure (Y-1), and (X) / (Y-1)=3.3. W-5: A compound with structure (X) where a=25, structure (Y-2), and (X) / (Y-2)=0.3. • W-6: Compounds that do not have structure (X) but have the following tris(trimethylsilyloxysilane) structure (Z) and Y-2 structure.

[0128] [ka]

[0129] • Z-1: Compounds in which a=88 in structure (X) and which do not have Y-1 and Y-2 structures. • Z-2: Compounds that do not have structure (X), structure (Y-1), and structure (Y-2), but have the tris(trimethylsilyloxysilane)(Z) and trifluoromethyl group structures.

[0130] (H) Component (solvent): ANON: Cyclohexanone • PGMEA: Propylene glycol monomethyl ether acetate

[0131] <Examples 1-59 and Comparative Examples 1-6> [Preparation of photosensitive resin composition] The aforementioned components were blended in the proportions shown in Tables 1 to 8 to prepare the photosensitive resin compositions of Examples 1 to 59 and Comparative Examples 1 to 6. The values ​​in the tables represent parts by mass, and all values ​​except for component (H) represent solid content. The total solid content of the photosensitive resin composition is 14% by mass. Component (D) represents the total parts by mass of carbon black-A or carbon black-B and the polymer dispersant.

[0132] [Table 1]

[0133] [Table 2]

[0134] [Table 3]

[0135] [Table 4]

[0136] [Table 5]

[0137] [Table 6]

[0138] [Table 7]

[0139] [Table 8]

[0140] [Formation and evaluation of light-shielding films] <Formation of light-shielding film> The photosensitive resin compositions prepared in each example were coated onto a glass substrate measuring 125 mm in length and 125 mm in width using a spin coater to achieve a post-baking film thickness of 1.2 μm. The resulting coating was then subjected to a pre-baking process, where it was heated at 90°C for 1 minute. Subsequently, the I-line illuminance was 30 mW / cm². 2 A super high-pressure mercury lamp emits 100 mJ / m³ 2 The photocuring reaction was carried out under conditions of irradiation with ultraviolet light. Next, the photocured coating film (exposure-treated coating film) was treated with a 0.05 mass% potassium hydroxide aqueous solution as a developer at a temperature of 25°C at a rate of 1 kgf / cm². 2 After developing with a pressure shower for 75 seconds, the pressure was 5 kgf / cm². 2 A light-shielding glass substrate with a light-shielding film (average film thickness: 1.2 μm) was manufactured by performing a post-bake process, which involved pressure spray washing followed by heating in a hot air dryer at 230°C for 30 minutes.

[0141] <XPS analysis of the film surface> The surface side (the side of the film opposite the glass substrate) of the obtained light-shielding film was measured using XPS (JEOL JPS-9010 instrument), and the spectrum was analyzed using the analysis software "SpecSurf Analysis" (JEOL). First, a range of 108.0 (±0.3) to 98.0 (±0.3) eV was set for the Si2p3 / 2 spectrum, and the background was removed and the spectrum corrected using the Shirley method. The measurement conditions used were an applied voltage of 10kV and an emission current of 10mA, using an MgKa line. In addition, to reduce the charge-up of the sample, electron beam irradiation was performed using a neutralization gun under conditions of an acceleration voltage of 2V and an emission current of 4.0mA, and the C1s peak energy was corrected to 284.8eV. For the measured area, the X-ray irradiation area was 3mm × 6mm, the detection area on the film surface was a circle with a diameter of 3mm, and the detection depth was 2~4nm.

[0142] <Ratio of peak area on film surface A SiO2 / A SiO Calculation > For peak fitting of Si2p3 / 2 in XPS, the SpecSurf Analysis database (SiO2: 103.9eV, SiO2: 101.8eV) was used as a reference, and the peak area (A) was set to 103.9~104.2eV, taking into account the shift due to charge-up. SiO2 ) and the peak area (A) of 101.8~102.3eV SiO ) Ratio A SiO2 / A SiO The following was calculated. Peak separation was performed using a nonlinear least squares method with a trial function (Gauss-Lorentz mixing function: mixing ratio Gauss 0.3, Lorentz 0.7). The area of ​​each peak was calculated by integrating the component waveforms.

[0143] <Calculation of the ratio of Si, C, O, and F content (atomic concentration) on the film surface> The ratios of Si, C, O, and F content (atomic concentrations) were calculated using the relative sensitivity factor method of XPS. The analytical conditions were as follows: The atomic concentration (atom%) was calculated by correcting the peak area of ​​the integrated spectrum of each element with a relative sensitivity factor (RSF), and the ratio of the content (atomic concentration) was calculated by determining the atomic concentration of F relative to the total atomic concentration of Si, C, O, and F. (Analysis conditions) Narrow measurements were performed on the Si2p, C1s, N1s, O1s, and F1s peaks. Measurements were taken in the energy ranges of 115–95eV for Si2p, 299–274eV for C1s, 408–394eV for N1s, 543–528eV for O1s, and 696–683eV for F1s. The dwell time was set to 100ms and the pass energy to 10eV. Si was scanned 25 times, while C1s, N1s, O1s, and F1s were scanned 4 times each. To compensate for peak shifts due to charging, the CH peak in C1s was corrected to 284.8eV.

[0144] <Membrane side reflectance measurement> Using glass substrates on which the light-shielding films (pixel patterns) obtained in each example were laminated, the reflectance [%] of the SCI method and SCE method was measured using a spectrophotometer (SD7000, manufactured by Nippon Denshoku Industries Ltd.) from the film surface side where the light-shielding film pattern was formed, under the conditions of a C light source and a 2° field of view. A pass was defined as less than 7.1% for the SCI method and 0.45% or less for the SCE method. The reflectances of these methods are described as "SCI reflectance" or "SCE reflectance," or simply "SCI" ​​or "SCE."

[0145] <Measurement of reflectance on the glass surface> Using glass substrates on which the light-shielding films (pixel patterns) obtained in each example were laminated, the reflectance [%] of the SCI method and SCE method was measured using a spectrophotometer (SD7000, manufactured by Nippon Denshoku Industries Ltd.) on the side of the glass substrate where the light-shielding film pattern was not formed, under the conditions of a C light source and a 2° field of view. A pass was defined as 5.2% or less for the SCI method and 0.45% or less for the SCE method.

[0146] (Consideration) The light-shielding films obtained in Examples 1-59 had a film-side SCI reflectance of less than 7.1% and a film-side SCE reflectance of 0.45% or less. Furthermore, the glass-side SCI reflectance was 5.2% or less and the SCE reflectance was 0.45% or less. Examples 1-8, 10-36, 38-47, and 49-57 had a composition in which compound G was 0.5% or less of the total mass of the photosensitive resin composition containing the solvent, and the film surface SCI reflectance was 6.1% or less, indicating a good composition as a light-shielding film. In actual examples 1, 3, 5-8, 11-13, 15, 18-19, 21, 25, 27, 29-32, 35, 43-44, and 49-52, the silica particle size was 50-80 nm, which is a desirable average particle size. As a result, the film surface SCI reflectance was 5.0% or less, indicating a good composition as a light-shielding film. Examples 1, 5, 18, 19, 31, 50, and 51, in particular, had a film surface-side SCI reflectance of less than 4.5% and high light-shielding properties, indicating a good composition as a cured film. Comparative Example 6 showed a high percentage of element F, was not environmentally friendly, and could not meet requirements such as regulations on perfluorinated compounds (PFAS). Comparative Examples 1 and 2 either did not contain surface-modified silica, or the silica particle size was too large, resulting in high film surface reflectivity due to the aggregation of silica particles, as well as high SCE reflectivity. Comparative Example 3 consisted of silica particles surface-treated with a group containing a 3-methacryloxypropyl group, resulting in poor compatibility with light-shielding materials and a tendency to aggregate, thus exhibiting high SCI reflectivity. • Comparative Example 4 is A SiO2 / A SiO The ratio was high, and silica was segregated to the film surface, resulting in low SCI reflectivity, but poor coatability led to high SCE reflectivity. Comparative Example 5 lacked the Y-1 or Y-2 structure, resulting in poor segregation of silica onto the film surface and a high SCI reflectance on the film surface.

Claims

1. A photosensitive resin composition for forming a light-shielding film, The following ingredients (A) to (F): (A) Alkali-soluble resin, (B) A photopolymerizable compound having at least one ethylenically unsaturated bond, (C) Photopolymerization initiator, (D) Light-blocking agent, (E) Silica particles, (F) Silane coupling agent A photosensitive resin composition characterized by containing and satisfying both (i) and (ii) below. (i) A film made of the cured product of the photosensitive resin composition is formed on a glass substrate with an average film thickness in the range of 0.5 to 4.0 μm, and the Si2p3 / 2 peak is measured on the surface of the film by X-ray photoelectron spectroscopy (XPS), and the peak fit analysis of the Si2p3 / 2 peak is 103.9 to 104.2 eV. ２ Peak area A ＳｉＯ２ And the peak area A of SiO at 101.8–102.3 eV ＳｉＯ The ratio (A ＳｉＯ２ / A ＳｉＯ The value must be between 0.10 and 10.

0. (ii) The ratio of the amount of element F to the total amount of elements Si, C, O, and F present on the surface of the film [F / (Si+C+O+F)] is 5.0% or less.

2. The photosensitive resin composition according to claim 1, characterized in that the component (A) is a polymerizable unsaturated group-containing alkali-soluble resin represented by the following general formula (II). 【Chemistry 1】 〔In formula (II), R １ , R ２ , R ３ and R ４ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, A represents -CO-, -SO ２ -, -C(CF ３ )([[]] ２ -), -Si(CH ３ )([[]] ２ -), -CH ２ -, -C(CH ３ )([[]] ２ -), -O-, a fluorene-9,9-diyl group or a direct bond, X represents a tetravalent carboxylic acid residue, Y １ and Y ２ each independently represents a hydrogen atom or -OC-Z-(COOH)m (where Z represents a divalent or trivalent carboxylic acid residue and m represents a number from 1 to 2), n represents an integer from 1 to 20. R ５ represents a hydrogen atom or a methyl group.〕​​​

3. The photosensitive resin composition according to claim 1, characterized in that the component (D) is an inorganic or organic black pigment having an average particle size of 50 to 250 nm.

4. Furthermore, the photosensitive resin composition according to claim 1 is characterized by comprising a compound (G) having a dimethylsiloxane unit represented by the following structure (X) and an ethylene glycol repeating unit represented by the following structure (Y-1) and / or a propylene glycol repeating unit represented by the following structure (Y-2), wherein the ratio of the number of units in one molecule, (X) / [(Y-1)+(Y-2)], is 0.1 to 100. 【Chemistry 2】 (However, a is 15 or greater.) 【Transformation 3】 【Chemistry 4】

5. The photosensitive resin composition according to claim 1, characterized in that the component (E) is silica particles having an average particle diameter of 50 to 180 nm.

6. The photosensitive resin composition according to claim 1, characterized in that the component (E) is silica particles surface-treated with a group containing a vinyl group and / or a phenyl group.

7. The ratio of the aforementioned peak areas (A ＳｉＯ２ / A ＳｉＯ The photosensitive resin composition according to claim 1, characterized in that ) is 0.25 to 10.

0.

8. The photosensitive resin composition according to claim 4, characterized in that the ratio of the number of units of component (G), (X) / [(Y-1)+(Y-2)], is 1.0 to 100.

9. A light-shielding film characterized by comprising a cured product of a photosensitive resin composition according to any one of claims 1 to 8.

10. A display device characterized by comprising the light-shielding film described in claim 9.

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