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

Abstract

The present invention addresses the problem of providing an environmentally friendly photosensitive resin composition, a light-shielding film, and a display device, which have both high light-shielding properties and reduced reflectance on both the glass substrate surface side and the film surface side, and which can satisfy the requirements of PFAS specifications and the like by using an extremely small amount of fluorine. The photosensitive resin composition of the present invention contains components (A) to (F), and satisfies the following (i) and (ii) at the same time. (i) When a hardened film of the composition is formed on a glass substrate with an average film thickness in the range of 0.5 to 4.0 [mu] m and the surface of the film is measured by XPS, the ratio of the peak area ASiO2 of SiO2 to the peak area ASiO (ASiO2 / ASiO) in a peak fitting analysis of the Si2p3 / 2 peak value (ASiO2 / ASiO) is 0.10 to 10.0. (ii) The ratio [F / (Si + C + O + F)] of the amount of elemental F present in the film surface to the total amount of Si, C, O, and elemental F is 5.0% or less.

Description

Technical Field

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

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

[0003] For black matrices, high light-blocking properties and low reflectivity are required. For example, in Patent Document 1, silica particles are specifically incorporated into the photosensitive resin composition. When performing elemental analysis using STEM-EDS (energy-dispersive X-ray diffraction) on the cross-section of a film formed from the cured photosensitive resin composition, the atomic ratio of Si near the film surface was studied. This led to a technique that provides high light-blocking properties, reduces film reflectivity during the formation of the light-blocking film, and also possesses patterning performance (developability) in alkaline development during the manufacture of the light-blocking film. Furthermore, in Patent Document 1, the reflectivity is evaluated by coating the photosensitive resin composition, allowing it to harden, and then measuring the reflectivity from the glass substrate side.

[0004] Furthermore, in various display devices and solid-state imaging elements, there are requirements for reducing the reflectivity of the light-shielding film coated on a transparent substrate such as glass, depending on the design of the device. There is also a desire to reduce the reflectivity of the side opposite to the side that contacts the transparent substrate (hereinafter sometimes referred to as the "film side").

[0005] For example, Patent Document 2 discloses a technique in which, in order to obtain a color-curing film for an image display device containing silica particles and having a Si content of 7.0 atm% or more in surface elemental composition analysis by X-ray photoelectron spectroscopy (XPS), smaller primary particle sizes are used and the doping amount is increased, thereby reducing the reflectivity of the surface side of the color-curing film. However, in Patent Document 2, when evaluating reflectivity, the reflectivity is measured only from the color-curing film side (the side other than the glass substrate side) of the substrate to which the color-curing film is attached. Furthermore, the color-curing film in Patent Document 2 uses fluorine-based compounds, which are not environmentally friendly and cannot meet the requirements of recent regulations regarding organofluorine compounds (PFAS).

[0006] In addition, Patent Document 3 proposes a technique in which silica particles are specially incorporated into a photosensitive resin composition. By using hollow particles as silica particles, the high dispersibility and low refractive index of the hollow particles are used to reduce the reflectivity of the hardened film (light-shielding film) side and the substrate (glass substrate) side respectively.

[0007] In addition, Patent Document 4 proposes a technique that targets the dispersant, silica particles, and solvent used in a photosensitive resin composition, specifying the acid value and amine value of the dispersant, and specifying the total mass of the dispersant relative to the total mass of the silica particles. By including a first solvent and a second solvent as solvents, it aims to suppress the aggregation of silica particles and improve dispersibility (mobility), thereby reducing the reflectivity of the substrate (glass substrate) side and the film surface side respectively.

[0008] However, in the technologies proposed in Patent Documents 3 and 4, in particular, in order to achieve high light-shielding properties and reduce reflectivity through the segregation of silica on the film surface, a method of relatively increasing the light-shielding component was conceived. However, according to the research of the inventors of this application, this would result in the formation of foreign matter, thus failing to meet the quality requirements. Therefore, there is still room for improvement in achieving both "high light-shielding properties" and "reducing the reflectivity of both the glass substrate surface and the film surface."

[0009] [Existing Technical Documents]

[0010] [Patent Literature]

[0011] [Patent Document 1] Japanese Patent Application Publication No. 2022-52426

[0012] [Patent Document 2] Japanese Patent No. 6845469

[0013] [Patent Document 3] Japanese Patent Application Publication No. 2020-166156

[0014] [Patent Document 4] Japanese Patent Application Publication No. 2024-68130. Summary of the Invention

[0015] [The problem the invention aims to solve]

[0016] Therefore, the inventors of this application conducted a detailed study based on the aforementioned prior art, and as a result discovered a technical matter not noticed in the prior art, namely, in the peak fitting analysis of the Si2p3 / 2 peak value in the measurement of the light-shielding film surface by X-ray photoelectron spectrometry (XPS), the peak area A of SiO2 was not considered. SiO2 The peak area A of SiO SiO The ratio (A) SiO2 / A SiOWithin a defined range, this invention achieves both high light-shielding properties and reduced reflectivity on both the glass substrate side and the film side, while using very little fluorine. As a result, an environmentally friendly light-shielding film that meets the requirements of PFAS standards can be obtained, thus completing the present invention.

[0017] Therefore, the object of the present invention is to provide an environmentally friendly photosensitive resin composition that combines high light-shielding properties with reduced reflectivity on both the glass substrate side and the film side, and uses very little fluorine to meet the requirements of PFAS specifications, as well as a light-shielding film made of the cured product thereof, and a display device equipped with the light-shielding film.

[0018] Furthermore, the present invention also aims to provide an evaluation method in which, during the development of a photosensitive resin composition using silica particles and a light-shielding film composed of its cured form, the peak area ratio A is evaluated using XPS. SiO2 / A SiO The study was conducted to evaluate the degree of reflectivity of the film surface (that is, the degree of silica particle segregation as described later).

[0019] [Methods used to solve problems]

[0020] In other words, the essence of the present invention is as follows.

[0021] [1] A photosensitive resin composition for forming a light-shielding film, comprising the following components (A) to (F):

[0022] (A) Alkali-soluble resin;

[0023] (B) Photopolymerizable compounds having at least one ethylene unsaturated bond;

[0024] (C) Photopolymerization initiator;

[0025] (D) Sunscreen;

[0026] (E) Silica particles; and

[0027] (F) Silane coupling agent;

[0028] And simultaneously satisfy both (i) and (ii) below.

[0029] (i) A film composed of a cured form of the photosensitive resin composition is formed on a glass substrate with an average film thickness ranging from 0.5 to 4.0 μm. When the surface of the film is measured by X-ray photoelectron spectroscopy (XPS), the peak area A of SiO2 at 103.9 to 104.2 eV is determined in the peak fitting analysis of the Si2p3 / 2 peak. SiO2 The peak area A of SiO at 101.8 to 102.3 eVSiO The ratio (A) SiO2 / A SiO The value ranges from 0.10 to 10.0.

[0030] (ii) The ratio of the amount of F element present on the surface of the film to the total amount of Si, C, O and F elements [F / (Si+C+O+F)] is less than 5.0%.

[0031] [2] The photosensitive resin composition as described in [1], wherein the aforementioned component (A) is an alkali-soluble resin containing polymerizable unsaturated groups represented by the following general formula (II).

[0032]

[0033] [In formula (II), R1, R2, R3 and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group; A represents -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, fluorene-9,9-diyl 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 value of 1 to 2); n represents an integer from 1 to 20; R5 represents a hydrogen atom or a methyl group].

[0034] [3] The photosensitive resin composition as described in [1], wherein the aforementioned component (D) is an inorganic or organic black pigment with an average particle size of 50 to 250 nm.

[0035] [4] The photosensitive resin composition as described in [1] further comprises compound (G), which is a dimethylsiloxane unit represented by structure (X) and an ethylene glycol repeating unit represented by structure (Y-1) and / or a propylene glycol repeating unit represented by structure (Y-2), wherein the ratio of (X) / [(Y-1)+(Y-2)] in a molecule is from 0.1 to 100.

[0036]

[0037] (where a is 15 or higher).

[0038]

[0039] [5] The photosensitive resin composition as described in [1], wherein the aforementioned component (E) is silica particles with an average particle size of 50 to 180 nm.

[0040] [6] The photosensitive resin composition as described in [1], wherein the aforementioned component (E) is silica particles that have been surface-treated via a vinyl and / or phenyl group.

[0041] [7] The photosensitive resin composition as described in [1], wherein the ratio of the aforementioned peak areas (A) SiO2 / A SiO The value ranges from 0.25 to 10.0.

[0042] [8] The photosensitive resin composition as described in [4], wherein the ratio of the number of units in the aforementioned component (G) (X) / [(Y-1)+(Y-2)] is from 1.0 to 100.

[0043] [9] A light-shielding film comprising a cured form of a photosensitive resin composition as described in any one of [1] to [8].

[0044]

[10] A display device having a light-shielding film as described in [9].

[0045] [The effects of the invention]

[0046] According to the present invention, a photosensitive resin composition that combines high light-shielding properties with reduced reflectivity on both the glass substrate side and the film side, and uses very little fluorine to meet the requirements of PFAS specifications and other environmentally friendly properties, a light-shielding film composed of a cured product formed therefrom, and a display device having the light-shielding film are provided. Attached Figure Description

[0047] Figure 1 The peak values ​​of SiO2 and SiO measured by XPS were used to show the membrane of Example 28. Detailed Implementation

[0048] The following describes embodiments of the present invention.

[0049] 1. Photosensitive resin composition

[0050] 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 ethylene unsaturated bond, (C) a photopolymerization initiator, (D) a light-shielding agent, (E) silica particles, and (F) a silane coupling agent. Furthermore, the photosensitive resin composition of the present invention may preferably further comprise compound (G) described below. Additionally, the photosensitive resin composition of the present invention may preferably also comprise (H) a solvent.

[0051] For example, sometimes (A) alkali-soluble resin is referred to as "component (A)", and the same applies to other components.

[0052] In addition, the photosensitive resin composition of the present invention satisfies both (i) and (ii) below.

[0053] (i) A film composed of a cured form of the photosensitive resin composition is formed on a glass substrate with an average film thickness ranging from 0.5 to 4.0 μm. When the surface of the film is measured by X-ray photoelectron spectroscopy (XPS), the peak area A of SiO2 at 103.9 to 104.2 eV is determined in the peak fitting analysis of the Si2p3 / 2 peak. SiO2 The peak area A of SiO at 101.8 to 102.3 eV SiO The ratio (A) SiO2 / A SiO The value ranges from 0.10 to 10.0.

[0054] (ii) The ratio of the amount of F element present on the surface of the film to the total amount of Si, C, O and F elements [F / (Si+C+O+F)] is less than 5.0%.

[0055] Let's begin with the explanation from (i) above.

[0056] As shown in (i), the photosensitive resin composition of the present invention is a film formed on a glass substrate with an average film thickness ranging from 0.5 to 4.0 μm by a cured form of the photosensitive resin composition. When the surface of the film is measured by X-ray photoelectron spectroscopy (XPS), the ratio A of the aforementioned peak areas is... SiO2 / A SiO The range is from 0.10 to 10.0. The ratio A of the peak area is... SiO2 / A SiO Such a range, as confirmed in the embodiments described below, can reduce the reflectivity on both the glass substrate surface side and the film surface side. For example, a preferred range for the peak area ratio is 0.25 to 10.0.

[0057] The reason for keeping the average film thickness within the aforementioned range during XPS measurements is that if the average film thickness is less than the lower limit, the light-blocking effect is insufficient, leading to translucency. On the other hand, if it exceeds the upper limit, there is a possibility of reduced patterning performance and impact on the state of the silica particles. In other words, given this viewpoint, if the measurement is not performed within the aforementioned average film thickness range, there is a concern that the overall purpose of XPS measurement in this invention cannot be met. A more preferred average film thickness is 0.5 to 3.5 μm, more preferably 0.5 to 3.0 μm. The average film thickness can be obtained using a stylus-type step shape measuring device. Furthermore, the film formation method is described below.

[0058] Regarding the reduction of reflectivity of films (hardened films, light-shielding films), as disclosed in the prior art, the refractive index of the hardened film (light-shielding film) can be reduced by incorporating silica particles. As a result, reflection caused by the refractive index difference between the glass substrate and the film is suppressed on the glass substrate side, or reflection caused by the refractive index difference between air and the film is suppressed on the film side, thereby reducing the reflectivity of the film. It is then conceivable that a large number (high concentration) of silica particles exist near the film surface (glass substrate side and film side), thereby more effectively achieving the aforementioned effect of reducing reflectivity. For example, as discussed in the aforementioned Patent Documents 3 and 4, due to the improved dispersibility of silica particles in the photosensitive resin composition and the reduced movement restriction caused by the aggregation of silica particles in the composition, a sufficient amount of silica particles can be unevenly distributed near the film surface (glass substrate side and film side).

[0059] Furthermore, regarding the degree of uneven distribution of silica particles, for example, Patent Document 1 uses XPS on the membrane surface to analyze the surface elemental composition, while Patent Document 2 uses STEM-EDS to perform energy-dispersive X-ray analysis on the cross-section of the membrane to study the content of Si. However, both methods only focus on Si. Therefore, when other components containing Si that do not originate from silica particles are used, they are not accurate methods for determining whether silica particles are segregated near the membrane surface.

[0060] Furthermore, according to the research of the inventors of this application, it has been confirmed that simply adding a large amount of silica can actually increase the refractive index difference between the air layer and the film surface, and it has been observed that low reflectivity on the film surface side may not be achieved. In addition, it has been learned that large amounts of silica can easily cause agglomeration, or that silica particles can be exposed to the outside of the film surface during the formation of the hardened film, which can increase the unevenness of the film surface and may have an adverse effect on the quality. Therefore, it has been determined that an appropriate doping ratio is necessary.

[0061] Therefore, the results of detailed studies are not only due to the high concentration of silica near the film surface, but also, in particular, by using components with SiO bonds (structure (X)) such as compound (G) as described later with silica particles, and focusing on the peak A of SiO2 originating from silica particles. SiO2 The peak A of SiO derived from compounds such as (G) SiO The ratio, along with the segregation effect of silica particles, was considered in relation to its impact on leveling properties (surface smoothness, wettability to the substrate) and quality, revealing a range within which the reflectivity of both the glass substrate surface and the film surface can be reduced. In other words, it was found that in this invention, as described above, when measured using XPS, the aforementioned peak area ratio A... SiO2 / A SiO With a concentration of 0.10 to 10.0, a large amount of silica particles can be segregated on the film surface, and it has been found that the presence (proportion) of SiO (the amount of components such as compound (G) mentioned below) which affect leveling and quality can be determined as mentioned above. This new technical matter has technical significance in this regard.

[0062] Here, the reason for using the Si2p3 / 2 peak value in the XPS measurement of this invention is that, generally speaking, the Si bonding state obtained by XPS measurement is derived from the analysis of this Si2p3 / 2 peak value, and there is a large amount of previous analysis data available for reference, such as the database in the software and literature. In addition, peak fitting analysis, also known as peak fitting processing, is implemented for the purpose of separating repeating peaks and estimating peak positions. The peak fitting procedure is generally performed in the following order: (1) background removal / correction; (2) selection of fitting function; (3) optimization using the nonlinear least squares method; (4) determination of the parameters of the fitting function; (5) evaluation / study using the database. As for the procedure, it can also be appropriately determined by referring to publicly known methods, so there is no limitation. In this invention, the procedures and conditions performed in the embodiments described below can be used.

[0063] In this invention, by performing measurements using XPS, especially when components having SiO bonds (structure (X)) such as the compound (G) described below are used together with silica particles, the peak value of SiO2 originating from silica particles can be separated from the peak value of SiO originating from the compound (G), and the ratio A of the areas of each peak determined accordingly can be found. SiO2 / A SiO The present invention is thus accomplished because the reflectivity of the film surface (glass substrate side and film surface side) is highly correlated with that of the film surface. That is, regarding the degree of silica segregation near the surface of the film formed by the cured form of the photosensitive resin composition, conventional methods for measuring the Si content cannot accurately reflect this degree of segregation. Currently, it is still difficult to predict the reflectivity of the resulting film surface based on the relationship between the dopant components and their amounts in the composition. However, in the photosensitive resin composition of the present invention, even with changes in the dopant components or structural modifications, the peak area ratio A can be increased. SiO2 / A SiO It is technically significant to achieve this by adjusting the methods within a given scope.

[0064] Regarding the peaks obtained through this method, for example, shown in Figure 1 . Figure 1 The solid peak value represents the measured value obtained by the method described later in <XPS Analysis of Membrane Surface>, and is obtained by comparing the peak area ratio A of the membrane surface as described later in <XPS Analysis of Membrane Surface>.SiO2 / A SiO The method described in the calculation section allows for peak separation, separating the peak values ​​of SiO2 (as shown by the dotted line) and SiO (as shown by the dashed line). Integrating these peak values ​​yields the area of ​​each peak. Then, based on the calculated peak area A... SiO2 A SiO Calculate the ratio A of the peak area SiO2 / A SiO .

[0065] Next, let's explain (ii).

[0066] As shown in (ii), the photosensitive resin composition of the present invention has a ratio of the amount of F element present on the surface of the film formed in (i) to the total amount of Si, C, O and F elements [F / (Si+C+O+F)] of 5.0% or less. This ratio is more 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 does not contain F.

[0067] That is, in the present invention, as a photosensitive resin composition, by minimizing the use of components containing F and components with a small amount of F, a film that meets the requirements of PFAS specifications, is environmentally friendly, and possesses the aforementioned characteristics (i) while having reduced reflectivity of the film surface can be obtained.

[0068] While there are no limitations on the method for determining the amount of each element, as described in the examples below, in the same XPS determination as in (i), a narrow scan analysis is used to scan and analyze the energy range in which the aforementioned specific elements appear at high resolution, thereby performing quantitative analysis of each element. The analytical conditions are preferably performed according to the method described in the examples, based on the peak intensity of the detected elements (Si, C, O, F) in the narrow spectrum, using the relative sensitivity factor method to correct the peak area, thereby determining the content (atomic concentration (atom%)), and calculating the ratio (%) of the F element content to the total content of Si, C, O, and F elements.

[0069] Furthermore, in the aforementioned (i) and (ii), the measurement range and depth are not limited as they can be appropriately set according to the measuring device, etc. Regarding the measurement range (planar range), it can be determined according to the X-ray irradiation range, and a circular range of approximately 1 mm to 10 mm is generally preferred. Additionally, the measurement depth is 2 to 8 nm, and 2 to 4 nm is generally preferred. That is, the depth range of the aforementioned "film surface," etc., is defined from the range of this measurement depth.

[0070] The following describes the specific blending components of the photosensitive resin composition of the present invention having the foregoing (i) and (ii).

[0071] <(A) Alkali-soluble resin>

[0072] The alkali-soluble resin is more preferably an alkali-soluble resin containing unsaturated groups, which is a resin having an acid value that imparts alkali developability and, when combined with the photopolymerizable compound of component (B) described below, possesses suitable photocurability. The alkali-soluble resin containing unsaturated groups can be any known type and is not limited thereto; however, from the perspective of high heat resistance and the ability to form high-precision patterns, the following description is preferred.

[0073] In the first example of an alkali-soluble resin containing unsaturated groups, which is preferably used as an alkali-soluble resin, a compound having two or more epoxy groups is reacted with (meth)acrylic acid (which represents acrylic acid and / or methacrylic acid) to obtain an epoxy (meth)acrylate compound having hydroxyl groups, and then reacted with (a) dicarboxylic acid or tricarboxylic acid or its monoanhydride and / or (b) tetracarboxylic acid or its dianhydride to obtain an epoxy (meth)acrylate acid adduct. Examples of compounds having two or more epoxy groups that derive into epoxy (meth)acrylate acid adducts include bisphenol-type epoxides and phenolic varnish-type epoxides. Specifically, bisphenol-type epoxides represented by the following general formula (I) can be appropriately listed.

[0074]

[0075] In general formula (I), R1, R2, R3, and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a phenyl group, and A represents -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, fluorene-9,9-diyl, or a direct bond. l is an integer from 0 to 10. Preferably, R1, R2, R3, and R4 are hydrogen atoms, and preferably A is fluorene-9,9-diyl. In addition, l usually has multiple values, so the average value is 0 to 10 (not limited to integers), but the average value of l is preferably 0 to 3. Furthermore, the following explanation uses the case where l = 0 in general formula (I).

[0076] Bisphenolic epoxides are epoxides with two glycidyl ether groups obtained by reacting bisphenols with epichlorohydrin. The reaction is generally accompanied by oligomerization of diglycidyl ether compounds, thus containing epoxides with more than two bisphenol skeletons.

[0077] The bisphenols used in this reaction can be listed as follows: bis(4-hydroxyphenyl)one, bis(4-hydroxy-3,5-dimethylphenyl)one, bis(4-hydroxy-3,5-dichlorophenyl)one, 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-hydroxy-3,5-dichlorophenyl)hexafluoropropane, bis(4-hydroxy-3,5-dichlorophenyl) Hexafluoropropane, bis(4-hydroxyphenyl)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-hydroxyphenyl)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'-biphenyl, 3,3'-biphenyl, etc. Among these, bisphenols having a fluorene-9,9-diyl group are particularly preferred.

[0078] Furthermore, regarding the monohydric anhydride of (a) dicarboxylic acid or tricarboxylic acid that reacts with the epoxy (meth)acrylate obtained from the reaction of this epoxide and (meth)acrylic acid, monohydric anhydrides of chain-type hydrocarbon dicarboxylic acid or tricarboxylic acid, alicyclic dicarboxylic acid or tricarboxylic acid, or aromatic dicarboxylic acid or tricarboxylic acid are used. Here, regarding the monohydric anhydride of chain-type hydrocarbon dicarboxylic acid or tricarboxylic acid, for example, monohydric anhydrides containing succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citric acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxyglutaric acid, pimelic acid, sebacic acid, octanoic acid, diethylene glycol, etc., monohydric anhydrides of dicarboxylic acid or tricarboxylic acid with any substituent can also be used. Furthermore, regarding the monohydric anhydrides of alicyclic dicarboxylic acids or tricarboxylic acids, examples include monohydric anhydrides containing cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylmethylenetetrahydrophthalic acid, chlorobridged acid, hexahydrophenyltriglyceric acid, norbornenedicarboxylic acid, etc., and monohydric anhydrides of dicarboxylic acids or tricarboxylic acids with any substituents. Similarly, regarding the monohydric anhydrides of aromatic dicarboxylic acids or tricarboxylic acids, examples include monohydric anhydrides containing phthalic acid, isophthalic acid, phenyltriglyceric acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, etc., and monohydric anhydrides of dicarboxylic acids or tricarboxylic acids with any substituents.

[0079] Furthermore, regarding the dianhydride of (b) tetracarboxylic acids that react with epoxy (meth)acrylates, dianhydrides of chain-type hydrocarbon tetracarboxylic acids, alicyclic tetracarboxylic acids, or aromatic tetracarboxylic acids are used. Here, for example, dianhydrides of chain-type hydrocarbon tetracarboxylic acids include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, etc., and dianhydrides of tetracarboxylic acids with any substituents may also be used. Similarly, for alicyclic tetracarboxylic acids, for example, dianhydrides of cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norcamphenetetracarboxylic acid, etc., dianhydrides of tetracarboxylic acids with any substituents may also be used. In addition, examples of dianhydrides of aromatic tetracarboxylic acids include: benzopyroxene, 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, etc., and dianhydrides of tetracarboxylic acids with any substituents can also be used.

[0080] The molar ratio (a) / (b) of the monoanhydride of (a) dicarboxylic acid or tricarboxylic acid and the dianhydride of (b) tetracarboxylic acid reacting with epoxy (meth)acrylate can be 0.01 or more and 10.0 or less, more preferably 0.02 or more and less than 3.0. If the molar ratio (a) / (b) is within the aforementioned range, it is easy to obtain the optimal molecular weight for forming a photosensitive resin composition with good photopatterning properties, and the alkali solubility is not compromised, which is therefore preferred.

[0081] The reaction of epoxides with (meth)acrylic acid, and the reaction of the resulting epoxy (meth)acrylate with the aforementioned polyprotic carboxylic acid or its anhydride, are not particularly limited and can be carried out by publicly known methods. For example, they can be manufactured by methods described in Japanese Patent Application Publication No. 8-278629 and Japanese Patent Application Publication No. 2008-9401. First, the method for reacting (meth)acrylic acid with epoxides includes, for example, the following method: adding the epoxy group of the epoxide and an equimolar amount of (meth)acrylic acid to a solvent, heating and stirring at 90 to 120°C while blowing in air in the presence of a catalyst (triethylbenzylammonium chloride, 2,6-diisobutylphenol, etc.) to allow the reaction to proceed. Second, the method for reacting the hydroxyl groups of the epoxy acrylate compound, which is the reaction product, with an anhydride includes, for example, the following method: adding a predetermined amount of epoxy acrylate compound, a dianhydride, and a monohydric anhydride to a solvent, heating and stirring at 90 to 130°C in the presence of a catalyst (tetraethylammonium bromide, triphenylphosphine, etc.) to allow the reaction to proceed. The epoxy acrylate acid adducts obtained in this method have a skeleton of general formula (II).

[0082]

[0083] In formula (II), R1, R2, R3, and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a phenyl group; A represents -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, fluorene-9,9-diyl, 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.

[0084] Secondly, regarding a second example of an alkali-soluble resin containing unsaturated groups that can be preferably applied to alkali-soluble resins, it includes a resin having (meth)acryloyl and carboxyl groups, which is a copolymer of (meth)acrylic acid, (meth)acrylate, etc. Examples of the aforementioned resins include an alkali-soluble resin containing unsaturated groups obtained by reacting a copolymer obtained by copolymerizing (meth)acrylate containing glycidyl methacrylate in a solvent with (meth)acrylic acid, and finally reacting it with an anhydride of dicarboxylic acid or tricarboxylic acid. The aforementioned copolymers can be referenced from: the copolymer with a number average molecular weight (Mn) of 2000 to 20000 and an acid value of 35 to 120 mgKOH / g composed of 20 to 90 mol% of "repeating units derived from diglycerides obtained by esterification of the hydroxyl groups at both ends with (meth)acrylic acid" and 10 to 80 mol% of "repeating units derived from one or more polymerizable unsaturated compounds that can be copolymerized therewith" as shown in Japanese Patent Application Publication No. 2018-141968, which is a polymer with a weight average molecular weight (Mw) of 3000 to 50000 and an acid value of 30 to 200 mgKOH / g comprising units derived from (meth)acryloyl compounds and units having (meth)acryloyl groups and di or tricarboxylic acid residues.

[0085] Furthermore, regarding the weight-average molecular weight (Mw) of the alkali-soluble resin, it is generally preferred to be between 2000 and 10000, and more preferably between 3000 and 8000. If the weight-average molecular weight (Mw) is less than 2000, the pattern adhesion during development cannot be maintained, and pattern peeling is likely to occur. In addition, if the weight-average molecular weight (Mw) exceeds 10000, development residue and residual film in unexposed areas are likely to remain. Additionally, the acid value of the alkali-soluble resin is preferably in the range of 30 to 200 mg KOH / g. This is because if this value is less than 30 mg KOH / g, there may be situations where alkali development cannot be performed smoothly, or special development conditions such as strong alkali are required. Furthermore, if it exceeds 200 mg KOH / g, the penetration of the alkali developer becomes too rapid, and peeling development is likely to occur.

[0086] The content of alkali-soluble resin in the total solids of the photosensitive resin composition is preferably 5 to 70% by mass, more preferably 5 to 60% by mass, and even more preferably 10 to 55% by mass. The content of alkali-soluble resin can be adjusted together with the photopolymerizable compound, etc., in component (B) described below.

[0087] <(B) Photopolymerizable compounds having at least one ethylene unsaturated bond>

[0088] Component (B) can be listed as, for example: 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyhexyl methacrylate, and other hydroxyl-containing methacrylates, or ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra ... (Meth)acrylates, 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, phosphonazine-modified epoxide hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and other (meth)acrylates, dendritic polymers having (meth)acryloyl groups, etc., may be used, one or more of these. Dendritic polymers having (meth)acryloyl groups, for example, can be exemplified by publicly known dendritic polymers obtained by adding a portion of the carbon-carbon double bond in the (meth)acryloyl group of a polyfunctional (meth)acrylate compound to a thiol group in a multi-mercaptoyl compound.

[0089] Component (B) functions to crosslink the molecules of the alkali-soluble resin. To achieve this function, it is preferable to use a component having two or more vinyl unsaturated bonds. Furthermore, the acrylic equivalent, obtained by dividing the molecular weight of the monomer by the number of (meth)acryloyl groups in one molecule, should be between 50 and 300.

[0090] Regarding the amount of component (B), the ratio of its content to component (A) is approximately 50 / 50 to 90 / 10 by mass, preferably 60 / 40 to 80 / 20. If the ratio of component (A) is less than 50 / 50, the cured product becomes brittle after photocuring. Furthermore, the low acid value of the coating in the unexposed area reduces its solubility in the alkaline developer, potentially resulting in uneven and less sharp pattern edges. Conversely, if the ratio of component (A) is greater than 90 / 10, the proportion of photoreactive functional groups in the resin is low, resulting in insufficient cross-linking. Additionally, the high acid value in the resin increases the solubility of the exposed area in the alkaline developer, potentially leading to a pattern that is thinner than the target linewidth or is prone to pattern defects.

[0091] <(C) Photopolymerization initiator>

[0092] Component (C) can include, for example: acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropionylbenzene, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, benzyl dimethyl ketal, and other acetophenone derivatives; benzophenone, 2-chlorobenzophenone, p,p'-bis(dimethylaminobenzophenone), 4,4'-bis(dimethylaminobenzophenone) (milchlerone), 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4,4'-diethylaminobenzophenone, and other benzophenone derivatives; benzoethylene glycol (benzil), benzoin Benzoin ethers, such as benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; biimidazole compounds, such as 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-triarylbiimidazole, and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2-biimidazole; and 2-trichloromethyl-5-styryl-1,3,4- diazole, 2-trichloromethyl-5-(p-cyanostylenyl)-1,3,4- diazole, 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4- Halogenated methyl diazole compounds such as diazoles; 2,4,6-trichloromethyl)-1,3,5-trichlorodiazole 2-Methyl-4,6-bis(trichloromethyl)-1,3,5-trimethyl 2-Phenylacet-4,6-bis(trichloromethyl)-1,3,5-tris(2, ... 2-(4-Chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-trichlorophenyl 2-(4-Methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-tris(meth ... 2-(4-Methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-tri 2-(4-Methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-tris(methoxystyryl) 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-tri 2-(4-Methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-tris(methylthiostyryl) Halomethyl-s-trimethyl This compound class includes: 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyl oxime), 1-(4-phenylthiophenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylthiophenyl)butane-1,2-dione-2-oxime-O-acetate, 1-(4-methylthiophenyl)butane-1-ketooxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-bicycloheptyl-1-ketooxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-adamantylmethane-1-ketooxime-O-benzoate, 1-[9-ethyl-6-( [2-Methylbenzoyl)-9H-carbazole-3-yl]-adamantylmethane-1-ketooxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-tetrahydrofuranylmethane-1-ketooxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-tetrahydrofuranylmethane-1-ketooxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-thiophenylmethane-1-ketooxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-thiophenylmethane-1-ketooxime-O-acetate, 1-[9 [9-Ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-morpholinylmethane-1-ketooxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-morpholinylmethane-1-ketooxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethane-1-ketooxime-O-bicycloheptane carboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethane-1-ketooxime-O-tricyclodecane carboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethane-1-ketooxime-O-adamantane carboxylate, 1- [4-(phenylhydrothio)phenyl]octane-1,2-dione = 2-O-benzoyl oxime, 1-[9-ethyl-6-(2-methylbenzoyl)carbazole-3-yl]acetophenone-O-acetyl oxime, (2-methylphenyl)(7-nitro-9,9-dipropyl-9H-fluoren-2-yl)-acetyl oxime, 1-[7-(2-methylbenzoyl)- O-acyl oxime compounds, including 9,9-dipropyl-9H-fluoren-2-yl]-1-(o-acetyl oxime) ketone, 1-(-9,9-dibutyl-7-nitro-9H-fluoren-2-yl)-1-O-acetyl oxime ketone, and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(o-acetyl oxime) ketone;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; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone; organic peroxides such as azobisisobutylnitrile, benzoyl peroxide, and cumene peroxide; and 2-mercaptobenzimidazole and 2-mercaptobenzo[]. Thiol compounds such as azoles, 2-mercaptobenzothiazoles, β-mercaptopropionic acid, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, stearyl-3-mercaptopropionate, trimethylolpropane-3-mercaptopropionate, tris(3-mercaptopropionyl)-[(3-mercaptopropionyloxy)-ethyl]-triisocyanate, pentaerythritol tetra(3-mercaptobutyrate), pentaerythritol tetra(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol thio(3-mercaptopropionate), 3,3'-thiodipropionic acid, dithiodipropionic acid, laurylthiopropionic acid, etc. are preferred. From the viewpoint of easily obtaining a photosensitive resin composition for a light-shielding film with high sensitivity, O-acyl oxime compounds are preferred. Alternatively, two or more of these photopolymerization initiators may be used. Furthermore, the photopolymerization initiator described in this invention is used in the sense of including a sensitizer.

[0093] Examples of O-acyloxime compounds that may be preferred to use include O-acyloxime photopolymerization initiators represented by the following general formulas (6) and (7). Among these groups of compounds, when using a light-shielding component at a high concentration, it is more preferable to use an O-acyloxime photopolymerization initiator with a molar absorptivity of 10,000 or more at 365 nm.

[0094]

[0095] In general formula (6), R9, R 10 Each of the following groups independently represents an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 4 to 12 carbon atoms; R 11 This refers to alkyl groups having 1 to 15 carbon atoms, aryl groups having 6 to 18 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms. Here, the alkyl and aryl groups may also be substituted via alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, alkanoyl groups having 1 to 10 carbon atoms, or halogens. The alkylene moiety may also contain unsaturated bonds, ether bonds, thioether bonds, or ester bonds. Furthermore, the alkyl group may be any type of straight-chain, branched, or cyclic alkyl group.

[0096]

[0097] In general formula (7), R 12 and R13 Each is independently a straight-chain or branched alkyl group having 1 to 10 carbon atoms, or a cycloalkyl, cycloalkylalkyl, or alkylcycloalkyl group having 4 to 10 carbon atoms, or may be a phenyl group substituted with an alkyl group having 1 to 6 carbon atoms. R 14 Each is independently a straight-chain or branched alkyl or alkenyl group having 2 to 10 carbon atoms, and a portion of the -CH2- group in the alkyl or alkenyl group may be substituted with an -O- group. Additionally, these R... 12 To R 14 Some of the hydrogen atoms in the radical can also be replaced by halogen atoms.

[0098] Furthermore, while it does not function as a photopolymerization initiator or sensitizer on its own, it can be used in combination with the aforementioned compounds to add compounds that enhance the photopolymerization initiator or sensitizer capabilities. Examples of such compounds include amine compounds that are effective when used in combination with benzophenone. Examples of the aforementioned amine compounds include: triethylamine, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, ethyl 2-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, etc.

[0099] Regarding the amount of component (C), it is more preferably 2 to 40 parts by mass relative to the total of 100 parts by mass of components (A) and (B), and more preferably 3 to 30 parts by mass.

[0100] <(D) Sunscreen>

[0101] The (D) component is not particularly limited, but is preferably an inorganic or organic black pigment, and more preferably a component selected from the group consisting of organic black pigments, inorganic black pigments, and mixed-color pseudo-blackening pigments. Examples of such organic black pigments include perylene black, aniline black, cyanine black, and lactam black. Examples of such inorganic black pigments include carbon black, chromium oxide, iron oxide, and titanium black. Examples of such mixed-color pseudo-blackening pigments include those that are made by mixing two or more pigments selected from red, blue, green, purple, yellow, cyanine, and magenta. Such a light-blocking agent can use only one of the above-mentioned light-blocking components, or two or more can be used in combination. Furthermore, from the viewpoint of good light-blocking properties, surface smoothness, dispersion stability, and compatibility with resin, carbon black is particularly preferred.

[0102] Such a light-blocking agent can preferably be the aforementioned light-blocking component (especially carbon black) with an average particle size of 50 to 250 nm, more preferably 80 to 200 nm. If the average particle size of this light-blocking component (especially carbon black) is less than the aforementioned lower limit, the light-blocking properties of the resulting light-blocking film tend to decrease. Moreover, due to the increased surface area and the increase in reaction points, it becomes easier to aggregate. If the average particle size exceeds the aforementioned upper limit, the smoothness of the light-blocking film decreases. In addition, the average particle size of the light-blocking component can be determined by particle size distribution measurement using methods such as dynamic light scattering.

[0103] Furthermore, the opaque agent is preferably pre-dispersed together with the dispersant in the solvent (H) described below to form an opaque dispersion before being incorporated into the photosensitive resin composition. Here, the solvent in which it is dispersed is part of component (H) described below, so any component listed in component (H) can be used, such as propylene glycol monomethyl ether acetate, cyclohexanone, etc. Regarding the blending ratio of component (D) forming the opaque dispersion, it is preferably used in the range of 20 to 70% by mass relative to the total solids 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 most preferably in the range of 40 to 60% by mass. In addition, if the opaque dispersion contains the aforementioned dispersant, the content here refers to the content containing the dispersant.

[0104] Furthermore, the aforementioned dispersant can be any publicly known dispersant, such as various polymeric dispersants. Examples of dispersants are not particularly limited; publicly known compounds conventionally used for dispersing pigments (compounds sold commercially under names such as dispersant, dispersing wetting agent, dispersing accelerator, etc.) can be used. Examples include: cationic polymers as dispersants, anionic polymers as dispersants, nonionic polymers as dispersants, and pigment derivative-type dispersants (dispersing aids). Particularly suitable are cationic polymers having cationic functional groups such as imidazole, pyrrole, pyridyl, primary, secondary, or tertiary amine groups as adsorption sites for 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. Regarding the amount of this dispersant incorporated, in component (D), 1 to 35% by mass is more preferably preferred.

[0105] <(E)Silica particles>

[0106] There are no particular restrictions on the manufacturing method (such as gas-phase reaction or liquid-phase reaction) or shape (spherical or non-spherical) of the silica particles of component (E). Furthermore, there are no particular limitations on the type of silica particles; solid silica particles or hollow silica particles can be used. Additionally, "hollow silica particles" refers to silica particles with cavities inside.

[0107] (E) The component can reduce the refractive index of a film (light-shielding film, hardened film) composed of a hardened photosensitive resin composition. As a result, reflection caused by the refractive index difference between the glass substrate and the film on the glass substrate side or by the refractive index difference between air and the film on the film surface side can be suppressed, thereby reducing the reflectivity of the film surface.

[0108] 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. It is believed that compared to small-diameter silica particles with an average particle size of several nm, silica particles with a size in the aforementioned range are less prone to particle aggregation. Therefore, if the particle size of component (E) is in the aforementioned range, component (E) can be segregated near the surface, thereby appropriately improving dispersion stability. Moreover, it is less likely that aggregation within the film will restrict the movement of component (E), allowing sufficient component (E) to segregate on the surface side of the film. Therefore, it is believed that reflectivity can be reduced on both the glass substrate side and the film surface side of the film. In addition, by keeping the average particle size of component (E) in the aforementioned range, in addition to the aforementioned effect of segregation, the reduction in film linearity and surface smoothness caused by component (E) segregated on the film surface side can be suppressed.

[0109] (E) The aforementioned average particle size of the component can be determined, for example, by the cumulative method using a particle size analyzer “FPAR-1000” (manufactured by Otsuka Electronics Co., Ltd.) with dynamic light scattering.

[0110] In this invention, regarding the (E) component, in order to moderately improve the aforementioned dispersion stability and to prevent the (E) component from being restricted in its movement due to aggregation within the film, thus allowing sufficient (E) component to segregate on the surface side of the film, a preferred embodiment is that the surface of the silica particles is surface-treated. There are no limitations on the surface treatment of the silica particles, and known methods can be cited. In particular, to improve compatibility with the (H) solvent described below and thereby improve the aforementioned dispersion stability, it is preferred to use silica particles surface-modified with a group containing a hydrophobic functional group. The hydrophobic functional group is preferably an aryl or alkyl group having 1 to 8 carbon atoms, such as phenyl, vinyl, styrene, epoxy, or cyclohexyl, and more preferably a group containing phenyl and / or vinyl groups.

[0111] Regarding the aforementioned surface-treated silica particles, in addition to commercially available products using silica particles surface-treated with the aforementioned functional groups, they can also be obtained by surface-treating untreated silica particles. As for the surface treatment method, there are no limitations on any method that can introduce the aforementioned functional groups onto the surface of the silica particles. Methods using publicly known surface treatment agents are examples. From the viewpoint of reactivity and operability with silica particles, the method of surface treatment using a silane coupling agent having the aforementioned functional groups is more preferred. Regarding the surface treatment method of silica particles using a silane coupling agent, publicly known methods can be appropriately employed, for example, methods using silane coupling agents represented by the following chemical formulas.

[0112]

[0113] (Where R6 independently represents each of the aforementioned aryl or alkyl groups having 1 to 8 carbon atoms, R7 independently represents each of the hydrogen atoms and alkyl groups having 1 to 4 carbon atoms, R8 independently represents each of the alkyl groups having 1 to 4 carbon atoms, and q represents 1 to 3).

[0114] There is no limitation on the amount of silane coupling agent relative to the silica particles, but it is more preferably 0.5 to 5% by mass, and more preferably 1 to 4% by mass, relative to the mass of the silica particles.

[0115] Here, the refractive index of component (E) is preferably between 1.10 and 1.47. Besides using the refractive index (1.45 to 1.47) of general silica particles, the refractive index of the light-shielding film can be lower than that of a light-shielding film containing only general silica particles by using hollow silica particles with a low refractive index. The refractive index can be determined from a transparent mixture obtained by mixing silica particles processed into powder with a standard refractive liquid with a known refractive index. Alternatively, the refractive index of the silica particles can be measured using an Abbe refractometer.

[0116] The shape of component (E) can be either spherical or elliptical. Of these, a spherical shape is preferred. The sphericity is preferably between 1.0 and 1.5. As long as the sphericity of the silica particles is within this range, the particle shape is close to a sphere. Therefore, it becomes possible to uniformly fill the in-plane direction (horizontal to the glass substrate surface) in a thinner film, maintaining the smoothness of the film surface while preventing silica particles from protruding from the film surface. Thus, a light-shielding film with 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 and shortest diameters are values ​​obtained by photographing component (E) with a transmission electron microscope and measuring its longest and shortest diameters from the resulting microscope images.

[0117] Component (E) can be mixed with other admixtures as a dispersion in solvent (H) described below. Alternatively, known dispersants that form a dispersion of silica particles can also be used.

[0118] The amount of component (E) is preferably used in the range of 2 to 20% by mass relative to the total solids of the photosensitive resin composition, more preferably in the range of 2.5 to 15% by mass. In the case where the solvent (H) described below is included, the amount is preferably 0.1 to 5% by mass relative to the total mass of the photosensitive resin composition containing the solvent, more preferably 0.1 to 2% by mass. If the amount of silica particles is within the aforementioned range, low reflectivity and good photopatterning and high opacity can be achieved. Furthermore, if the silica particle dispersion contains the aforementioned dispersant, the same applies as in the case of component (D), where the content indicates the content of the dispersant also included. The amount of this dispersant in component (E) is preferably 1 to 40% by mass.

[0119] <(F)Silane Coupling Agent>

[0120] Examples of silane coupling agents for component (F) include: epoxy compounds such as 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropyltriethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; (meth)acrylate compounds such as 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-methacryloyloxypropyltriethoxysilane; vinyl compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, and p-styryltrimethoxysilane; isocyanates such as 3-isocyanopropyltrimethoxysilane and 3-isocyanopropyltriethoxysilane; and urea compounds such as 3-ureopropyltrimethoxysilane and 3-ureopropyltriethoxysilane. By using silane coupling agents, the adhesion to the glass substrate can be improved.

[0121] The amount of silane coupling agent used is preferably 0.05 to 10% by mass relative to the total solids of the photosensitive resin composition, more preferably 0.1 to 5% by mass.

[0122] <Compound(G)>

[0123] In this invention, it is more preferably a compound (G) comprising a dimethylsiloxane unit represented by structure (X) and an ethylene glycol repeating unit represented by structure (Y-1) and / or a propylene glycol repeating unit represented by structure (Y-2), wherein the ratio of the number of units in one molecule of compound (G) (X) / [(Y-1)+(Y-2)] is from 0.1 to 100. By further comprising this compound (G), the aforementioned peak area ratio A can be obtained.SiO2 / A SiO The aforementioned membrane. That is, although the exact mechanism of action is not yet clear, it is speculated that further use of a compound (G) containing this structure (X) and structures (Y-1) and / or (Y-2) in a predetermined ratio, and having a clearly defined structure consisting of hydrophobic and hydrophilic groups, could enhance the interaction with silica particles in the photosensitive resin composition and increase their migration towards the membrane surface. Accordingly, it is believed that allowing silica particles to exist in large quantities (high concentration) near the membrane surface (glass substrate side and membrane side) could cause segregation, thereby reducing the reflectivity of the membrane surface.

[0124]

[0125] In structure (X), a is 15 or more. By using a compound (G) having a structure (X) with a value of 15 or more, it is expected that a balanced interaction with silica particles can be achieved while maintaining good hydrophobicity. Preferably, a is 20 or more. There is no upper limit to the value of a, but excessive hydrophobicity may lead to stronger interactions with other materials than with silica particles, and there is a possibility that silica particles cannot exist in large quantities (high concentration) on the film surface. Therefore, a is preferably 150 or less.

[0126]

[0127] For this compound (G), the ratio of the number of the aforementioned 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.

[0128] Here, as such a compound (G), there are no restrictions on the use of any compound having the aforementioned structure (X) and structure (Y-1) and / or structure (Y-2) in a predetermined ratio of unit numbers. Examples include copolymers of polydimethylsiloxane with polyethylene glycol and / or polypropylene glycol; copolymers of polydimethylsiloxane with propylmethylsiloxane incorporating polyethylene glycol and / or polypropylene glycol structures; copolymers of polydimethylsiloxane with propyl groups in a portion of the side chain and polyethylene glycol and / or polypropylene glycol; copolymers of polydimethylsiloxane with hydrosilyl groups in a portion of the side chain and polyethylene glycol and / or polypropylene glycol; copolymers of polydimethylsiloxane with poly(ethylene glycol / propylene glycol); copolymers formed by incorporating polyethylene glycol and / or propylene glycol into the side chain of polydimethylsiloxane; copolymers of structures formed by incorporating (meth)acrylate groups into the side chain and / or ends of polydimethylsiloxane with polyethylene glycol mono(meth)acrylate and / or polypropylene glycol mono(meth)acrylate; and copolymers of structures formed by incorporating (meth)acrylate groups into the side chain and / or ends of polydimethylsiloxane with poly(ethylene glycol) di(meth)acrylate, etc. A more preferred embodiment is a copolymer of polydimethylsiloxane with polyethylene glycol and / or polypropylene glycol, a copolymer of polydimethylsiloxane with polyethylene glycol and / or polypropylene glycol having propyl groups in a portion of the side chain, or a copolymer of a structure formed by introducing (meth)acrylate groups into the side chain and / or ends of polydimethylsiloxane with polyethylene glycol mono(meth)acrylate and / or polypropylene glycol mono(meth)acrylate. Furthermore, the term "poly(ethylene glycol / propylene glycol)" refers to a random copolymer of ethylene glycol and propylene glycol. The copolymer can be a random copolymer or a block copolymer.

[0129] The number of units in structure (X) and structures (Y-1) and / or structure (Y-2) can be determined using publicly known methods. For example, it can be calculated from the proportion of each component containing each unit in the aforementioned copolymers, or it can be calculated from nuclear magnetic resonance (NMR) measurements. For example, the method for calculating from NMR measurements can be found in the electronic supplement "Supporting information" of Colloid Polym Sci, vol. 285, 673–680 (2007) regarding poly(dimethylsiloxane)-graft-poly(ethylene oxide). 1 Molecular structure analysis obtained by H-NMR, etc.

[0130] The amount of compound (G) used is preferably in the range of 0.005 to 10% by mass relative to the total solids of the photosensitive resin composition. In the case of including the solvent (H) described below, the amount is preferably 0.001 to 1.0% by mass relative to the total mass of the photosensitive resin composition including the solvent. More preferably, it is 0.001 to 0.5% by mass relative to the total mass.

[0131] <(H)solvent>

[0132] In the photosensitive resin composition of the present invention, in addition to the components (A) to (G) mentioned above, a solvent belonging to component (H) is preferably used. 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; acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone. Ketones such as pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as methyl celecoxib, ethyl celecoxib, methyl carbitol, ethyl carbitol, butyl carbitol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; ethyl acetate, Esters such as butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxypropionate, 3-ethoxypropionate, celuso acetate, ethylceluso acetate, butylceluso acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate are included. Organic solvents can be used alone or in combination.

[0133] <Other Ingredients>

[0134] In the photosensitive resin composition, other resin components other than epoxy resin (A), hardeners, hardening accelerators, thermal polymerization inhibitors and additives such as antioxidants, plasticizers, fillers other than silica, and defoamers may also be added as needed.

[0135] Other examples of resin components include: vinyl resin, polyester resin, polyamide resin, polyimide resin, polyurethane resin, polyether resin, melamine resin, epoxy resin, etc.

[0136] Examples of curing agents include amine compounds, polycarboxylic acid compounds, phenolic resins, amino resins, dicyandiamine, Lewis acid compounds, etc., which help cure epoxy resins. Examples of curing accelerators include tertiary amines, quaternary ammonium salts, tertiary phosphine, quaternary phosphonium salts, borate esters, Lewis acids, organometallic compounds, imidazoles, etc., which help promote the curing of epoxy resins.

[0137] Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, gallophenol, tert-butylcatechol, and phenthiazolinone. Hindered phenolic compounds, etc. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc. Examples of fillers include glass fiber, mica, alumina, etc. Examples of defoamers include acrylic compounds, etc.

[0138] <Solid form fraction>

[0139] The photosensitive resin composition of the present invention contains the aforementioned components (A) to (F) and, as desired, compounds (G) and solvent (H) as main components. The total content of (A) to (F) and, as desired, compounds (G) in the solid fraction (which includes monomers that become solid fractions after curing), excluding the solvent of component (H), is preferably 70% by mass, 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 the photosensitive resin composition of the present invention may contain solvent in the range of 60% to 90% by mass.

[0140] 2.Light-shielding film

[0141] The light-shielding film of the present invention is a film composed of a cured product of the aforementioned photosensitive resin composition. Furthermore, as mentioned above, an average film thickness of 0.5 μm to 4.0 μm is more preferred.

[0142] Furthermore, the light-shielding film of the present invention is a film composed of a photocurable form of a photosensitive resin composition. The term "photocurable form" as used herein refers to any material that is cured by light at any stage of the curing process of the photosensitive resin composition, including those cured by heat curing (post-baking) after light curing. That is, the photocurable form described herein can be a cured material obtained solely by light curing, or a cured material obtained by heat curing after light curing. Thus, the light-shielding film of the present invention is obtained by curing the aforementioned photosensitive resin composition of the present invention by light (and, depending on the need, by curing with heat after light curing). There are no particular limitations on the methods that can be used to form a light-shielding film with a specific pattern. For example, the following method can be ideally used: using a solution (containing the above-mentioned component (H)) as a photosensitive resin composition, coating the solution photosensitive resin composition onto a substrate, performing a heat treatment (pre-baking) to remove the component (H), then performing an exposure treatment using a mask for forming the desired light-shielding film pattern, so that the photosensitive (photocurable) resin in the photosensitive part (exposed part) is photocured, then performing a development treatment to remove the photosensitive resin composition in the unexposed part, and further performing a heat treatment (post-baking) as needed to form a light-shielding film (light-shielding film pattern).

[0143] The following is a brief description of a method that can be ideally used to form this type of light-shielding film.

[0144] In this method of forming a light-shielding film, the aforementioned solution-state photosensitive resin composition is first coated onto a substrate. Methods for coating this solution-state photosensitive resin composition onto the substrate include, for example, the known solution impregnation method. Besides spray coating, methods using a roller coater, land coater, slot coater, spin coater, etc., are also possible. Furthermore, any substrate required for forming the light-shielding film can be used; examples include known transparent substrates for display devices (e.g., glass substrates).

[0145] Furthermore, in this method of forming a light-shielding film, after coating the aforementioned solution-state photosensitive resin composition onto a substrate, a heat treatment (pre-baking) is performed to remove the solvent from the composition. The heating temperature and heating time during this pre-baking can be appropriately set according to the type of solvent used; for example, the heating temperature can be set to 60 to 110°C (set in a manner not exceeding the heat resistance temperature of the aforementioned transparent substrate), and the heating time can be set to 1 to 5 minutes. Through this heat treatment, a dried coating of the photosensitive resin composition can be obtained.

[0146] Furthermore, in this method of forming a light-shielding film, the pre-baked coating (dry coating of the photosensitive resin composition) is exposed using a mask for forming a desired light-shielding film pattern, thereby photocuring the resin in the photosensitive portion (light-exposed portion) of the coating. There are no particular limitations on the conditions used in this exposure process; publicly known exposure conditions used when forming a light-shielding film using photosensitive resin can be appropriately utilized, as long as suitable conditions are adopted according to the types of components (A), (B), and (C) used.

[0147] Furthermore, in this method of forming a light-shielding film, a developing treatment is performed on the exposed coating to remove the photosensitive resin composition from the unexposed portions of the coating. This developing treatment method is not particularly limited, and any known developing method can be appropriately employed. Additionally, since an alkali-soluble resin is used as component (A) in the aforementioned photosensitive resin composition, it is preferable to use an alkaline developing solution for this developing treatment (alkaline developing treatment). Such an alkaline developing solution can be a known alkaline developing solution, such as an aqueous solution of an alkali metal or alkaline earth metal carbonate or hydroxide. Furthermore, by performing this developing treatment to remove the unexposed portions of the resin composition, a patterned light-shielding film (light-shielding film pattern: pixel pattern) can be formed. Furthermore, to ensure that the obtained light-shielding film is sufficiently hardened and the developing solution is sufficiently removed, the aforementioned light-shielding film (light-shielding film pattern) may be further subjected to a heat treatment (post-baking).

[0148] Post-baking can be performed using publicly known methods (heating with an oven, hot air blower, heating plate, infrared heater, etc., vacuum drying, or a combination thereof). The heating temperature is the temperature at which the coating formally hardens (post-baking), and is not particularly limited as long as the heat resistance of the substrate is taken into consideration. A heating temperature of 80 to 250°C is preferably applied for 20 to 120 minutes.

[0149] In this way, a light-shielding film composed of a photocurable photosensitive resin composition can be formed. In addition, the method of forming such a light-shielding film is not limited to the aforementioned method. In addition to forming fine patterns through exposure, development and other operations as described above, a method of forming a desired pattern by screen printing can also be appropriately used to obtain a light-shielding film.

[0150] The light-shielding film of this invention, thus formed, preferably has an OD value of 3.5 / μm or more, more preferably 3.7 / μm or more per 1μm of film thickness. Regarding reflectivity, as shown in the embodiments described below, it is preferable to measure in both SCI and SCE modes on the glass substrate side and the film side. For the glass substrate side, it is preferably 5.2% or less in SCI mode and 0.45% or less in SCE mode. More preferably, it is 4.9% or less in SCI mode and 0.4% or less in SCE mode. On the other hand, for the film side, it is preferably less than 7.1% in SCI mode and 0.45% or less in SCE mode. More preferably, it is 6.1% or less in SCI mode and 0.45% or less in SCE mode. In terms of even better reflectance, it is less than 4.7% in SCI mode and less than 0.40% in SCE mode.

[0151] 3. Display device

[0152] The display device of the present invention includes the aforementioned light-shielding film of the present invention. There are no particular limitations on the types of such display devices; examples include liquid crystal display devices, organic electric field light-emitting devices (OLEDs), touch panels, etc. Furthermore, as long as such a display device of the present invention includes the aforementioned light-shielding film, other configurations are not particularly limited. Moreover, such a display device of the present invention is preferably one in which the light-shielding film of the present invention is provided on the back side of the transparent substrate on the display surface side of the display device (having a device for viewing the transparent substrate with the light-shielding film through the transparent substrate). Then, according to the display device of the present invention, the light-shielding film sufficiently reduces reflection on both the glass substrate surface side and the film surface side, thereby further improving viewing quality, etc.

[0153] [Example]

[0154] The embodiments of the present invention are described in detail below with reference to examples and comparative examples, but the present invention is not limited to these. Unless otherwise specified, "parts" refers to parts by mass.

[0155] First, an example of synthesizing an alkali-soluble resin of component (A) of the present invention is shown (resin synthesis example). The resin in the resin synthesis example was evaluated according to the following.

[0156] [Solids concentration]

[0157] The weight of 1g of the resin solution obtained in the resin synthesis example after being impregnated in a glass filter [weight: W0(g)] [W1(g)] and the weight of the solution after being heated at 160°C for 2 hours [W2(g)] are obtained by the following formula.

[0158] Solid fraction concentration (wt%) = 100 × (W2 - W0) / (W1 - W0)

[0159] [Acid Value]

[0160] Dissolve the resin solution in two Alkane was determined by titration with a 1 / 10 N-KOH aqueous solution using a potentiometric titration apparatus “COM-1600” (manufactured by Hiranuma Sangyo Co., Ltd.).

[0161] [Molecular weight]

[0162] The weight-average molecular weight (Mw) was determined by gel permeation chromatography (GPC) using a "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuper H-2000 (2 columns) + TSKgelSuper H-3000 (1 column) + TSKgelSuper H-4000 (1 column) + TSKgelSuper H-5000 (1 column) (manufactured by Tosoh Corporation), temperature: 40℃, speed: 0.6 ml / min). The Mw was calculated by using the standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit) as a conversion value.

[0163] The abbreviations used in the resin synthesis examples are as follows.

[0164] AA: Acrylic acid

[0165] BPFE: Bisphenol fluorene-type epoxide [the reaction product of 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyl ethylene oxide. In compounds of general formula (I), A is fluorene-9,9-diyl and R1 to R4 are hydrogen compounds].

[0166] BPDA: 3,3',4,4'-Biphenyltetracarboxylic acid dianhydride

[0167] THPA: 1,2,3,6-Tetrahydrophthalic anhydride

[0168] PGMEA: Propylene Glycol Monomethyl Ether Acetate

[0169] TEAB: Tetraethylammonium bromide

[0170] [Example of resin synthesis]

[0171] In a four-necked flask (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 placed and stirred at 100-105 °C for 20 hours to allow the reaction to proceed. Then, 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 the mixture was stirred at 120-125 °C for 6 hours to obtain a resin solution containing a polymerizable unsaturated group that is alkali-soluble. The resulting resin solution had a solids concentration of 56.1% by mass, an acid value (converted from solids) of 103 mg KOH / g, and a Mw of 3600 as determined by GPC analysis.

[0172] In addition, examples 1 to 11 of the synthesis of silica particles of component (E) of the present invention and comparative examples 1 to 3 are shown. Furthermore, the evaluation of the average particle size of components (D) and (E) is carried out as follows.

[0173] [Average Particle Size]

[0174] The average particle size of (D) the opacifier and (E) the silica particles were determined separately as follows: First, propylene glycol monomethyl ether acetate (PGMEA) was used as a solvent to disperse the particles of the test object in it at a particle concentration of 0.1 to 0.5% by mass, thus preparing a dispersion as the test sample. Then, the particle size distribution of the particles in the obtained dispersion (test sample) was determined using a particle size analyzer (Otsuka Electronics Co., Ltd. "Particle Size Analyzer FPAR-1000") by dynamic light scattering, and the average particle size was determined by analyzing the obtained particle size distribution using the cumulative method. The value thus determined was used as the average particle size of the particles of the test object (opacifier and silica particles).

[0175] [Synthesis example 1]

[0176] A mixture of 400 parts tert-butanol, 200 parts SNOWTEX ST-YL (40% aqueous solution, solids content) manufactured by Nissan Chemical, and 1 part phenyltrimethoxysilane (Shin-Etsu Chemical Industry, KBM-103) was heated under atmospheric conditions and refluxed for 5 minutes, then cooled to room temperature. Propylene glycol monomethyl ether acetate was then added under reduced pressure, and the mixture was azeotropically reacted to remove water and tert-butanol. Further addition of propylene glycol monomethyl ether acetate prepared a silica-containing dispersion with a 30 wt% PGMEA solution. The average particle size of the silica particles was 62 nm.

[0177] [Synthesis example 2]

[0178] The 1 part of phenyltrimethoxysilane in Synthesis Example 1 was changed to 2.7 parts, but the dispersion containing silica particles was prepared using the same procedure as in Synthesis Example 1. The average particle size of the silica particles was 64 nm.

[0179] [Synthesis example 3]

[0180] In Synthesis Example 1, 1 part of phenyltrimethoxysilane was replaced with 0.8 parts of diphenyldimethoxysilane (Shin-Etsu Chemical Industry Co., Ltd., KBM-202S). Otherwise, a dispersion containing silica particles was prepared using the same procedure as in Synthesis Example 1. The average particle size of the silica particles was 62 nm.

[0181] [Synthesis Example 4]

[0182] In Synthesis Example 1, 1 part of phenyltrimethoxysilane was replaced with 20 parts of phenyltriethoxysilane (Shin-Etsu Chemical Industry Co., Ltd., KBE-103). Otherwise, a dispersion containing silica particles was prepared using the same procedure as in Synthesis Example 1. The average particle size of the silica particles was 63 nm.

[0183] [Synthesis example 5]

[0184] In Synthesis Example 1, 1 part of phenyltrimethoxysilane was replaced with 10 parts of phenyltriethoxysilane and 0.5 parts of vinyltrimethoxysilane (Shin-Etsu Chemical Industry Co., Ltd., KBM-1003). Otherwise, a dispersion containing silica particles was prepared using the same procedure as in Synthesis Example 1. The average particle size of the silica particles was 67 nm.

[0185] [Synthesis example 6]

[0186] In Synthesis Example 1, 1 part of phenyltrimethoxysilane was replaced with 2 parts of p-styryltrimethoxysilane (Shin-Etsu Chemical Industry Co., Ltd., KBM-1403). Otherwise, a dispersion containing silica particles was prepared using the same procedure as in Synthesis Example 1. The average particle size of the silica particles was 68 nm.

[0187] [Synthesis Example 7]

[0188] In Synthesis Example 1, 200 parts of SNOWTEX ST-YL were replaced with 200 parts of a silica particle dispersion prepared by preparing a 40% solids aqueous solution of silica particles (43-00-701) manufactured by Corefront Corporation. The 1 part of phenyltrimethoxysilane was also replaced with 1.5 parts. Otherwise, the silica particle dispersion was prepared using the same procedure as in Synthesis Example 1. The average particle size of the silica particles was 70 nm.

[0189] [Synthesis example 8]

[0190] The 1.5 parts of phenyltrimethoxysilane in Synthesis Example 7 were changed to 3 parts, but the same procedure as in Synthesis Example 7 was followed to prepare a dispersion containing silica particles. The average particle size of the silica particles was 70 nm.

[0191] [Synthesis Example 9]

[0192] In Synthesis Example 1, 200 parts of SNOWTEX ST-YL were replaced with 200 parts of SNOWTEX ST-ZL (40% solids) manufactured by Nissan Chemical Co., Ltd., and 1 part of phenyltrimethoxysilane was replaced with 0.8 parts of diphenyldimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-202S). Otherwise, a dispersion containing silica particles was prepared using the same procedure as in Synthesis Example 1. The average particle size of the silica particles was 83 nm.

[0193] [Synthesis Example 10]

[0194] In Synthesis Example 1, 200 parts of SNOWTEX ST-YL were replaced with SNOWTEX MP-1040 (40% solids) manufactured by Nissan Chemical, and 1 part of phenyltrimethoxysilane was replaced with 1.8 parts of p-styryltrimethoxysilane. Otherwise, a dispersion containing silica particles was prepared using the same procedure as in Synthesis Example 1. The average particle size of the silica particles was 105 nm.

[0195] [Synthesis Example 11]

[0196] The 1 part of phenyltrimethoxysilane in Synthesis Example 1 was changed to 6 parts, but the dispersion containing silica particles was prepared using the same procedure as in Synthesis Example 1. The average particle size of the silica particles was 65 nm.

[0197] [Comparative Synthesis Example 1]

[0198] Under atmospheric conditions, 400 parts of tert-butanol and 200 parts of SNOWTEX ST-YL (40% aqueous solution of solids) from Nissan Chemical were heated and refluxed for 5 minutes, then cooled to room temperature. Propylene glycol monomethyl ether acetate was then added under reduced pressure, and the mixture was azeotropically reacted to remove water and tert-butanol. Further addition of propylene glycol monomethyl ether acetate prepared a silica particle dispersion containing a 30 wt% PGMEA solution.

[0199] [Comparative Synthesis Example 2]

[0200] In Synthesis Example 2, 200 parts of SNOWTEX ST-YL were replaced with Nikko Chemical MP-2040, and 1 part of phenyltrimethoxysilane was replaced with 2 parts. Otherwise, a dispersion containing silica particles was prepared using the same procedure as in Synthesis Example 2. The average particle size of the silica particles was 200 nm.

[0201] [Comparative Synthesis Example 3]

[0202] In Synthesis Example 2, one part of phenyltrimethoxysilane was replaced with 3-methacryloyloxypropyltrimethoxysilane (Shin-Etsu Chemical Industry Co., Ltd., KBM-503). Otherwise, a dispersion containing silica particles was prepared using the same procedure as in Synthesis Example 2. The average particle size of the silica particles was 63 nm.

[0203] 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.

[0204] (A) Component (alkali-soluble resin): The alkali-soluble resin solution containing unsaturated groups obtained in the resin synthesis example.

[0205] (B) Ingredients (photopolymerizable compound): A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name "DPHA" manufactured by Nippon Kayaku Co., Ltd.).

[0206] (C) Ingredients (photopolymerization initiator): ADEKAARKLS NCI-831, manufactured by ADEKA Corporation. "ADEKAARKLS" is a registered trademark of the company.

[0207] (D) Ingredients (Opacifier):

[0208] <D-1、D-2>

[0209] Carbon black-A or B is used as the light-blocking component, and D-1 (CB dispersion (I)) or D-2 (CB dispersion (II)) is used to introduce it.

[0210] • D-1 (CB dispersion (I)): A dispersion of PGMEA with a carbon black-A (CB-A) concentration of 25% by mass and a polymeric dispersant concentration of 3% by mass (the average particle size of the CB-A dispersion obtained by the cumulative method is 110 nm).

[0211] • D-2 (CB dispersion (II)): A dispersion of carbon black-B (CB-B) with a concentration of 25% by mass and a polymeric dispersant of 3% by mass, consisting of PGMEA (the average particle size of the CB-B dispersion obtained by the cumulative method is 130 nm).

[0212] <d-3>

[0213] Using lactam black (BASF's Irgaphor Black S 0100CF) as a light-blocking component, D-3 (lactam black dispersion (III)) was used to introduce it.

[0214] • D-3 (lactam black dispersion (III)): A PGMEA dispersion with 20% by mass of lactam black and 3% by mass of polymeric dispersant (average particle size of 220 nm obtained by cumulative method in the dispersion).

[0215] (E) Components (silica particles): Use E-1 to E-17 below.

[0216] E-1: The dispersion containing silica particles prepared in Synthesis Example 1

[0217] E-2: The dispersion containing silica particles prepared in Synthesis Example 2

[0218] •E-3: The dispersion containing silica particles prepared in Synthesis Example 3

[0219] • E-4: The dispersion containing silica particles prepared in Synthesis Example 4

[0220] • E-5: The dispersion containing silica particles prepared in Synthesis Example 5

[0221] • E-6: The dispersion containing silica particles prepared in Synthesis Example 6

[0222] • E-7: The dispersion containing silica particles prepared in Synthesis Example 7

[0223] • E-8: The dispersion containing silica particles prepared in Synthesis Example 8

[0224] • E-9: The dispersion containing silica particles prepared in Synthesis Example 9

[0225] • E-10: The dispersion containing silica particles prepared in Synthesis Example 10

[0226] • E-11: Admatechs ADMANANO YA050C series (30% by mass of PGMEA dispersion of surface-treated silica particles with a vinyl base, average particle size 50 nm)

[0227] E-12: MSD-71 manufactured by Sakai Chemical Co., Ltd. (30% by mass of PGMEA dispersion of silica particles surface-treated with phenyl groups, average particle size 101 nm)

[0228] E-13: Silica (30% by mass of PGMEA dispersion, average particle size 130 nm) manufactured by CIK Nanotec.

[0229] • E-14: The dispersion containing silica particles prepared in Synthesis Example 11

[0230] • E-15: Comparative Synthesis Example 1: Dispersion containing silica particles

[0231] • E-16: Comparative Synthesis Example 2: Dispersion containing silica particles

[0232] • E-17: Comparative Synthesis Example 3: Dispersion containing silica particles

[0233] (F) Ingredients (F-1: Silane Coupling Agent): Uretopropyltriethoxysilane (50% solids in methanol solution dilution) (Trade Name: KBE-585A, manufactured by Shin-Etsu Chemical Industry Co., Ltd.)

[0234] Compound (G): Use W-1 to W-6 and Z-1 to Z-2 as described below.

[0235] • W-1: A compound with structure (X) of a = 75 and structure (Y-1) of (X) / (Y-1) = 38.

[0236] W-2: A compound with structure (X) of a = 90 and structure (Y-1) of (X) / (Y-1) = 30.

[0237] W-3: A compound with structure (X) of a = 115 and structure (Y-1) of (X) / (Y-1) = 23.

[0238] W-4: A compound with structure (X) of a = 20 and structure (Y-1) of (X) / (Y-1) = 3.3.

[0239] W-5: A compound with structure (X) of a = 25 and structure (Y-2) of (X) / (Y-2) = 0.3.

[0240] • W-6: A compound that does not have structure (X) but has the following trimethylsiloxysilane structure (Z) and Y-2 structure.

[0241]

[0242] • Z-1: Compounds with structure (X) a = 88 that do not possess the Y-1 and Y-2 structures.

[0243] • Z-2: A compound that does not have structures (X), (Y-1), and (Y-2), but instead has the aforementioned trimethylsiloxysilane (Z) and trifluoromethyl structures.

[0244] (H) Component (Solvent):

[0245] ·ANON: Cyclohexanone

[0246] ·PGMEA: Propylene glycol monomethyl ether acetate

[0247] <Examples 1 to 59 and Comparative Examples 1 to 6>

[0248] [Preparation of Photosensitive Resin Composition]

[0249] The photosensitive resin compositions of Examples 1 to 59 and Comparative Examples 1 to 6 were prepared by blending the aforementioned blending components according to the proportions shown in Tables 1 to 8. Furthermore, the values ​​in the tables represent parts by mass, and values ​​other than component (H) represent solids. The total solids of the photosensitive resin compositions were 14% by mass. Additionally, component (D) represents the total parts by mass of carbon black-A or carbon black-B and the polymeric dispersant.

[0250] [Table 1]

[0251]

[0252] [Table 2]

[0253]

[0254] [Table 3]

[0255]

[0256] [Table 4]

[0257]

[0258] [Table 5]

[0259]

[0260] [Table 6]

[0261]

[0262] [Table 7]

[0263]

[0264] [Table 8]

[0265]

[0266] [Formation and evaluation of light-blocking film]

[0267] <Formation of the light-shielding film>

[0268] The photosensitive resin compositions prepared in the various embodiments were coated onto a glass substrate with dimensions of 125 mm in length and 125 mm in width using a spin coater, and the resulting film was baked to a thickness of 1.2 μm. The coating was then subjected to a pre-baking treatment at 90°C for 1 minute, followed by exposure to an I-line illuminance of 30 mW / cm². 2 Ultra-high pressure mercury lamps irradiate 100 mJ / m 2 The photocuring reaction was carried out under ultraviolet light conditions. Then, for the photocured coating (the exposed coating), a 0.05% by mass potassium hydroxide aqueous solution was used as the developer, and the coating was subjected to a photocuring reaction at 25°C at a rate of 1 kgf / cm². 2 After pressure rinsing and developing for 75 seconds, a 5 kgf / cm² test was performed. 2 Pressurized spray washing followed by hot air drying at 230°C for 30 minutes (post-baking) produces a glass substrate with a light-shielding film (average film thickness: 1.2μm) laminated on it.

[0269] XPS Analysis of Membrane Surface

[0270] The surface side (the side opposite to the glass substrate) of the obtained light-shielding film was measured using XPS (JPS-9010 model, NEC), and the spectrum was analyzed using the "SpecSurf Analysis" software (NEC). First, the Si2p3 / 2 spectrum was set to a range of 108.0 (±0.3) to 98.0 (±0.3) eV, and background was removed using the Shirley method for spectral correction. The measurement conditions used a MgKa line with an applied voltage of 10 kV and an emission current of 10 mA. Furthermore, to reduce the charge-up effect of the sample, electron beam irradiation was performed using a neutralization gun at an accelerating voltage of 2 V and an emission current of 4.0 mA, with the C1s peak energy set to 284.8 eV for correction. Regarding the measurement area, the X-ray irradiation range was 3 mm × 6 mm, the detection range on the film surface was a circle with a diameter of 3 mm, and the detection depth was 2 to 4 nm.

[0271] <Peak area ratio of membrane surface A SiO2 / A SiO Calculation >

[0272] In the peak fitting of Si2p3 / 2 in XPS, referring to the database on SpecSurf Analysis (SiO2: 103.9 eV, SiO: 101.8 eV), and considering the deviation caused by the charging effect, the peak area (A) from 103.9 to 104.2 eV was calculated. SiO2 The peak area (A) is between 101.8 and 102.3 eV. SiO The ratio of A to A SiO2 / A SiO Peak separation is achieved using a nonlinear least squares method with a trial function (Gaussian-Lorentz mixture function: mixture ratio - Gaussian 0.3, Lorentz 0.7). The area of ​​each peak is calculated by integrating the component waveforms.

[0273] <Calculation of the atomic concentration ratios of Si, C, O, and F on the film surface>

[0274] The ratio of the contents (atomic concentrations) of Si, C, O, and F was calculated using the relative sensitivity factor method of XPS. The analytical conditions are as follows. The atomic concentration (atom%) was calculated by correcting the peak area of ​​the spectrum of each element using the relative sensitivity factor (RSF), and the F atomic concentration was calculated relative to the total atomic concentration of Si, C, O, and F. Based on this, the ratio of their contents (atomic concentrations) was calculated.

[0275] (Analysis conditions)

[0276] Narrow measurements were performed on the peak values ​​of Si2p, C1s, N1s, O1s, and F1s. Si2p was measured in the energy range of 115 to 95 eV, C1s in 299 to 274 eV, N1s in 408 to 394 eV, O1s in 543 to 528 eV, and F1s in 696 to 683 eV. The drain time was 100 ms, and the pass energy was set to 10 eV. Si was measured with 25 scans, while C1s, N1s, O1s, and F1s were measured with 4 scans each. To correct for peak shifts caused by charging, the CH peak value in C1s was corrected to 284.8 eV.

[0277] <Measuring the Reflectivity of the Film Surface>

[0278] Using glass substrates formed by stacking light-shielding films (pixel patterns) obtained in various embodiments, the reflectance [%] of SCI mode and SCE mode was measured from the film surface side where the light-shielding film pattern was formed using a spectrophotometer (SD7000 manufactured by Nippon Denshoku Kogyo Co., Ltd.) under conditions of C light source and 2° field of view. In SCI mode, less than 7.1% was considered acceptable, and in SCE mode, less than 0.45% was considered acceptable. The reflectance of these modes is recorded as "SCI reflectance" or "SCE reflectance", or simply as "SCI" ​​or "SCE".

[0279] <Measurement of Side Reflectivity of Glass Surface>

[0280] Using glass substrates formed by stacking the light-shielding films (pixel patterns) obtained in various embodiments, the reflectance [%] in SCI mode and SCE mode was measured on the side of the glass substrate without the light-shielding film pattern, using a spectrophotometer (SD7000 manufactured by Nippon Denshoku Kogyo Co., Ltd.) under conditions of C light source and 2° field of view. In SCI mode, 5.2% or less was considered acceptable, and in SCE mode, 0.45% or less was considered acceptable.

[0281] (Inspection)

[0282] The light-shielding films obtained in Examples 1 to 59 have a surface SCI reflectance of less than 7.1% and a surface SCE reflectance of less than 0.45%. Furthermore, the surface SCI reflectance is less than 5.2% and the surface SCE reflectance is less than 0.45%.

[0283] • In Examples 1 to 8, 10 to 36, 38 to 47, and 49 to 57, the content of compound G is 0.5% or less relative to the total mass of the photosensitive resin composition containing the solvent, and the SCI reflectance on the film side is 6.1% or less, which is a good composition for a light-shielding film.

[0284] In real-time examples 1, 3, 5 to 8, 11 to 13, 15, 18 to 19, 21, 25, 27, 29 to 32, 35, 43 to 44, and 49 to 52, the particle size of the silica particles is 50 to 80 nm, which is a preferred average particle size. Therefore, the SCI reflectance on the film surface is less than 5.0%, which is a good composition for a light-shielding film.

[0285] In particular, in Examples 1, 5, 18, 19, 31, 50, and 51, the SCI reflectance on the film surface is less than 4.5% and has high light-blocking properties, which is a good composition for the curing film.

[0286] • The high proportion of F detected in Comparative Example 6 is not environmentally friendly, nor does it meet the requirements of regulations such as those for organofluorine compounds (PFAS).

[0287] • Comparative Examples 1 and 2 are not surface-modified silica, and the silica particles are too large. As a result, the silica particles aggregate together, leading to high film surface reflectivity and high SCE reflectivity.

[0288] • Comparative Example 3 consists of silica particles that have undergone surface treatment with a group containing 3-methacryloyloxypropyl. Therefore, they lack compatibility with light-shielding materials and are prone to agglomeration, resulting in high SCI reflectivity.

[0289] • In Comparative Example 4, A SiO2 / A SiO The reflectivity of SCI is high, while that of SCE is low due to silica segregation to the film surface. SCI has low reflectivity but lacks coatability.

[0290] Comparative Example 5 does not have a Y-1 or Y-2 structure, so it lacks the effect of causing silica to segregate on the film surface, resulting in high SCI reflectivity on the film surface side.

Claims

1. A photosensitive resin composition for forming a light-shielding film, comprising the following components (A) to (F): (A) Alkali-soluble resin; (B) Photopolymerizable compounds having at least one ethylene unsaturated bond; (C) Photopolymerization initiator; (D) Sunscreen; (E) Silica particles; and (F) Silane coupling agent; And simultaneously satisfy both (i) and (ii): (i) A film composed of a cured form of the photosensitive resin composition is formed on a glass substrate with an average film thickness ranging from 0.5 to 4.0 μm. When the surface of the film is measured by X-ray photoelectron spectroscopy (XPS), the peak area A of SiO2 at 103.9 to 104.2 eV is determined by peak fitting analysis of the Si2p3 / 2 peak. SiO2 The peak area A of SiO at 101.8 to 102.3 eV SiO The ratio (A) SiO2 / A SiO The value ranges from 0.10 to 10.

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

2. The photosensitive resin composition according to claim 1, wherein the aforementioned component (A) is an alkali-soluble resin containing a polymerizable unsaturated group represented by the following general formula (II); In formula (II), R1, R2, R3, and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a phenyl group; A represents -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, fluorene-9,9-dimethyl or 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 the number from 1 to 2; n represents an integer from 1 to 20; R5 represents a hydrogen atom or a methyl group.

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

4. The photosensitive resin composition according to claim 1, further comprising compound (G), which is a dimethylsiloxane unit represented by structure (X) and an ethylene glycol repeating unit represented by structure (Y-1) and / or a propylene glycol repeating unit represented by structure (Y-2), wherein the ratio of (X) / [(Y-1)+(Y-2)] in a molecule is from 0.1 to 100; in, a is 15 or higher; 5. The photosensitive resin composition according to claim 1, wherein the aforementioned component (E) is silica particles with an average particle size of 50 to 180 nm.

6. The photosensitive resin composition according to claim 1, wherein the aforementioned component (E) is silica particles that have been surface-treated with vinyl and / or phenyl groups.

7. The photosensitive resin composition according to claim 1, wherein the ratio of the aforementioned peak areas (A) SiO2 / A SiO The value ranges from 0.25 to 10.

0.

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

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

10. A display device comprising a light-shielding film according to claim 9.

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