polymer

Abstract

To provide a polymer that can form a photosensitive resin composition capable of imparting excellent resolution and reliability to a light-blocking pattern with high optical density.SOLUTION: A polymer is used in a photosensitive resin composition. The polymer comprises (a) a (meth)acrylate constitutional unit with an alicyclic hydrocarbon group, (b) a constitutional unit with an aromatic group, (c) a constitutional unit derived from (meth)acrylic acid, and (d) a (meth)acrylate constitutional unit with an ethylenically unsaturated group, with a double bond equivalent of 250-400 g / mol.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates to polymers. [Background technology]

[0002] Image display devices such as televisions, digital signage, smartwatches, smartphones, AR devices, and VR devices are equipped with multiple color-emitting sections arranged in a matrix and light-shielding patterns that separate these multiple color-emitting sections. Such light-shielding patterns are intended to suppress crosstalk (sometimes called "color mixing") between adjacent color-emitting sections and are generally formed using a photosensitive resin composition. Specifically, a light-shielding pattern is obtained by applying a photosensitive resin composition to a substrate to form a photosensitive resin layer, partially exposing the photosensitive resin layer to form a partially cured layer, and developing the cured sections as a pattern using a developer. For example, Patent Document 1 below proposes that a photosensitive resin composition containing a colorant, a dispersant, an alkali-soluble resin, and a photopolymerization initiator is used to impart excellent light-shielding properties to a light-shielding pattern. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] International Publication No. 2015 / 046178 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] Incidentally, in recent years, micro-LED displays have been attracting attention as a next-generation image display device. Micro-LED displays use micro-LEDs as the color-emitting element. Because micro-LEDs have high quantum efficiency, they enable long lifespan and low power consumption, and because they are self-emissive elements, they enable wide viewing angles and high brightness, making them promising for application in micro-LED displays.

[0005] However, the photosensitive resin composition described in Patent Document 1 had the following problems. In other words, when the photosensitive resin composition described in Patent Document 1 is used to form a light-shielding pattern on a substrate, and the color-developing part is a micro-LED, there is room for improvement in terms of resolution in the light-shielding pattern when the light-shielding pattern has a high optical density. Furthermore, when the photosensitive resin composition described in Patent Document 1 is used to form a light-shielding pattern with a high optical density on a substrate, there is room for improvement in terms of suppressing the reduction in the thickness of the light-shielding pattern when the light-shielding pattern is left under high temperature and high humidity, i.e., in terms of reliability.

[0006] This disclosure has been made in view of the above-mentioned problems, and aims to provide a polymer that can form a photosensitive resin composition that can impart excellent resolution and reliability in light-shielding patterns having high optical density. [Means for solving the problem]

[0007] To address the above issues, one aspect of this disclosure provides the alkali-soluble binders described in [1] to [4] below. [1] A polymer used in a photosensitive resin composition, comprising a constituent unit (a) represented by the following formula (1), a constituent unit (b) represented by the following formula (2), a constituent unit (c) represented by the following formula (3), and a constituent unit (d) represented by the following formula (4), wherein the double bond equivalent is 250 to 400 g / mol. [ka] (In formula (1) above, R 1 (where represents a hydrogen atom or a methyl group, and X represents an alicyclic hydrocarbon group which may have substituents.) [ka] (In the above formula (2), R 2represents a hydrogen atom or a methyl group, and Y represents an aromatic group which may have a substituent.)

Chemical formula

Chemical formula

[0008] According to the polymer of the present disclosure, a photosensitive resin composition capable of imparting excellent resolution and reliability in a light-shielding pattern having a high optical density can be formed.

[0009] It is presumed that the reason for obtaining the above effects by the polymer of the present disclosure is as follows. That is, the polymer of the present disclosure is blended with a photopolymerizable monomer having an ethylenically unsaturated group, a photoinitiator, and a colorant to form a photosensitive resin composition. This photosensitive resin composition is applied onto a substrate to form a photosensitive resin layer. When the photosensitive resin layer is partially exposed from the side opposite to the substrate, light reaches sufficiently to the portion of the exposed part of the photosensitive resin layer that is away from the substrate. Therefore, in the presence of a photoinitiator, light causes the polymer, the photopolymerizable monomer, and the photopolymerizable monomers to react with each other and cure sufficiently. On the other hand, if the concentration of the colorant in the photosensitive resin layer is high and the thickness of the photosensitive resin layer is large, light hardly reaches the portion of the exposed part of the photosensitive resin layer that is close to the substrate due to the presence of the colorant. Therefore, even in the presence of a photoinitiator, the reaction between the polymer and the photopolymerizable monomer and the reaction between the photopolymerizable monomers hardly occur, and insufficient curing tends to occur during exposure. However, when the partially cured layer obtained after exposure of the photosensitive resin layer is heated, since the double bond equivalent of the polymer is 250 to 400 g / mol, even after exposure, the reaction between the polymer and the photopolymerizable monomer and the reaction between the photopolymerizable monomers proceed moderately and it becomes easy to cure. As a result, the photosensitive resin layer is uniformly cured along its thickness direction. Therefore, when the partially cured layer obtained after exposure of the photosensitive resin layer is developed with an alkaline developer, the uncured portion is dissolved by the polymer being dissolved in the alkaline developer, and for the cured portion due to exposure, dissolution or swelling by the developer due to insufficient curing is suppressed. As a result, excellent resolution is obtained in the resulting light-shielding pattern. Further, since the double bond equivalent of the polymer is 250 to 400 g / mol and the polymer is moderately crosslinked by exposure by having the above structural unit (a), structural unit (b), structural unit (c), and structural unit (d), even when the light-shielding pattern is placed in a high-temperature and high-humidity environment, a decrease in the film thickness of the light-shielding pattern is suppressed. From the above, it is presumed that the above effects can be obtained by the polymer of the present disclosure.

Advantages of the Invention

[0010] The present disclosure provides a polymer capable of forming a photosensitive resin composition that can impart excellent resolution and reliability in light-shielding patterns having high optical density. [Brief explanation of the drawing]

[0011] [Figure 1] This is a partial cross-sectional view showing the photosensitive resin layer formation step of a method for manufacturing a light-shielding patterned substrate produced using a photosensitive resin composition containing the polymer according to this disclosure. [Figure 2] This is a partial cross-sectional view showing the exposure step of a method for manufacturing a light-shielding patterned substrate produced using a photosensitive resin composition containing the polymer according to this disclosure. [Figure 3] This is a partial cross-sectional view showing the second laminate obtained in the exposure process shown in Figure 2. [Figure 4] This is a partial cross-sectional view showing a heating step in a method for manufacturing a light-shielding patterned substrate produced using a photosensitive resin composition containing the polymer according to this disclosure. [Figure 5] This is a partial cross-sectional view showing the developing step of a method for manufacturing a light-shielding patterned substrate produced using a photosensitive resin composition containing the polymer according to this disclosure. [Figure 6] Figure 5 is a plan view showing a substrate with a light-shielding pattern. [Figure 7] This is a partial cross-sectional view showing the microLED mounting step of a method for manufacturing a microLED display using a photosensitive resin composition containing the polymer according to this disclosure. [Modes for carrying out the invention]

[0012] Hereinafter, embodiments for carrying out this disclosure will be described in detail, with reference to drawings as appropriate. However, this disclosure is not limited to the embodiments described below. In this specification, "(meth)acrylic acid" means acrylic acid or methacrylic acid, and "(meth)acrylate" means acrylate or the corresponding methacrylate.

[0013] <polymer> The polymer of the present disclosure is a polymer used in a photosensitive resin composition, and includes a structural unit (a) represented by the following formula (1), a structural unit (b) represented by the following formula (2), a structural unit (c) represented by the following formula (3), and a structural unit (d) represented by the following formula (4). The double bond equivalent of the polymer of the present disclosure is 250 to 400 g / mol. .

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0014] (A) Polymer The polymer is an alkali-soluble binder polymer and includes a structural unit (a) represented by the above formula (1), a structural unit (b) represented by the above formula (2), a structural unit (c) represented by the above formula (3), and a structural unit (d) represented by the above formula (4).

[0015] In formula (1) representing the constituent unit (a), X represents an alicyclic hydrocarbon group which may have substituents. The number of carbon atoms in the alicyclic hydrocarbon group may be between 7 and 20. Examples of substituents include halogen atoms such as fluoro, chloro, and bromo, and hydroxyl groups. Examples of alicyclic hydrocarbon groups include adamantyl, tricyclodecyl, isobornyl, and cyclohexyl groups. The constituent unit (a) can be introduced by using an alicyclic hydrocarbon group-containing polymerizable monomer as the polymerizable monomer used when producing a polymer by copolymerization. A polymerizable monomer containing an alicyclic hydrocarbon group can be represented, for example, by the following general formula (1A). CH2=C(R 1 )-COOX…(1A)

[0016] Examples of polymerizable monomers containing alicyclic hydrocarbon groups represented by the above general formula (1A) include adamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, isobornyl (meth)acrylate, and cyclohexyl (meth)acrylate. These polymerizable monomers containing alicyclic hydrocarbon groups may be used individually or in combination of two or more.

[0017] In formula (2) representing the constituent unit (b), Y represents an aromatic group which may have substituents. An aromatic group is defined as having an aromatic ring, and is represented, for example, by -PQ. Here, P is represented by a single bond or -COO-, and Q represents an aromatic hydrocarbon group which may have substituents. Examples of aromatic hydrocarbon groups include phenyl groups, aryl groups such as naphthyl groups, aralkyl groups such as benzyl groups, and styryl groups. The constituent unit (b) can be introduced by using an aromatic hydrocarbon group-containing polymerizable monomer as the polymerizable monomer used when producing a polymer by copolymerization. Polymerizable monomers containing aromatic hydrocarbon groups are represented by the following general formula (2A). CH2=C(R2 )-Y …(2A)

[0018] Examples of polymerizable monomers containing aromatic hydrocarbon groups represented by the above general formula (2A) include aromatic hydrocarbon group-containing (meth)acrylates such as benzyl (meth)acrylate, phenyl (meth)acrylate, and naphthyl (meth)acrylate, and aromatic vinyl compounds such as styrene. These polymerizable monomers containing aromatic hydrocarbon groups may be used individually or in combination of two or more.

[0019] The constituent unit (c) can be introduced by using (meth)acrylic acid as a polymerizable monomer when producing polymers by copolymerization. (Meth)acrylic acid is highly reactive and readily available.

[0020] The constituent unit (d) can be introduced, for example, by using a polymerizable monomer represented by the following formula (4A) as a polymerizable monomer used when manufacturing a polymer. [ka] The constituent unit (d) can also be introduced by adding a glycidyl (meth)acrylate to a portion of the carboxyl group of the constituent unit (c).

[0021] The above polymer has ethylenically unsaturated groups. Therefore, during exposure, the polymer reacts with the photopolymerizable monomer in the portion of the photosensitive resin layer that is far from the substrate, resulting in more complete curing. Furthermore, even in the portion of the photosensitive resin layer that is close to the substrate, the polymer reacts with the photopolymerizable monomer during heating of the partially cured layer obtained after exposure of the photosensitive resin layer, resulting in more complete curing.

[0022] In polymers, when the sum of the above-mentioned constituent units (a), (b), (c), and (d) is taken as the standard (100 mol%), the proportion of constituent unit (a) is not particularly limited as long as it is greater than 0 mol%, but it may be 0.1 mol% or more, 0.5 mol% or more, or 1 mol% or more. The proportion of constituent unit (a) may be 30 mol% or less, 29 mol% or less, or 28 mol% or less.

[0023] In polymers, when the sum of the above-mentioned constituent units (a), (b), (c), and (d) is taken as the standard (100 mol%), the proportion of constituent unit (b) is not particularly limited as long as it is greater than 0 mol%, but it may be 0.1 mol% or more, 0.5 mol% or more, or 1.0 mol% or more. The proportion of constituent unit (b) may be less than 20 mol%, 19 mol% or less, or 18 mol% or less. When the proportion of constituent unit (b) is less than 20 mol%, there is a tendency to suppress the reduction in line width even when the light-shielding pattern is left in a high-temperature, high-humidity environment.

[0024] In polymers, when the sum of the above-mentioned constituent units (a), (b), (c), and (d) is taken as the standard (100 mol%), the proportion of constituent unit (c) is not particularly limited as long as it is greater than 0 mol%, but it may be 1 mol% or more, 2 mol% or more, or 3 mol% or more. The proportion of constituent unit (c) may be 35 mol% or less, 34 mol% or less, or 33 mol% or less.

[0025] In polymers, when the sum of the above-mentioned constituent units (a), (b), (c), and (d) is taken as the standard (100 mol%), the proportion of constituent unit (d) is not particularly limited as long as it can be within the range of 250 to 400 double bond equivalents, but it may be 45 mol% or more, 47 mol% or more, or 49 mol% or more. The proportion of constituent unit (d) may be 85 mol% or less, 83 mol% or less, or 81 mol% or less.

[0026] The double bond equivalent of the polymer is 250 to 400 g / mol. When the double bond equivalent of the polymer is 250 g / mol or more, tackiness is less likely to occur in the photosensitive resin composition compared to when the double bond equivalent is less than 250 g / mol, making it easier to obtain a useful polymer. Furthermore, when the double bond equivalent of the polymer is 400 g / mol or less, the resolution is higher or the reliability is higher compared to when the double bond equivalent is greater than 400 g / mol. The double bond equivalent of the polymer may be 260 g / mol or more, 270 g / mol or more, or 280 g / mol or more. The double bond equivalent of the polymer may be 390 g / mol or less, 380 g / mol or less, or 370 g / mol or less. The double bond equivalent of a polymer is the mass of the polymer per mole of polymerizable unsaturated bonds, and is calculated based on the amount of monomer used.

[0027] The solid content acid value of the polymer is not particularly limited, but may be 25 mg KOH / g or higher, or 30 mg KOH / g or higher. When the solid content acid value of the polymer is 25 mg KOH / g or higher, the resolution of the light-shielding pattern can be improved even with a low exposure during exposure. The solid content acid value of the polymer may be 125 mg KOH / g or less, or 120 mg KOH / g or less. A solid content acid value of 125 mg KOH / g or less allows for further improvement of the resolution of the light-shielding pattern. The solids acid value refers to the number of milligrams of potassium hydroxide required to neutralize the acid present in 1 gram of polymer.

[0028] The weight-average molecular weight of the polymer may be 3,000 to 30,000, 3,500 to 25,000, or 4,000 to 20,000, from the viewpoint of balancing mechanical strength and alkali developability. For superior developer resistance after exposure, the weight-average molecular weight may be 4,000 or higher. Furthermore, from the viewpoint of development time, the weight-average molecular weight may be 20,000 or lower. However, since the above-mentioned developability is greatly influenced by the solid content acid value, hydroxyl value, and resin skeleton, the weight-average molecular weight of the polymer is not particularly limited to the above ranges. The weight-average molecular weight was measured by gel permeation chromatography (GPC) and converted using a calibration curve created with standard polystyrene.

[0029] Polymers can be used individually or in combination of two or more types.

[0030] <Photosensitive resin composition> The polymers of this disclosure may be used in photosensitive resin compositions. In addition to the (A) polymer described above (hereinafter sometimes referred to as component (A)), the photosensitive resin composition contains (B) a photopolymerizable monomer having an ethylenically unsaturated group (hereinafter sometimes referred to as component (B)), (C) a colorant (hereinafter sometimes referred to as component (C)), and (D) a photopolymerization initiator (hereinafter sometimes referred to as component (D)). The photosensitive resin composition may also contain (E) a polyfunctional thiol compound (hereinafter sometimes referred to as component (E)). The photopolymerizable monomer, colorant, photopolymerization initiator and polyfunctional thiol compound will be described below.

[0031] (B) Photopolymerizable monomers Photopolymerizable monomers have an ethylenically unsaturated group.

[0032] Examples of photopolymerizable monomers having an ethylenically unsaturated group include compounds obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid, bisphenol A-based (meth)acrylate compounds such as 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane, urethane monomers such as compounds obtained by reacting a glycidyl group-containing compound with an α,β-unsaturated carboxylic acid, and (meth)acrylate compounds having a urethane bond, as well as γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-o-phthalate, β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, and alkyl (meth)acrylates.

[0033] Compounds obtained by reacting polyhydric alcohols with α,β-unsaturated carboxylic acids include, for example, polyethylene glycol di(meth)acrylate having 2 to 14 ethylene groups, polypropylene glycol di(meth)acrylate having 2 to 14 propylene groups, polyethylene polypropylene glycol di(meth)acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxytri(meth)acrylate, and trimethylolpropane diethoxytri(meth)acrylate. Examples include hydrate, trimethylolpropane triethoxytri(meth)acrylate, trimethylolpropane tetraethoxytri(meth)acrylate, trimethylolpropane pentaethoxytri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, polypropylene glycol di(meth)acrylate with 2 to 14 propylene groups, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0034] Examples of the above-mentioned urethane monomers include addition reaction products of (meth)acrylic monomers having a hydroxyl group at the β position with diisocyanate compounds such as isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate, tris[(meth)acryloxytetraethylene glycol isocyanate]hexamethylene isocyanurate, EO-modified urethane di(meth)acrylate, and EO,PO-modified urethane di(meth)acrylate. "EO" represents ethylene oxide, and EO-modified compounds have a block structure of ethylene oxide groups. "PO" represents propylene oxide, and PO-modified compounds have a block structure of propylene oxide groups.

[0035] In photopolymerizable monomers, the number of functional groups in one molecule may be two or more, or three or more. Furthermore, two or more photopolymerizable monomers, such as one with two or more functional groups and another with three or more functional groups, may be used in combination.

[0036] In photopolymerizable monomers, if there are three or more functional groups in one molecule, all three or more functional groups may be ethylenically unsaturated groups, but the three or more functional groups may also include hydroxyl groups in addition to ethylenically unsaturated groups. In this case, the developability of the partially cured layer obtained after exposure of the photosensitive resin layer is further improved. Furthermore, swelling of the cured portion of the partially cured layer due to exposure during development can be suppressed by the developer, and the resolution of the photosensitive resin composition can be further improved.

[0037] Furthermore, the number of functional groups in one molecule may be 26 or less, or 5 or less.

[0038] The photopolymerizable monomers can be obtained by using the above-mentioned compounds individually or in combination of two or more.

[0039] The content of photopolymerizable monomers in the photosensitive resin composition may be 5 to 50 parts by mass, or 5 to 30 parts by mass, per 100 parts by mass of the total amount of polymer and photopolymerizable monomers. When the content of photopolymerizable monomers is 5 parts by mass or more, the photocurability of the photosensitive resin layer tends to be good, and when it is 50 parts by mass or less, when a photosensitive resin layer is formed on a substrate using the photosensitive resin composition, the photosensitive resin layer tends to have excellent shape retention before exposure.

[0040] (C) Coloring agent Examples of colorants include pigments and dyes. The pigment may be an organic pigment or an inorganic pigment, but it may be an organic pigment. When an organic pigment is used, it is possible to transmit ultraviolet light, so compared to when an inorganic pigment is used, light can reach a sufficiently deep position from the surface of the photosensitive resin layer during exposure, and insufficient curing of the exposed area can be further suppressed. Therefore, dissolution or swelling of the cured area due to exposure during development can be further suppressed, and the resolution of the light-shielding pattern can be further improved. Two or more colorants may be included.

[0041] Examples of organic pigments include lactam black, perylene black, and aniline black.

[0042] Examples of inorganic pigments include carbon black and titanium black.

[0043] Examples of dyes include leuco dyes.

[0044] The colorant content in the total solids is not particularly limited as long as it is greater than 0% by mass, but from the viewpoint of improving the light-shielding properties of the light-shielding pattern formed, it may be 4% by mass or more, or 6% by mass or more. However, the colorant content in the total solids may be 15% by mass or less, 12% by mass or less, or 4% by mass or less. When the colorant content in the total solids is 15% by mass or less, the depth to which light penetrates from the surface can be increased when the photosensitive resin layer formed using the photosensitive resin composition is exposed, and insufficient curing of the exposed area can be suppressed. Therefore, the dissolution or swelling of the cured area due to exposure during development with a developer is sufficiently suppressed. In particular, when the colorant content in the total solids is 4% by mass or less, the decrease in the thickness of the light-shielding pattern tends to be suppressed even after the light-shielding pattern has been left under high temperature and high humidity conditions.

[0045] (D) Photopolymerization initiator A photopolymerization initiator is a compound that initiates the reaction between a polymer and a photopolymerizable monomer, as well as the reaction between photopolymerizable monomers themselves. The photopolymerization initiator can be appropriately selected according to the wavelength of light of the exposure machine used, and known initiators such as photoradical polymerization initiators and photocationic polymerization initiators can be used. A single photopolymerization initiator or a combination of two or more can be used.

[0046] Examples of photoradical polymerization initiators include aromatic ketones such as benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, 4,4'-bis(dimethylamino)benzophenone (Michler ketone), 4,4'-bis(diethylamino)benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone; quinones such as alkylanthraquinone and phenanthrenequinone; benzoin compounds such as benzoin and alkylbenzoin; benzoin ether compounds such as benzoin alkyl ether and benzoin phenyl ether; and benzyl Benzyl derivatives such as dimethyl ketal, 2,4,5-triarylimidazole dimers such as 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4-di(p-methoxyphenyl)-5-phenylimidazole dimer, and 2,4-dimethoxyphenyl)-4,5-diphenylimidazole dimer, N-phenylglycine, N-phenylglycine derivatives, and acridine derivatives such as 9-phenylacridine, 1-[4-(phenylthio)phenyl]-1,2-octanedion Examples include oxime esters such as 2-(O-benzoyl oxime), coumarin compounds such as 7-diethylamino-4-methylcoumarin, thioxanthone compounds such as 2,4-diethylthioxanthone, and acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.

[0047] In particular, acylphosphine oxide-based photopolymerization initiators have a photobleaching function, so after decomposition by exposure, they become less absorbent of light. Therefore, during exposure, light can reach a sufficiently deep position from the surface of the photosensitive resin layer as time progresses, thus suppressing insufficient curing in the exposed areas. As a result, dissolution or swelling of the cured areas due to exposure during development can be suppressed, and the resolution of the light-shielding pattern can be further improved. Acylphosphine oxide photopolymerization initiators are those having an acylphosphine oxide group (>P(=O)-C(=O)-group), and examples include (2,6-dimethoxybenzoyl)-2,4,6-pentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (product name: IRGACURE-TPO, manufactured by BASF), ethyl-2,4,6-trimethylbenzoylphenylphosphine, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (product name: IRGACURE-819, manufactured by BASF), (2,5-dihydroxyphenyl)diphenylphosphine oxide, (p-hydroxyphenyl)diphenylphosphine oxide, bis(p-hydroxyphenyl)phenylphosphine oxide, tris(p-hydroxyphenyl)phosphine oxide, and the like.

[0048] As photocationic polymerization initiators, onium salts that release Lewis acids when irradiated with active energy rays may be used. Examples of such onium salts include aromatic sulfonium salts of group VIIa elements, aromatic onium salts of group VIa elements, aromatic onium salts of group Va elements, etc. Specifically, examples include triarylsulfonium hexafluoroantimonate, triphenylphenacylphosphonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, bis-[4-(diphenylsulfonio)phenyl]sulfide bis-dihexafluoroantimonate, bis-[4-(di4'-hydroxyethoxyphenylsulfonio)phenyl]sulfide bis-dihexafluoroantimonate, bis-[4-(diphenylsulfonio)phenyl]sulfide bis-dihexafluorophosphate, and diphenyliodonium tetrafluoroborate.

[0049] The content ratio of the photopolymerization initiator in the photosensitive resin composition may be 2.0 to 15.0 parts by mass, 3.0 to 12.0 parts by mass, or 4.0 to 10.0 parts by mass per 100 parts by mass of the total amount of polymer and photopolymerizable monomer, from the viewpoint of achieving both photosensitivity and internal photocurability.

[0050] (E) Polyfunctional thiol compounds The photosensitive resin composition may further contain a polyfunctional thiol compound. When the photosensitive resin layer obtained by exposing the photosensitive resin composition is heated, the polyfunctional thiol compound undergoes a radical chain reaction, which allows the reaction between photopolymerizable monomers and between photopolymerizable monomers and the mercapto groups of the polyfunctional thiol compound to proceed appropriately even after exposure, making it easier to cure the photosensitive resin layer. Furthermore, the polyfunctional thiol compound helps to form a sufficient crosslinked structure in the exposed area of ​​the partially cured layer, while also easing the stress applied between the light-shielding pattern and the substrate 10, thereby maintaining the adhesion of the light-shielding pattern to the substrate and improving reliability. The polyfunctional thiol compound may contain two or more mercapto groups per molecule, three or more, or four or more. When the polyfunctional thiol compound contains three or more mercapto groups per molecule, the resolution of the light-shielding pattern can be further improved even with a low exposure amount during exposure. The number of mercapto groups in a single molecule may be six or less. In this case, it becomes easier to control the residual film and pattern width of the light-shielding pattern.

[0051] Examples of polyfunctional thiol compounds include primary polyfunctional thiols and secondary polyfunctional thiols. Among these, secondary polyfunctional thiols have high storage stability and can suppress odors.

[0052] Examples of secondary polyfunctional thiols include pentaerythritol tetrakis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), and 1,3,5-tris[2-(3-mercaptobutanoyloxy)ethyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0053] Examples of primary polyfunctional thiols include trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis(3-mercaptopropionate), and dipentaerythritol hexakis(3-mercaptopropionate).

[0054] Polyfunctional thiol compounds can be used individually or in combination of two or more types.

[0055] The content ratio of the polyfunctional thiol compound relative to 100 parts by mass of the total amount of polymer and photopolymerizable monomer may be 0.05 to 10.0 parts by mass, 0.1 to 8.0 parts by mass, or 0.2 to 6.0 parts by mass. When the content ratio of the polyfunctional thiol compound is 0.05 to 10.0 parts by mass, it becomes easier to achieve both photosensitivity and internal photocurability.

[0056] The content ratio of the polyfunctional thiol compound to 100 parts by mass of the total amount of the photopolymerizable monomer and the polyfunctional thiol compound may be 1.0 part by mass or more, 3.0 parts by mass or more, or 5.0 parts by mass or more. In this case, the resolution of the light-shielding pattern can be effectively improved even with a low exposure amount during exposure. The content of the polyfunctional thiol compound may be 60.0 parts by mass or less, 50.0 parts by mass or less, or 30.0 parts by mass or less. In this case, the resolution of the light-shielding pattern can be further improved, and the widening of the pattern width can be suppressed.

[0057] (Other ingredients) The photosensitive resin composition may further contain solvents such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N,N-dimethylformamide, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and ethyl lactate, as needed. These can be used individually or in combination of two or more. The amount of solvent should be appropriately determined, for example, so that the total solid content concentration in the photosensitive resin composition is about 10 to 60% by mass.

[0058] The photosensitive resin composition may further contain additives as needed, such as plasticizers, fillers, defoamers, flame retardants, stabilizers, adhesion promoters, leveling agents, release accelerators, antioxidants, fragrances, and thermal crosslinking agents. Each of these can be used individually or in combination of two or more. The amount of each of these additives may be 0.01 to 20 parts by mass per 100 parts by mass of the total of the polymer and photopolymerizable monomer.

[0059] <Substrate with light-shielding pattern and method for manufacturing the same> Next, a method for manufacturing a light-shielding patterned substrate using the above-mentioned photosensitive resin composition will be described with reference to Figures 1 to 6. Figures 1, 2, 4, and 5 are schematic cross-sectional views showing a series of steps in the manufacturing method of a light-shielding patterned substrate, Figure 3 is a partial cross-sectional view showing the second laminate obtained in the exposure step of Figure 2, and Figure 6 is a plan view showing the light-shielding patterned substrate of Figure 5. The method for manufacturing a substrate with a light-shielding pattern comprises: a photosensitive resin layer formation step (see Figure 1) to obtain a first laminate 100 by forming a photosensitive resin layer 20 on a substrate 10 using the photosensitive resin composition of this embodiment described above; an exposure step (see Figures 2 and 3) to obtain a second laminate 110 by exposing the photosensitive resin layer 20 provided on the substrate 10 to light (partially irradiating the photosensitive resin layer 2 with light L) to form a partially cured layer 30; a heating step (see Figure 4) to heat the partially cured layer 30 of the second laminate 110; and a developing step (see Figure 5) to obtain a substrate 120 with a light-shielding pattern by alkali developing the partially cured layer 30 of the second laminate 110 and performing a post-curing step as necessary to form a light-shielding pattern 21.

[0060] (Photosensitive resin layer formation process) Examples of substrates 10 in the photosensitive resin layer formation process include glass substrates, sapphire substrates, plastic substrates such as polycarbonate and cycloolefin polymers, and circuit boards such as TFTs or CMOSs.

[0061] The height of the photosensitive resin layer 20 from the substrate 10 varies depending on the application, but from the viewpoint of achieving both coating properties and photocurability, the thickness after drying may be 1 to 200 μm or 10 to 100 μm. However, this disclosure is effective when the height of the photosensitive resin layer 20 from the substrate 10 is 5 μm or more, and is particularly effective when it is 10 μm or more. When the height of the photosensitive resin layer 20 from the substrate 10 is 5 μm or more, light does not sufficiently reach the portion of the photosensitive resin layer 20 that is on the substrate 10 side during exposure. Even in such cases, the photosensitive resin composition containing the polymer of this disclosure can be cured uniformly along the thickness direction of the photosensitive resin layer 20. However, the height of the photosensitive resin layer 20 from the substrate 10 may be 50 μm or less, or 30 μm or less, for the reason of making it easier to improve the resolution of the light-shielding pattern 21.

[0062] The photosensitive resin layer 20 can be formed by applying a solution of the above-described photosensitive resin composition (coating solution for forming the photosensitive resin layer) onto the substrate 10 and drying it. However, in this case, the amount of residual organic solvent in the photosensitive resin layer 20 may be 2% by mass or less in order to prevent the diffusion of the organic solvent in subsequent processes.

[0063] The coating can be carried out by known methods such as the roll coating method, comma coating method, gravure coating method, air knife coating method, die coating method, bar coating method, spray coating method, and spin coating method. After coating, drying to remove organic solvents, etc., can be carried out at 70 to 150°C for about 1 to 30 minutes using a hot air convection dryer or the like.

[0064] (Exposure process) One method of exposure in the exposure process is to irradiate a predetermined portion of the photosensitive resin layer 20 with light (active light) in an image-like manner through a mask M having multiple apertures (mask exposure method) (see Figure 2). As the light source for the active light, known light sources that effectively emit ultraviolet light, visible light, etc., such as carbon arc lamps, mercury vapor arc lamps, ultra-high pressure mercury lamps, high pressure mercury lamps, and xenon lamps can be used. In addition, Ar ion lasers, semiconductor lasers, etc., that effectively emit ultraviolet light, visible light, etc., can also be used. Furthermore, photographic floodlights, solar lamps, etc., that effectively emit visible light can also be used. Alternatively, a method of irradiating the active light in an image-like manner using a direct drawing method such as laser exposure may be adopted. In this case, the mask M is not required.

[0065] The exposure amount in the exposure process varies depending on the equipment used and the composition of the photosensitive resin layer 20, but in terms of excellent photocurability, 30 mJ / cm² is suitable. 2 Above 50 mJ / cm² 2 The above is sufficient. The exposure amount in the exposure process should be 500 mJ / cm² in terms of resolution. 2 The following, or 400 mJ / cm² 2 The following is acceptable:

[0066] Exposure can be performed in air, a vacuum, or other environments, and the exposure atmosphere is not particularly restricted.

[0067] After exposure, the photosensitive resin layer 20 becomes a partially cured layer 30. Specifically, the exposed portion of the photosensitive resin layer 20 becomes a cured portion acting as a light-shielding pattern 21, while the unexposed portion of the photosensitive resin layer 20 becomes an uncured portion 22 (see Figure 3).

[0068] (Heating process) The heating step is performed by heating the partially cured layer 30, in order to appropriately promote the curing reaction between photopolymerizable monomers or between photopolymerizable monomers and the mercapto groups of the polyfunctional thiol compound, particularly in the portion of the light-shielding pattern 21 that is on the substrate 10 side. By heating the partially cured layer 30, the polyfunctional thiol compound undergoes a radical chain reaction, which allows the reaction between photopolymerizable monomers or between photopolymerizable monomers and the mercapto groups of the polyfunctional thiol compound to proceed appropriately and facilitate curing even after exposure.

[0069] In the heating process, when heating the partially hardened layer 30, heating means such as a hot plate H (see Figure 4), a box-type dryer, a reflow oven, or a clean oven can be used.

[0070] During the heating process, the temperature may be 70-150°C or 85-130°C. The heating time may be 1-30 minutes or 2-20 minutes.

[0071] (Development process) In the developing process, alkaline development is carried out using a developing solution such as an alkaline aqueous solution, by known methods such as spraying, agitation immersion, brushing, and scrubbing.

[0072] The developing solution can be any solution capable of dissolving the polymer, such as an alkaline aqueous solution that is safe, stable, and easy to handle. Examples of bases used in the alkaline aqueous solution include alkali hydroxides such as lithium, sodium, potassium, or ammonium hydroxides; alkali carbonates such as lithium, sodium, potassium, or ammonium carbonates or bicarbonates; alkali metal phosphates such as potassium phosphate and sodium phosphate; and alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate.

[0073] Furthermore, suitable alkaline aqueous solutions for development include 0.1-5% by mass tetraammonium hydroxide aqueous solution, 0.1-5% by mass sodium carbonate aqueous solution, 0.1-5% by mass potassium carbonate aqueous solution, 0.1-5% by mass sodium hydroxide aqueous solution, 0.1-5% by mass sodium tetraborate aqueous solution, etc. The pH of the alkaline aqueous solution used for development may be in the range of 9-11, and its temperature is adjusted according to the developability of the photosensitive resin layer 20. Surface surfactants, defoamers, small amounts of organic solvents to accelerate development may also be added to the alkaline aqueous solution.

[0074] In addition, an aqueous developer consisting of an alkaline aqueous solution and one or more organic solvents can be used. Examples of bases included in the alkaline aqueous solution, besides those mentioned above, include borax, sodium metasilicate, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3-propanediol, 1,3-diaminopropanol-2, and morpholine. Examples of organic solvents include diacetone alcohol, acetone, ethyl acetate, alkoxyethanol having alkoxy groups with 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether. These can be used individually or in combination of two or more.

[0075] The developing solutions mentioned above may be used in combination of two or more types, if necessary.

[0076] Development methods include, for example, the dip method, paddle method, spray method, brushing, and slurping. Of these, using the high-pressure spray method improves the resolution of the light-shielding pattern. The development time is not particularly limited and may be, for example, 3 seconds or more, or 5 seconds or more. A development time of 5 seconds or more reduces the likelihood of overdevelopment and reduces manufacturing variations in the line width and thickness of the light-shielding pattern. The development time may be 300 seconds or less, or 200 seconds or less. Figure 6 is a plan view showing the substrate 120 with a light-shielding pattern obtained by the development process. As shown in Figure 6, the light-shielding pattern 21 has multiple openings (through holes). In Figure 6, S represents the width of the opening, i.e., the space width, and L represents the line width of the light-shielding pattern 21.

[0077] (Post-curing process) The post-curing process is a step that hardens the hardened areas after development. One method of exposure in the post-curing process is to irradiate the cured area with light (active light). The same light source used in the exposure process can be used as the light source for the active light.

[0078] The exposure dose in the post-curing process varies depending on the equipment used and the composition of the curing part, but 100 mJ / cm² is suitable for achieving excellent photocuring properties. 2 Above 300 mJ / cm², or 300 mJ / cm² 2 The above is acceptable. The exposure dose in the post-curing process is 10,000 mJ / cm². 2 The following, or 5000 mJ / cm² 2 The following is acceptable:

[0079] The post-curing process can be carried out in air, vacuum, etc., and the atmosphere of the post-curing process is not particularly limited.

[0080] If a post-curing process is performed, the further cured portion resulting from the post-curing process ultimately becomes the light-shielding pattern 21.

[0081] <Image display device and method for manufacturing the same> Next, embodiments of an image display device using the light-shielding substrate described above and a method for manufacturing the same will be described with reference to Figure 7. Figure 7 is a partial cross-sectional view showing the micro-LED mounting process of an embodiment of the method for manufacturing an image display device according to the present disclosure.

[0082] The manufacturing method for the image display device of this embodiment comprises a light-shielding pattern substrate forming step of forming a light-shielding pattern substrate 120 by the light-shielding pattern substrate manufacturing method described above, and a micro-LED mounting step of mounting micro-LEDs 40 as light-emitting elements on the substrate 10 (see Figure 7). An image display device 200 is obtained by the above manufacturing method for the image display device.

[0083] In the process of forming a substrate with a light-shielding pattern, a circuit board is used as the substrate 10. The circuit board has micro LEDs 40 mounted on it, and the micro LEDs 40 can be turned on and off by being electrically connected. Furthermore, the coloring agent contained in the photosensitive resin composition used to form the light-shielding pattern 21 may be black from the viewpoint of further suppressing crosstalk. Moreover, the manufacturing method of the image display device of this embodiment is effective when the height of the photosensitive resin layer 20 from the substrate 10 is 5 μm or more, and is particularly effective when it is 10 μm or more. When the height of the photosensitive resin layer 20 from the substrate 10 is 5 μm or more, that is, in an image display device having a light-shielding pattern 21 and micro LEDs 40 on the substrate 10, the height of the micro LEDs 40 mounted on the substrate 10 is 5 μm or more, crosstalk due to light from adjacent micro LEDs 40 can be sufficiently suppressed.

[0084] In the micro-LED packaging process, micro-LEDs refer to tiny LEDs (semiconductor light-emitting diodes), elements for LED fabrication, materials for LED fabrication, components with incorporated LEDs, LED wafers, etc. Examples include LED elements using gallium nitride, indium gallium nitride, silicon, etc.

[0085] The shape of the micro-LED 40 is not particularly limited, but examples include shapes with a main surface that is square, rectangular, rhombus, trapezoidal, polygonal, or curved, such as a circle, ellipse, or arc. The micro-LED 40 may also have an uneven shape in the thickness direction. As for the size of the micro-LED 40, for example, if the main surface is square, the length of one side may be 0.1 to 2000 μm, and if the main surface is rectangular, the length of the long side may be 0.2 μm to 2000 μm and the length of the short side may be 0.1 to 1500 μm. The thickness of the micro-LED 40 is, for example, 0.1 to 20 μm.

[0086] The micro-LEDs 40 are placed within openings formed in the light-shielding pattern 21 and electrically connected to the substrate 10. The micro-LEDs 40 can be micro-LEDs formed on other substrates, such as a sapphire substrate, and individually cut out. The micro-LEDs 40 can be appropriately selected from blue-emitting, red-emitting, and green-emitting micro-LEDs. In this case, the height of the micro-LEDs 40 from the substrate 10 may be less than or equal to the height of the light-shielding pattern 21 from the substrate 10. In this case, crosstalk from adjacent micro-LEDs 40 can be further suppressed.

[0087] Furthermore, the process of forming a substrate with a light-shielding pattern and the process of mounting micro-LEDs may be performed either after the process of forming a substrate with a light-shielding pattern or after the process of mounting micro-LEDs. In addition, a color filter may be provided on the side of the micro-LED 40 opposite to the substrate 10 as needed.

[0088] According to the manufacturing method of the image display device of this embodiment, a substrate 120 with a light-shielding pattern having excellent resolution and reliability in the light-shielding pattern 21 can be manufactured by the manufacturing method of the substrate with a light-shielding pattern. As a result, in an image display device 200 having a light-shielding pattern 21 and micro-LEDs 40 on the substrate 10, crosstalk caused by light from adjacent micro-LEDs 40 can be suppressed, and the mounting density of the micro-LEDs 40 can also be improved. As a result, an image display device 200 with high image quality and high resolution can be manufactured.

[0089] The method for manufacturing the image display device may also include a micro-LED formation step of forming micro-LEDs 40 on a substrate 10, and a light-shielding pattern substrate formation step of forming a light-shielding pattern substrate 120 by the method for manufacturing a light-shielding pattern substrate described above.

[0090] According to the above-described method for manufacturing an image display device, a substrate with a light-shielding pattern can be manufactured using a method for manufacturing a substrate with a light-shielding pattern, which provides excellent resolution and reliability in light-shielding patterns with high optical density. Therefore, in an image display device having a light-shielding pattern and micro-LEDs on the substrate, crosstalk caused by light from adjacent micro-LEDs is suppressed, and the light-shielding pattern can be formed to match the formed micro-LEDs. As a result, a high-quality and high-resolution image display device can be manufactured.

[0091] In the above embodiments, an image display device having a light-shielding substrate and a micro-LED as a light-emitting element was given as an image display device of the present disclosure. However, the image display device of the present disclosure may be any image display device including the above-mentioned light-shielding substrate, for example, an image display device including a light-shielding substrate and an organic light-emitting element or a quantum dot light-emitting element as a light-emitting element. [Examples]

[0092] The present disclosure will be further described below with reference to examples and comparative examples, but the present disclosure is not limited to the following examples.

[0093] <Examples 1-9 and Comparative Examples 1-7> <Preparation of polymer solution> Polymer solutions 1 to 16 (hereinafter sometimes simply referred to as "binder polymer solutions") were prepared as follows. The constituent units 1 to 8 of the polymer (hereinafter sometimes simply referred to as "binder polymer") are as follows. Here, constituent unit 1 is included in constituent unit (a), constituent unit 2 is included in constituent unit (b), constituent unit 3 is included in constituent unit (c), and constituent units 4 and 6 are included in constituent unit (d). [ka] [ka]

[0094] (Example 1: Binder polymer solution 1) 180.1 g of propylene glycol monomethyl ether (PGME) was added as a solvent to a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube. The mixture was stirred while replacing the gas in the flask with nitrogen gas, and the temperature was raised to 120°C. Next, a monomer mixture consisting of 39.6 g (0.18 mol) of tricyclodecanyl methacrylate, 3.52 g (0.02 mol) of benzyl methacrylate, and 68.8 g (0.80 mol) of methacrylic acid was prepared separately by adding 5.93 g of t-butyl peroxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, Perbutyl® O). This monomer and polymerization initiator mixture was added dropwise to the flask from a dropping funnel over a period of 1 hour. After the addition was complete, the liquid in the flask was stirred at 120°C for a further 2 hours to carry out the copolymerization reaction and synthesize a precursor solution of binder polymer 1. Subsequently, the gas in the flask was replaced with air, and 88.0 g (0.62 mol) of glycidyl methacrylate, 0.6 g of triphenylphosphine (catalyst), and 0.6 g of methylhydroquinone (polymerization inhibitor) were added to the above precursor solution of binder polymer 1. Subsequently, the reaction was continued at 110°C for 10 hours to obtain a resin solution. The weight-average molecular weight of binder polymer 1 contained in this resin solution was 18,500, the double bond equivalent was 340 g / mol, and the glass transition temperature (Tg) was 58.7°C. Furthermore, the proportions of each constituent unit 1 to 8 in binder polymer 1 were as shown in Table 1, based on the total of all constituent units 1 to 8 as the standard (100 mol%). PGME was further added to this resin solution to prepare binder polymer solution 1 (solid content concentration 46.3% by mass) as a binder polymer solution. At this time, binder polymer solution 1 was prepared so that binder polymer 1 and PGME were mixed in the mass ratios shown in Table 3. The term "solids" refers to the residue remaining after heating the binder polymer solution at 130°C for 2 hours, with binder polymer 1 being the main component of the solids. The resin acid value of binder polymer solution 1 was 28.1 KOH mg / g, and the solids acid value of the solids contained in binder polymer solution 1 was 60.7 KOH mg / g.

[0095] (Example 2: Binder polymer solution 2) A resin solution was obtained in the same manner as binder polymer solution 1, except that 5.93 g of t-butyl peroxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, Perbutyl® O) was changed to 8.62 g. The weight-average molecular weight of binder polymer 2 contained in this resin solution was 13100, the double bond equivalent was 340 g / mol, and the glass transition temperature (Tg) of binder polymer 2 was 58.7°C. Furthermore, the proportions of each constituent unit 1 to 8 in binder polymer 2 were as shown in Table 1, based on the total of all constituent units 1 to 8 as the standard (100 mol%). PGME was further added to this resin solution to prepare binder polymer solution 2 (solid content concentration 49.1% by mass) as a binder polymer solution. At this time, binder polymer solution 2 was prepared so that binder polymer 2 and PGME were mixed in the mass ratio shown in Table 3. The resin acid value of this binder polymer solution 2 was 29.9 KOH mg / g, and the solid content acid value of the solids contained in binder polymer solution 2 was 58.9 KOH mg / g.

[0096] (Example 3: Binder polymer solution 3) 180.1 g of PGME was added as a solvent to a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube. The mixture was stirred while replacing the liquid in the flask with nitrogen gas, and the temperature was raised to 120°C. Next, a monomer mixture consisting of 39.6 g (0.18 mol) of tricyclodecanyl methacrylate, 3.52 g (0.02 mol) of benzyl methacrylate, and 68.8 g (0.8 mol) of methacrylic acid was prepared separately by adding 7.39 g of t-butyl peroxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, Perbutyl® O). This monomer and polymerization initiator mixture was added dropwise to the flask from a dropping funnel over a period of 1 hour. After the addition was complete, the liquid in the flask was stirred at 120°C for a further 2 hours to carry out the copolymerization reaction and synthesize a precursor solution of binder polymer 3. Subsequently, the gas in the flask was replaced with air, and 102.24 g (0.72 mol) of glycidyl methacrylate, 0.64 g of triphenylphosphine (catalyst), and 0.64 g of methylhydroquinone (polymerization inhibitor) were added to the above-mentioned precursor solution of binder polymer 3. Subsequently, the reaction was continued at 110°C for 10 hours to obtain a resin solution. The weight-average molecular weight of binder polymer 3 contained in this resin solution was 15,500, the double bond equivalent was 310 g / mol, and the glass transition temperature (Tg) of binder polymer 3 was 50.5°C. Furthermore, the proportions of each constituent unit 1 to 8 in binder polymer 3 were as shown in Table 1, based on the total of all constituent units 1 to 8 as the standard (100 mol%). PGME was further added to the binder polymer 3 solution to prepare binder polymer solution 3 (solid content concentration 48.9% by mass). At this time, binder polymer solution 3 was prepared so that binder polymer 3 and PGME were mixed in the mass ratio shown in Table 3. The resin acid value of this binder polymer solution 3 was 14.9 KOH mg / g, and the solid content acid value of the solids contained in binder polymer solution 3 was 30.5 KOH mg / g.

[0097] (Example 4: Binder polymer solution 4) A resin solution was obtained in the same manner as binder polymer solution 3, except that the amount of t-butyl peroxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, Perbutyl® O) was changed from 7.39 g to 9.74 g. The weight-average molecular weight of binder polymer 4 contained in this resin solution was 12500, the double bond equivalent was 310 g / mol, and the glass transition temperature (Tg) of binder polymer 4 was 50.5°C. Furthermore, the proportions of each constituent unit 1 to 8 in binder polymer 4 were as shown in Table 1, based on the total of all constituent units 1 to 8 as the standard (100 mol%). PGME was further added to this resin solution to prepare binder polymer solution 4 (solid content concentration 51.1% by mass). At this time, binder polymer solution 4 was prepared so that binder polymer 4 and PGME were mixed in the mass ratio shown in Table 3. The resin acid value of this binder polymer solution 4 was 16.2 KOH mg / g, and the solid content acid value of the solids contained in binder polymer solution 4 was 31.7 KOH mg / g.

[0098] (Example 5: Binder polymer solution 5) A resin solution was obtained in the same manner as binder polymer solution 3, except that 7.39 g of t-butyl peroxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, Perbutyl® O) was changed to 14.55 g. The weight-average molecular weight of binder polymer 5 contained in this resin solution was 9300, the double bond equivalent was 310 g / mol, and the glass transition temperature (Tg) of binder polymer 5 was 50.5°C. Furthermore, the proportions of each constituent unit 1 to 8 in binder polymer 5 were as shown in Table 1, based on the total of all constituent units 1 to 8 as the standard (100 mol%). PGME was further added to this resin solution to prepare binder polymer solution 5 (solid content concentration 53.2% by mass) as a binder polymer solution. At this time, binder polymer solution 5 was prepared so that binder polymer 5 and PGME were mixed in the mass ratio shown in Table 3. The resin acid value of this binder polymer solution 5 was 16.4 KOH mg / g, and the solid content acid value of the solids contained in binder polymer solution 5 was 30.8 KOH mg / g.

[0099] (Example 6: Binder polymer solution 6) 180.1 g of PGME was added as a solvent to a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube. The mixture was stirred while replacing the gas in the flask with nitrogen gas, and the temperature was raised to 120°C. Next, a monomer mixture consisting of 4.40 g (0.02 mol) of tricyclodecanyl methacrylate, 31.68 g (0.18 mol) of benzyl methacrylate, and 68.8 g (0.8 mol) of methacrylic acid was prepared separately by adding 5.56 g of t-butyl peroxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, Perbutyl® O). This monomer and polymerization initiator mixture was added dropwise to the flask from a dropping funnel over a period of 1 hour. After the addition was complete, the liquid in the flask was stirred at 120°C for a further 2 hours to carry out the copolymerization reaction and synthesize a precursor solution of binder polymer 6. Subsequently, the gas in the flask was replaced with air, and 88.04 g (0.62 mol) of glycidyl methacrylate, 0.6 g of triphenylphosphine (catalyst), and 0.6 g of methylhydroquinone (polymerization inhibitor) were added to the above-mentioned precursor solution of binder polymer 6. Subsequently, the reaction was continued at 110°C for 10 hours to obtain a resin solution. The weight-average molecular weight of binder polymer 6 contained in this resin solution was 20100, the double bond equivalent was 320 g / mol, and the glass transition temperature (Tg) of binder polymer 6 was 43.1°C. Furthermore, the proportions of each constituent unit 1 to 8 in binder polymer 6 were as shown in Table 1, based on the total of all constituent units 1 to 8 as the base (100 mol%). PGME was further added to this resin solution to prepare binder polymer solution 6 (solid content concentration 46.1% by mass) as a binder polymer solution. At this time, binder polymer solution 6 was prepared so that binder polymer 6 and PGME were mixed in the mass ratio shown in Table 4. The resin acid value of this binder polymer solution 6 was 31.0 KOH mg / g, and the solid content acid value of the solids contained in binder polymer solution 6 was 67.2 KOH mg / g.

[0100] (Example 7: Binder polymer solution 7) 180.1 g of PGME was added as a solvent to a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube. The mixture was stirred while replacing the gas in the flask with nitrogen gas, and the temperature was raised to 120°C. Next, a monomer mixture consisting of 39.6 g (0.18 mol) of tricyclodecanyl methacrylate, 3.52 g (0.02 mol) of benzyl methacrylate, and 68.8 g (0.8 mol) of methacrylic acid was prepared separately by adding 5.60 g of t-butyl peroxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, Perbutyl® O). This monomer and polymerization initiator mixture was added dropwise to the flask from a dropping funnel over a period of 1 hour. After the addition was complete, the liquid in the flask was stirred at 120°C for a further 2 hours to carry out the copolymerization reaction and synthesize a precursor solution of binder polymer 7. Subsequently, the gas in the flask was replaced with air, and 1.00 g (0.50 mol) of glycidyl methacrylate 7, 0.6 g of triphenylphosphine (catalyst), and 0.6 g of methylhydroquinone (polymerization inhibitor) were added to the above-mentioned precursor solution of binder polymer 7. Subsequently, the reaction was continued at 110°C for 10 hours to obtain a resin solution. The weight-average molecular weight of binder polymer 7 contained in this resin solution was 17700, the double bond equivalent was 380 g / mol, and the glass transition temperature (Tg) of binder polymer 7 was 70.9°C. Furthermore, the proportions of each constituent unit 1 to 8 in the binder polymer were as shown in Table 1, based on the total of all constituent units 1 to 8 as the standard (100 mol%). PGME was further added to this resin solution to prepare binder polymer solution 7 (solid content concentration 42.8% by mass) as a binder polymer solution. At this time, binder polymer solution 7 was prepared so that binder polymer 7 and PGME were mixed in the mass ratio shown in Table 4. The resin acid value of this binder polymer solution 7 was 43.4 KOH mg / g, and the solid content acid value of the solids contained in binder polymer solution 7 was 101.4 KOH mg / g.

[0101] (Example 8: Binder polymer solution 8) 180.1 g of PGME was added as a solvent to a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube. The mixture was stirred while replacing the gas in the flask with nitrogen gas, and the temperature was raised to 120°C. Next, a monomer mixture consisting of 61.6 g (0.28 mol) of tricyclodecanyl methacrylate, 3.52 g (0.02 mol) of benzyl methacrylate, and 60.2 g (0.7 mol) of methacrylic acid was prepared separately by adding 5.64 g of t-butyl peroxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, Perbutyl® O). This monomer and polymerization initiator mixture was added dropwise to the flask from a dropping funnel over a period of 1 hour. After the addition was complete, the liquid in the flask was stirred at 120°C for a further 2 hours to carry out the copolymerization reaction and synthesize a precursor solution of binder polymer 8. Subsequently, the gas in the flask was replaced with air, and 73.84 g (0.52 mol) of glycidyl methacrylate, 0.6 g of triphenylphosphine (catalyst), and 0.6 g of methylhydroquinone (polymerization inhibitor) were added to the above-mentioned precursor solution of binder polymer 8. Subsequently, the reaction was continued at 110°C for 10 hours to obtain a resin solution. The weight-average molecular weight of binder polymer 8 contained in this resin solution was 14600, the double bond equivalent was 400 g / mol, and the glass transition temperature (Tg) of binder polymer 8 was 73.0°C. Furthermore, the proportions of each constituent unit 1 to 8 in the binder polymer were as shown in Table 1, based on the total of all constituent units 1 to 8 as the standard (100 mol%). PGME was further added to this resin solution to prepare binder polymer solution 8 (solid content concentration 46.0% by mass) as a binder polymer solution. At this time, binder polymer solution 8 was prepared so that binder polymer 8 and PGME were mixed in the mass ratio shown in Table 4. The resin acid value of this binder polymer solution 8 was 28.5 KOH mg / g, and the solid content acid value of the solids contained in binder polymer solution 8 was 62.0 KOH mg / g.

[0102] (Example 9: Binder polymer solution 9) 180.1 g of PGME was added as a solvent to a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube. The mixture was stirred while replacing the gas in the flask with nitrogen gas, and the temperature was raised to 120°C. Next, a monomer mixture consisting of 2.20 g (0.01 mol) of tricyclodecanyl methacrylate, 1.76 g (0.01 mol) of benzyl methacrylate, and 84.28 g (0.98 mol) of methacrylic acid was prepared separately by adding 7.77 g of t-butyl peroxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, Perbutyl® O). This monomer and polymerization initiator mixture was added dropwise to the flask from a dropping funnel over a period of 1 hour. After the addition was complete, the liquid in the flask was stirred at 120°C for a further 2 hours to carry out the copolymerization reaction and synthesize a precursor solution of binder polymer 9. Subsequently, the gas in the flask was replaced with air, and 73.84 g (0.52 mol) of glycidyl methacrylate, 0.6 g of triphenylphosphine (catalyst), and 0.6 g of methylhydroquinone (polymerization inhibitor) were added to the above-mentioned precursor solution of binder polymer 9. Subsequently, the reaction was continued at 110°C for 10 hours to obtain a resin solution. The weight-average molecular weight of binder polymer 9 contained in this resin solution was 16,500, the double bond equivalent was 270 g / mol, and the glass transition temperature (Tg) of binder polymer 9 was 36.9°C. Furthermore, the proportions of each constituent unit 1 to 8 in the binder polymer were as shown in Table 1, based on the total of all constituent units 1 to 8 as the standard (100 mol%). PGME was further added to this resin solution to prepare binder polymer solution 9 (solid content concentration 44.1% by mass) as a binder polymer solution. At this time, binder polymer solution 9 was prepared so that binder polymer 9 and PGME were mixed in the mass ratio shown in Table 4. The resin acid value of this binder polymer solution 9 was 29.1 KOH mg / g, and the solid content acid value of the solids contained in binder polymer solution 9 was 66.0 KOH mg / g.

[0103] (Comparative Example 1: Binder polymer solution 10) 180.1 g of PGME was added as a solvent to a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube. The mixture was stirred while replacing the gas in the flask with nitrogen gas, and the temperature was raised to 120°C. Next, a monomer mixture consisting of 39.6 g (0.18 mol) tricyclodecanyl methacrylate, 3.52 g (0.02 mol) benzyl methacrylate, and 68.8 g (0.8 mol) methacrylic acid was prepared separately by adding 3.36 g of t-butyl peroxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, Perbutyl® O). This monomer and polymerization initiator mixture was added dropwise to the flask from a dropping funnel over a period of 1 hour. After the addition was complete, the liquid in the flask was stirred at 120°C for a further 2 hours to carry out the copolymerization reaction and synthesize a precursor solution of binder polymer 10. Subsequently, the gas in the flask was replaced with air, and 41.18 g (0.29 mol) glycidyl methacrylate, 0.45 g triphenylphosphine (catalyst), and 0.45 g methylhydroquinone (polymerization inhibitor) were added to the above-mentioned precursor solution of binder polymer 10. Subsequently, the reaction was continued at 110°C for 10 hours to obtain a resin solution. The weight-average molecular weight of binder polymer 10 contained in this resin solution was 18500, the double bond equivalent was 550 g / mol, and the glass transition temperature (Tg) of binder polymer 10 was 102.4°C. Furthermore, the proportions of each constituent unit 1 to 8 in the binder polymer were as shown in Table 2, based on the total of all constituent units 1 to 8 as the standard (100 mol%). PGME was further added to this resin solution to prepare binder polymer solution 10 (solid content concentration 39.3% by mass) as a binder polymer solution. At this time, binder polymer solution 10 was prepared so that binder polymer 10 and PGME were mixed in the mass ratio shown in Table 5. The resin acid value of this binder polymer solution 10 was 75.6 KOH mg / g, and the solid content acid value of the solids contained in binder polymer solution 10 was 192.4 KOH mg / g.

[0104] (Comparative Example 2: Binder Polymer Solution 11) 180.1 g of PGME was added as a solvent to a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube. The mixture was stirred while replacing the gas in the flask with nitrogen gas, and the temperature was raised to 120°C. Next, a monomer mixture consisting of 39.6 g (0.18 mol) of tricyclodecanyl methacrylate, 3.52 g (0.02 mol) of benzyl methacrylate, and 68.8 g (0.8 mol) of methacrylic acid was prepared separately by adding 5.15 g of t-butyl peroxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, Perbutyl® O). This monomer and polymerization initiator mixture was added dropwise to the flask from a dropping funnel over a period of 1 hour. After the addition was complete, the liquid in the flask was stirred at 120°C for a further 2 hours to carry out the copolymerization reaction and synthesize a precursor solution of binder polymer 11. Subsequently, the gas in the flask was replaced with air, and 56.80 g (0.40 mol) of glycidyl methacrylate, 0.50 g of triphenylphosphine (catalyst), and 0.50 g of methylhydroquinone (polymerization inhibitor) were added to the above-mentioned precursor solution of binder polymer 11. Subsequently, the reaction was continued at 110°C for 10 hours to obtain a resin solution. The weight-average molecular weight of the binder polymer 11 contained in this resin solution was 17400, the double bond equivalent was 440 g / mol, and the glass transition temperature (Tg) of the binder polymer 11 was 83.8°C. Furthermore, the proportions of each constituent unit 1 to 8 in the binder polymer were as shown in Table 2, based on the total of all constituent units 1 to 8 as the standard (100 mol%). PGME was further added to this resin solution to prepare a binder polymer solution 11 (solid content concentration 41.9% by mass) as a binder polymer solution. At this time, the binder polymer solution 11 was prepared so that the binder polymer 11 and PGME were mixed in the mass ratio shown in Table 5. The resin acid value of this binder polymer solution 11 was 58.0 KOH mg / g, and the solid content acid value of the solids contained in the binder polymer solution 11 was 138.4 KOH mg / g.

[0105] (Comparative Example 3: Binder Polymer Solution 12) 167.1 g of PGMEA was added as a solvent to a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube. The mixture was stirred while replacing the gas in the flask with nitrogen gas, and the temperature was raised to 120°C. Next, a monomer mixture consisting of 66.0 g (0.3 mol) tricyclodecanyl methacrylate, 10.4 g (0.1 mol) styrene, and 85.2 g (0.6 mol) glycidyl methacrylate was prepared separately by adding 19.4 g of t-butyl peroxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, Perbutyl® O). This monomer and polymerization initiator mixture was added dropwise to the flask from a dropping funnel over a period of 1 hour. After the addition was complete, the liquid in the flask was stirred at 120°C for a further 2 hours to carry out the copolymerization reaction and produce a precursor of binder polymer 12. Subsequently, the gas in the flask was replaced with air, and 41.9 g (0.58 mol) acrylic acid, 0.61 g triphenylphosphine (catalyst), and 0.31 g methylhydroquinone (polymerization inhibitor) were added to the above binder polymer 12 precursor solution. The reaction was then continued at 110°C for 10 hours. Next, 68.4 g (0.45 mol) of tetrahydrophthalic anhydride was added to the flask, and the reaction was continued at 110°C for 3 hours to obtain a resin solution. The weight-average molecular weight of binder polymer 12 contained in this resin solution was 8300, the double bond equivalent was 500 g / mol, and the glass transition temperature (Tg) of binder polymer 12 was 39.0°C. Furthermore, the proportions of each constituent unit 1 to 8 in the binder polymer were as shown in Table 2, based on the total of all constituent units 1 to 8 as the standard (100 mol%). PGMEA was further added to this resin solution to prepare a binder polymer solution 12 (solid content concentration 57.6% by mass) as a binder polymer solution. At this time, the binder polymer solution 12 was prepared so that the binder polymer 12 and PGMEA were mixed in the mass ratio shown in Table 5. The resin acid value of this binder polymer solution 12 was 51.6 KOH mg / g, and the solid content acid value of the solids contained in the binder polymer solution 12 was 89.6 KOH mg / g.

[0106] (Comparative Example 4: Binder Polymer Solution 13) 167.1 g of PGMEA was added as a solvent to a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube. The mixture was stirred while replacing the gas in the flask with nitrogen gas, and the temperature was raised to 120°C. Next, a monomer mixture consisting of 66.0 g (0.3 mol) tricyclodecanyl methacrylate, 10.4 g (0.1 mol) styrene, and 85.2 g (0.6 mol) glycidyl methacrylate was prepared separately by adding 10.7 g of t-butyl peroxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, Perbutyl® O). This monomer and polymerization initiator mixture was added dropwise to the flask from a dropping funnel over a period of 1 hour. After the addition was complete, the liquid in the flask was stirred at 120°C for a further 2 hours to carry out the copolymerization reaction and produce a precursor of binder polymer 13. Subsequently, the gas in the flask was replaced with air, and 41.9 g (0.58 mol) acrylic acid, 0.61 g triphenylphosphine (catalyst), and 0.31 g methylhydroquinone (polymerization inhibitor) were added to the above binder polymer 13 precursor solution. The reaction was then continued at 110°C for 10 hours. Next, 66.88 g (0.44 mol) of tetrahydrophthalic anhydride was added to the flask, and the reaction was continued at 110°C for 3 hours to obtain a resin solution. The weight-average molecular weight of binder polymer 13 contained in this resin solution was 14700, the double bond equivalent was 480 g / mol, and the glass transition temperature (Tg) of binder polymer 13 was 40.0°C. Furthermore, the proportions of each constituent unit 1 to 8 in the binder polymer were as shown in Table 2, based on the total of all constituent units 1 to 8 as the standard (100 mol%). PGMEA was further added to this resin solution to prepare a binder polymer solution 13 (solid content concentration 53.2% by mass) as a binder polymer solution. At this time, the binder polymer solution 13 was prepared so that the binder polymer 13 and PGMEA were mixed in the mass ratio shown in Table 5. The resin acid value of this binder polymer solution 13 was 46.9 KOH mg / g, and the solid content acid value of the solids contained in the binder polymer solution 13 was 88.2 KOH mg / g.

[0107] (Comparative Example 5: Binder polymer solution 14) 167.1 g of PGMEA was added as a solvent to a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube. The mixture was stirred while replacing the gas in the flask with nitrogen gas, and the temperature was raised to 120°C. Next, a monomer mixture consisting of 66.0 g (0.3 mol) tricyclodecanyl methacrylate, 10.4 g (0.1 mol) styrene, and 85.2 g (0.6 mol) glycidyl methacrylate was prepared separately by adding 16.16 g of t-butyl peroxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, Perbutyl® O). This monomer and polymerization initiator mixture was added dropwise to the flask from a dropping funnel over a period of 1 hour. After the addition was complete, the liquid in the flask was stirred at 120°C for a further 2 hours to carry out the copolymerization reaction and produce a precursor of binder polymer 14. Subsequently, the gas in the flask was replaced with air, and 41.9 g (0.58 mol) acrylic acid, 0.61 g triphenylphosphine (catalyst), and 0.31 g methylhydroquinone (polymerization inhibitor) were added to the above binder polymer 14 precursor solution. The reaction was then continued at 110°C for 10 hours. Next, 41.05 g (0.27 mol) of tetrahydrophthalic anhydride was added to the flask, and the reaction was continued at 110°C for 3 hours to obtain a resin solution. The weight-average molecular weight of binder polymer 14 contained in this resin solution was 7200, the double bond equivalent was 450 g / mol, and the glass transition temperature (Tg) of binder polymer 14 was 47.6°C. Furthermore, the proportions of each constituent unit 1 to 8 in the binder polymer were as shown in Table 2, based on the total of all constituent units 1 to 8 as the standard (100 mol%). PGMEA was further added to this resin solution to prepare a binder polymer solution 14 (solid content concentration 57.6% by mass) as a binder polymer solution. At this time, the binder polymer solution 14 was prepared so that the binder polymer 14 and PGMEA were mixed in the mass ratio shown in Table 5. The resin acid value of this binder polymer solution 14 was 36.8 KOH mg / g, and the solid content acid value of the solids contained in the binder polymer solution 14 was 63.9 KOH mg / g.

[0108] (Comparative Example 6: Binder polymer solution 15) 152.5g of PGMEA was added as a solvent to a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube. The mixture was stirred while replacing the gas in the flask with nitrogen gas, and the temperature was raised to 120°C. Next, a monomer mixture consisting of 66.0 g (0.30 mol) tricyclodecanyl methacrylate, 10.4 g (0.10 mol) styrene, and 85.2 g (0.60 mol) glycidyl methacrylate was prepared separately by adding 10.3 g of t-butyl peroxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, Perbutyl® O). This monomer and polymerization initiator mixture was added dropwise to the flask from a dropping funnel over a period of 1 hour. After the addition was complete, the liquid in the flask was stirred at 120°C for a further 2 hours to carry out the copolymerization reaction and produce a precursor of binder polymer 15. Subsequently, the gas in the flask was replaced with air, and 41.9 g (0.58 mol) acrylic acid, 0.61 g triphenylphosphine (catalyst), and 0.31 g methylhydroquinone (polymerization inhibitor) were added to the above binder polymer 15 precursor solution. The reaction was then continued at 110°C for 10 hours. Next, 33.00 g (0.33 mol) of succinic anhydride was added to the flask, and the reaction was continued at 110°C for 3 hours to obtain a resin solution. The weight-average molecular weight of binder polymer 15 contained in this resin solution was 15,000, the double bond equivalent was 420 g / mol, and the glass transition temperature (Tg) of binder polymer 15 was 48.4°C. Furthermore, the proportions of each constituent unit 1 to 8 in the binder polymer were as shown in Table 2, based on the total of all constituent units 1 to 8 as the base (100 mol%). PGMEA was further added to this resin solution to prepare binder polymer solution 15 (solid content concentration 53.3% by mass) as a binder polymer solution. At this time, binder polymer solution 15 was prepared so that binder polymer 15 and PGMEA were mixed in the mass ratio shown in Table 5. The resin acid value of this binder polymer solution 15 was 40.2 KOH mg / g, and the solid content acid value of the solids contained in binder polymer solution 15 was 75.4 KOH mg / g.

[0109] (Comparative Example 7: Binder polymer solution 16) 167.1 g of PGMEA was added as a solvent to a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube. The mixture was stirred while replacing the gas in the flask with nitrogen gas, and the temperature was raised to 120°C. Next, a monomer mixture consisting of 66.0 g (0.30 mol) of tricyclodecanyl methacrylate, 23.9 g (0.23 mol) of styrene, and 66.7 g (0.47 mol) of glycidyl methacrylate was prepared separately by adding 17.2 g of t-butyl peroxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, Perbutyl® O). This monomer and polymerization initiator mixture was added dropwise to the flask from a dropping funnel over a period of 1 hour. After the addition was complete, the liquid in the flask was stirred at 120°C for a further 2 hours to carry out the copolymerization reaction and produce a precursor of binder polymer 16. Subsequently, the gas in the flask was replaced with air, and 32.8 g (0.46 mol) of acrylic acid, 0.61 g of triphenylphosphine (catalyst), and 0.31 g of methylhydroquinone (polymerization inhibitor) were added to the above binder polymer 16 precursor solution. The reaction was then continued at 110°C for 10 hours. Next, 22.00 g (0.22 mol) of succinic anhydride was added to the flask, and the reaction was continued at 110°C for 3 hours to obtain a resin solution. The weight-average molecular weight of binder polymer 16 contained in this resin solution was 8100, the double bond equivalent was 420 g / mol, and the glass transition temperature (Tg) of binder polymer 16 was 60.1°C. Furthermore, the proportions of each constituent unit 1 to 8 in the binder polymer were as shown in Table 2, based on the total of all constituent units 1 to 8 as the base (100 mol%). PGMEA was further added to this resin solution to prepare binder polymer solution 16 (solid content concentration 58.4% by mass) as a binder polymer solution. At this time, binder polymer solution 16 was prepared so that binder polymer 16 and PGMEA were mixed in the mass ratio shown in Table 5. The resin acid value of this binder polymer solution 16 was 33.2 KOH mg / g, and the solid content acid value of the solids contained in binder polymer solution 1 was 56.8 KOH mg / g.

[0110] <Method for measuring physical properties> The above-mentioned resin acid value, solid content acid value, double bond equivalent, weight-average molecular weight, and glass transition temperature are values ​​obtained by the method described below. (1) Resin acid value The resin acid value is the acid value of the binder polymer solution measured using a mixed indicator of bromothymol blue and phenol lett, in accordance with JIS K6901 5.3.2. The resin acid value represents the number of milligrams of potassium hydroxide required to neutralize the acidic components contained in 1 g of the binder polymer solution. (2) Solid content acid value The solids acid value is calculated using the following formula. Solid content acid value = 100 × resin acid value / (solid content concentration (mass%) of binder polymer solution) (3) Double bond equivalent The double bond equivalent is the mass of the polymer per mole of polymerizable unsaturated bonds, and is a calculated value based on the amount of monomer used. (4) Weight average molecular weight (Mw) The weight-average molecular weight refers to the weight-average molecular weight converted to standard polystyrene, measured using gel permeation chromatography (GPC) under the following conditions. Column: SHODEX (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko Corporation) Column temperature: 40℃ Sample: 0.2% tetrahydrofuran solution of copolymer Developing solvent: tetrahydrofuran Detector: Differential refractometer (Showdex® RI-71S) (manufactured by Showa Denko Corporation) Flow rate: 1mL / min (5) Glass transition temperature (Tg) The Tg of the binder polymer was measured using a differential scanning calorimeter (DSC7000X, Hitachi High-Tech Science Corporation). Specifically, 1 g was taken from each binder polymer solution, dried at 130°C for 120 minutes to evaporate the solvent, and 10 mg of each sample was taken from the resulting solid content. Then, differential scanning calorimetry (DSC) was performed by changing the temperature of the sample from -0°C to 200°C at a heating rate of 10°C / min, and the observed endothermic onset temperature due to glass transition was defined as the glass transition temperature (Tg). If two Tg values ​​were observed, the average of the two Tg values ​​was used as the Tg of the binder polymer.

[0111] [Table 1] [Table 2]

[0112] <Preparation of photosensitive resin composition> Components (A), (B), (C), (D), (E), and (F) shown in Tables 3, 4, or 5 were blended to the concentrations (unit: mass%) shown in the same table, and mixed for 15 minutes using a stirrer to prepare photosensitive resin compositions, specifically coating solutions No. 1 to 16 for forming a photosensitive resin layer.

[0113] [Table 3]

[0114] [Table 4]

[0115] [Table 5]

[0116] In Tables 3, 4, or 5, the details of components (A), (B), (C), (D), (E), and (F) are as follows. (A) component Solutions 1-16: Binder polymer solutions 1-16 prepared by the method described above.

[0117] (B) Component Photopolymerizable monomer: Trimethylolpropane oliacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., product name "A-TMPT")

[0118] (C) Component Polyfunctional thiol compound: Pentaerythritol tetrakis(3-mercaptobutyrate) (KarenzMT® PE1 (SH group count = 4), manufactured by Showa Denko K.K.)

[0119] (D) Component A mixture obtained by mixing lactam black (solid content) represented by the following structural formula as a pigment, a non-amine dispersant (solid content) as a dispersant, and PGMEA in a mass ratio of 15.0:4.5:80.5 (lactam black-based organic pigment dispersion (product name "SF BLACK BJ4379", manufactured by Sanyo Shikkei Co., Ltd., solid content: 19.5% by mass, lactam black-based organic pigment: 15% by mass)).

[0120] (E) Component Photopolymerization initiator: 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (product name "Lunacure TPO", manufactured by DKSH Japan Co., Ltd.)

[0121] (F) component Adhesion enhancer: Si coupling agent (product name "KBM-803", manufactured by Shin-Etsu Chemical Co., Ltd.)

[0122] <Formation of light-blocking patterns> The photosensitive resin layer forming solution obtained as described above was dropped onto a glass plate with a thickness of 3.0 mm, and a coating film was formed by spin coating to obtain a laminate with a coating film on the glass plate. Subsequently, this laminate was placed on a hot plate and heated at 120°C for 2 minutes to remove the solvent, thereby producing a first laminate having a photosensitive resin layer. When obtaining the first laminate, the thickness of the coating film was adjusted by adjusting the rotation speed in the spin coating method so that the thickness of the photosensitive resin layer was 15 ± 1 μm. Next, the first laminate was partially exposed to ultraviolet light using an ultraviolet exposure machine (product name "MA-20", manufactured by Mikasa Corporation) via a lattice-shaped glass mask (manufactured by Shin-ei Co., Ltd.) as a photomask, to obtain a second laminate with a partially cured layer. The glass mask used had a space width (S) of 40 μm and a line width (L) of 30 μm. The exposure dose was the value shown in Tables 3, 4, or 5 (unit: mJ / cm²). 2 ) Next, the second layer was placed on a hot plate and heated at 100°C for 1 minute (post-bake) as shown in Table 3, Table 4, or Table 5. Next, the second laminate was placed on an adsorption stage, and spray development was performed using a developer (product name "AD-1200", manufactured by Mikasa Corporation). After washing, a third laminate having only the hardened portion on a glass plate was obtained. For spray development, 2.38% TMAH (tetramethylammonium hydroxide) was used as the developer and the development was carried out at 23°C for the development time shown in Tables 3, 4, or 5. Here, the development time is the minimum time required for the unhardened portion of the partially hardened layer to completely dissolve in the developer. Washing was performed with pure water at 23°C for 30 seconds. Subsequently, the third layer was subjected to full-surface ultraviolet exposure using an ultraviolet exposure machine (product name "MA-20," manufactured by Mikasa Corporation). The exposure dose at this time was 1000 mJ / cm². 2 That's what I decided. In this way, a light-shielding pattern was formed on the glass plate. In this way, a light-shielding patterned substrate was formed on a glass plate, with a light-shielding pattern having a thickness of 15 μm. Next, a light-shielding patterned substrate was formed in the same manner as described above, except that the glass mask used had line widths (L) of 25 μm, 20 μm, 15 μm, 10 μm, 8 μm, 6 μm, or 4 μm. In this manner, eight types of substrates with light-shielding patterns were formed.

[0123] <Performance Evaluation> The optical density, resolution, and reliability of substrates with light-shielding patterns were evaluated as follows. (1) Optical density (OD value) The OD value of the light-shielding pattern obtained as described above was calculated based on the relationship between the OD value and the content of the colorant in the total solids contained in the photosensitive resin layer forming coating solution, which was determined in advance, and the content of the colorant in the total solids contained in the photosensitive resin layer forming coating solution. The results are shown in Tables 3, 4, and 5. The reason for indirectly determining the OD value of the light-shielding pattern as described above is that the minimum measurement limit for transmittance in the transmittance measuring device (product name "Spectroscopic Haze Meter SH 7000", manufactured by Nippon Denshoku Industries Co., Ltd.) that will be used to measure transmittance is 0.03% (corresponding to an OD value of approximately 2.4), and it becomes difficult to calculate the OD value when it exceeds 2.4. The above relationship was determined as follows. First, for each example or comparative example, five types of photosensitive resin layer forming coating solutions were prepared, the same as for each example or comparative example except that the content of the colorant in the total solids was 0% by mass, 4% by mass, 6% by mass, 8% by mass, and 10% by mass. Then, each of the five types of photosensitive resin layer forming coating solutions was dropped onto a glass plate with a thickness of 3.0 mm, and a coating film was formed by the spin coating method to obtain a laminate formed on the glass plate. At this time, the rotation speed in the spin coating method was adjusted for each of the five types of photosensitive resin layer forming coating solutions to obtain three laminates with different coating film thicknesses and transmittance after solvent removal that were within the transmittance measurement limit of the transmittance measuring device. Subsequently, these three laminates were each placed on a hot plate and heated at 120°C for 2 minutes to remove the solvent, and a first laminate formed by a photosensitive resin layer on the glass plate was obtained. Next, the first laminate was exposed to ultraviolet light using an ultraviolet exposure machine (product name "MA-20", manufactured by Mikasa Corporation) to obtain a cured body. The exposure dose at this time was 200 mJ / cm². 2 That's what I decided. Next, the cured material was placed on a hot plate and heated at 60°C for 5 minutes. In this way, a sample for transmittance measurement was prepared by forming a cured layer with a thickness of 15 μm on a glass plate. Then, the transmittance of the sample for transmittance measurement was measured using the transmittance measuring device described above, and the OD value was calculated based on this transmittance and the following formula. OD value = -log 10 (Transmittance at a wavelength of 610 nm / 100) Then, the OD values ​​calculated as described above were plotted against the thickness of the hardened layer of the transmittance measurement sample, and straight lines passing through the plotted points were formed. At this time, a straight line was formed for each percentage of colorant content in the total solid content, resulting in a total of five lines. Next, from the five intersection points of the line with a hardened layer thickness of 15 μm and the five lines obtained as described above, five OD values ​​were determined for colorant content of 0 mass%, 4 mass%, 6 mass%, 8 mass%, and 10 mass% in the total solids when the hardened layer thickness is 15 μm. Then, these five OD values ​​were plotted to form a straight line passing through the plotted points. In this way, the above relationship was determined. From the above relationship, it was found that there is a proportional relationship between the content of colorant in the total solids and the OD value. The passing criteria for OD values ​​were as follows: (Passing criteria) The OD value must be 3.0 or higher.

[0124] (2) Resolution The light-shielding pattern of the substrate with the light-shielding pattern prepared as described above was observed in the thickness direction of the glass plate using a laser microscope (product name "3D MEASURING LASER MICROSCOPE OLS5000", manufactured by OLYMPUS), and the line width was measured to determine the smallest line width that satisfies the following conditions. The results are shown in Tables 3, 4, and 5. In Tables 3, 4, and 5, "-" indicates that the coating liquid for forming the photosensitive resin layer, as a photosensitive resin composition, was not photosensitive, and therefore a light-shielding pattern could not be formed, and thus a line width that satisfies the following conditions could not be determined. (conditions) • Thickness: The thickness of the light-shielding pattern must be 90% or more of the thickness of the photosensitive resin layer before exposure. • Shape: The grid pattern must be formed without chipping or distortion. The resolution passing criteria were as follows: (Passing criteria) Line width must be 15 μm or less.

[0125] (3) Reliability Of the eight types of light-shielding patterned substrates prepared as described above, the light-shielding pattern of the substrate prepared using a glass mask with a line width (L) of 15 μm was left in an environment of 85°C and 85% RH for 500 hours. Then, the residual film percentage (%) in the thickness direction of the light-shielding pattern was calculated based on the following formula. The results are shown in Tables 3, 4, and 5. In Tables 3, 4, and 5, "-" indicates that the residual film percentage was not calculated. Remaining film rate (%)=100×a1 / a0 (In the above formula, a0 represents the initial thickness of the light-shielding pattern (μm), and a1 represents the thickness of the light-shielding pattern (μm) after being left in an environment of 85°C and 85%RH for 500 hours.) The reliability acceptance criteria were as follows: (Passing criteria) The residual film rate must be 80% or higher.

[0126] As shown in Tables 3, 4, and 5, the photosensitive resin compositions containing binder polymers of Examples 1 to 9 met the acceptance criteria in terms of resolution and reliability even in light-shielding patterns with high OD values. In contrast, the photosensitive resin compositions containing binder polymers of Comparative Examples 1 to 7 did not meet the acceptance criteria in terms of resolution and reliability in light-shielding patterns with high OD values. In particular, the surface of the light-shielding patterns formed using the photosensitive resin compositions containing binder polymers of Examples 1 to 9 (the surface opposite to the surface of the glass plate which is the substrate) was almost flat. In contrast, the surface of the light-shielding patterns formed using the photosensitive resin compositions containing binder polymers of Comparative Examples 2 to 5 and 7 was curved in a bowl shape. When the surface of the light-shielding pattern is not curved and is almost flat, advantages such as easier acquisition of display smoothness and uniform image quality when external factors such as external light reflection or when a sealing layer is provided on top of the light-shielding pattern are present can be obtained. From the above, it has been confirmed that the polymer of this disclosure can form a photosensitive resin composition that can provide excellent resolution and reliability in light-shielding patterns with high optical density. [Explanation of Symbols]

[0127] 10...Substrate, 20...Photosensitive resin layer, 21...Light-shielding pattern, 30...Partially cured layer, 40...Micro LED, 120...Substrate with light-shielding pattern, 200...Micro LED display.

Claims

1. A polymer used in a photosensitive resin composition, It includes a constituent unit (a) represented by the following formula (1), a constituent unit (b) represented by the following formula (2), a constituent unit (c) represented by the following formula (3), and a constituent unit (d) represented by the following formula (4), A polymer with a double bond equivalent of 250 to 400 g / mol. 【Chemistry 1】 (In formula (1) above, R １ (where represents a hydrogen atom or a methyl group, and X represents an alicyclic hydrocarbon group which may have substituents.) 【Chemistry 2】 (In formula (2) above, R ２ (where represents a hydrogen atom or a methyl group, Y is represented as -COOQ, and Q represents an aromatic hydrocarbon group which may have substituents.) 【Transformation 3】 (In formula (3) above, R ３ (This represents a hydrogen atom or a methyl group.) 【Chemistry 4】 (In the above formula (4), R ４ and R ５ Each of these independently represents either a hydrogen atom or a methyl group.

2. The polymer according to claim 1, wherein the solid content acid value is 25 to 125 mg KOH / g.

3. The polymer according to claim 1, wherein in formula (1), the alicyclic hydrocarbon group is a tricyclodecyl group.

Images