Method for manufacturing an LED mounting substrate with a hardened film

Abstract

The purpose of the present invention is to provide a production method for an LED-mounted substrate with a cured film that excels in manufacturing efficiency and that is capable of, with respect to an LED-mounted substrate, collectively implementing the leaving behind of a post-developing coating film so as to cover a patterned post-developing coating film (partitioning wall) for separating LEDs, and surrounding portions of bumps and electrodes, and that is further capable of selectively removing an unneeded portion using a photosensitivity method. This purpose can be achieved through a production method for an LED-mounted substrate with a cured film in which specified processing steps are sequentially carried out with respect to an LED-mounted substrate having a substrate that comprises wiring electrodes, a plurality of bumps that are formed on the wiring electrodes, and a plurality of LED elements that are mounted on the bumps, said production method being characterized in that in a step for developing and removing an unneeded portion in a dried film after light exposure, a post-development film is caused to remain on at least surrounding portions of the bumps and the wiring electrodes.

Description

Technical Field

[0001] The present invention relates to a method for manufacturing an LED mounting substrate with a cured film.

Background Art

[0002] In recent years, with the development of information terminal devices such as smartphones and tablets, and the high definition of flat panel displays including televisions, the demand for higher performance of displays has been increasing further. Among them, as a high-performance display, a micro LED display using micro-sized LEDs has attracted attention. This display is a display that performs full-color display using micro LEDs driven by an active matrix method or the like as a light source, and has excellent contrast and color reproducibility.

[0003] For this micro LED display, it is necessary to arrange a patterned cured film (partition wall) that separates the light sources with a size corresponding to the micro LEDs that are the light sources. As a method for forming a patterned cured film, a photolithography method using a pattern mask is well known (Patent Document 1). In addition, these partition walls are required to have light-shielding properties that prevent color mixing between adjacent micro LEDs, as well as reflection characteristics that efficiently extract light from the micro LEDs.

[0004] In addition, for the production of a micro LED display, since a very large number of micro LEDs, ranging from hundreds of thousands to tens of millions, are required, an efficient mounting method on a substrate is required. For example, after applying a conductive photoresist or the like containing conductive fine particles on the surface of a printed wiring board, exposing and developing it to form conductive bumps on the electrodes of the printed wiring board, and then joining the conductive bumps and the LED electrodes through a conductive adhesive. Also, since the mounting of LEDs has become finer in pitch, the importance of a cured film (Patent Document 3) for the purpose of protecting the electrodes and improving the light extraction efficiency has also increased.

Prior Art Documents

Patent Document

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0006] As a method of mounting an LED on a substrate, in the technique described in Patent Document 2, since an adhesive is separately required to bond a conductive bump and an LED electrode, there is a problem that the number of processes increases and the production efficiency is poor. Further, in the underfill formation technique described in Patent Document 3, when forming a sealing film using a liquid resin material on the electrode portion of the LED mounted on the substrate, it is necessary to form a frame for blocking the spread of the liquid resin material, etc., and there is a problem that the production efficiency is poor.

[0007] Therefore, the present invention provides a method for manufacturing an LED mounting substrate with a cured film, which can perform, in one batch, a patterned developed coating film (partition wall) that separates the LEDs and covering the periphery of the bumps and electrodes on the LED mounting substrate, and selectively remove unnecessary portions using a photosensitive method, and has excellent production efficiency.

Means for Solving the Problems

[0008] As a result of intensive studies, the present inventors have found that the above problems can be solved by the following method for manufacturing an LED mounting substrate with a cured film. [1] A method for manufacturing an LED mounting substrate with a cured film, which sequentially performs the following processing steps (1) to (5) on an LED mounting substrate on which a plurality of substrates having wiring electrodes, bumps formed on the wiring electrodes, and LED elements mounted on the bumps are mounted. (1) Apply a photosensitive resin composition to the LED mounting substrate to fill the gap between the LED element and the wiring electrode on the substrate and the space between adjacent LED elements with a coating film. (2) Dry the coating film to form a dry film. (3) Expose the dry film. (4) Develop and remove the unnecessary portions in the dry film after exposure. (5) Cure the film with unnecessary portions removed after development to form a cured film. [2] In the treatment step (4) described in [1], the step of developing and removing the unnecessary portions in the dry film after exposure, the method for manufacturing an LED mounting substrate with a cured film according to [1], characterized in that the film after development remains at least around the bump and the wiring electrode. [3] The method for manufacturing an LED mounting substrate with a cured film according to [1] or [2], wherein the bump formed on the wiring electrode contains (A) an organic component and (B) conductive particles. [4] The method for manufacturing an LED mounting substrate with a cured film according to any one of [1] to [3], wherein the bump contains (A) an acrylic copolymer having a carboxyl group in the organic component and an epoxy resin, and the proportion of the (B) conductive particles in the total weight of the bump is 50 to 90 wt%. [5] The method for manufacturing an LED mounting substrate with a cured film according to any one of [1] to [4], wherein the bump is formed by exposing and developing a conductive paste containing (A) an organic component and (B) conductive particles to form a pattern. [6] The method for manufacturing an LED mounting substrate with a cured film according to any one of [1] to [5], wherein the photosensitive resin composition contains (C) a resin, (D) a photoinitiator, (E) a photopolymerizable compound, (F) an organic solvent, and (G) a coloring pigment. [7] The method for manufacturing an LED mounting substrate with a cured film according to [6], characterized in that the (G) coloring pigment contains at least (G-1) a white pigment. [8] The method for manufacturing an LED mounting substrate with a cured film according to [6] or [7], wherein the (C) resin is (C-1) a siloxane resin. [9] An LED mounting substrate with a cured film manufactured by the method according to any one of [1] to [8].

[10] An element comprising the LED mounting substrate with a cured film according to [9].

[11] An LED mounting substrate having a substrate with electrodes, bumps made of a composite material of an organic component and conductive particles formed on the electrodes, and a plurality of LED elements mounted on the bumps, wherein at least a part of the periphery of the bumps and the LED elements is covered with a cured film of a photosensitive resin composition, and the cured film of the photosensitive resin composition is also provided between adjacent LD elements. [Effect of the Invention]

[0009] The present invention provides a method for manufacturing an LED mounting substrate with a cured film, which is excellent in production efficiency, and can collectively perform covering the LED mounting substrate with a patterned developed coating film (partition wall) for separating LEDs and the periphery of bumps and wiring electrodes. [Brief Description of the Drawings]

[0010]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Embodiment for Carrying out the Invention

[0011] In the present invention, a photosensitive resin composition is applied to an LED mounting substrate on which a plurality of substrates having wiring electrodes, bumps formed on the wiring electrodes, and LED elements mounted on the bumps are mounted, and the gap between the LED element and the substrate having the wiring electrodes and the space between adjacent LED elements are collectively filled with a coating film. A step of drying the coating film to form a dry film, a step of exposing the dry film, a step of developing and removing unnecessary portions in the dry film after the exposure, and a step of curing the coating film after the development to form a cured film are sequentially performed. This is a method for manufacturing an LED mounting substrate with a cured film.

[0012] <LED mounting substrate> The LED mounting substrate in the present invention refers to, for example, a substrate as shown in FIGS. 1 and 2. FIG. 1 is a view of the LED mounting substrate seen from above, and FIG. 2 is a cross-sectional view taken along line A-A' of FIG. 1. Wiring electrodes 2 are arranged on and inside the substrate 1, and a part of the wiring electrodes at the portion connected to the LED electrode 3 is exposed. On the exposed wiring electrodes, bumps 4 formed of a conductive material are formed, and the LED element 5 is mounted via the bumps. Examples of the substrate include a glass plate, a resin plate, a resin film, and the like. Examples of the wiring electrodes include metal electrodes and the like. As for the LED element, there may be two LED electrodes on one side or one LED electrode on each of the two sides.

[0013] <Step of providing a coating film of the photosensitive resin composition> As a process of forming a coating film of a photosensitive resin composition on an LED mounting substrate, for example, methods using microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, slit coating, etc. can be mentioned. Among them, from the viewpoint of improving film flatness, spin coating and slit coating are preferable. Using these methods, the gaps between the LED elements and the wiring electrodes on the substrate and the spaces between adjacent LED elements are filled with the coating film. The filling here means providing a coating film in the gaps between the LED elements and the wiring electrodes on the substrate and the spaces between adjacent LED elements. The photosensitive resin composition is preferably a photosensitive colored resin composition. A photosensitive colored resin composition refers to a colored photosensitive resin composition that is not colorless and transparent. By being a photosensitive colored resin composition, the light emission characteristics of the LED mounting substrate are improved by improving the light extraction efficiency from the LED elements and suppressing stray light, etc. Fig. 3 shows a schematic diagram of a state in which a coating film of a photosensitive resin composition is formed on an LED mounting substrate.

[0014] <Process of drying the coating film to form a dry film> As a process of drying the coating film to form a dry film, for example, methods using heating devices such as hot plates, vacuum dryers, vacuum hot plates, ovens, etc. can be mentioned. The drying temperature is preferably 10 to 110 °C, and the drying time is preferably 30 seconds to 30 minutes. Fig. 4 shows a schematic diagram of a state in which a dry film of a photosensitive resin composition is formed on an LED mounting substrate.

[0015] <Process of exposing the dry film> Regarding the process of exposing the dry film, the exposure may be performed through a desired mask or without a mask. Examples of exposure machines include steppers, mirror projection mask aligners (MPA), parallel light mask aligners (hereinafter, "PLA"), etc. The exposure intensity is 10 to 4000 J / m 2The degree (converted to the exposure dose at a wavelength of 365 nm) is common. Examples of the exposure light source include ultraviolet rays such as i-line, g-line, and h-line, KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, and the like. Fig. 5 shows a schematic diagram when exposing the dry film of the photosensitive resin composition through a mask.

[0016] <Step of developing and removing unnecessary portions in the dry film after the exposure> Examples of the step of developing and removing unnecessary portions in the dry film after the exposure include developing methods such as shower, dipping, and paddle. The immersion time in the developer is preferably 5 seconds to 5 minutes. Examples of the developer include inorganic alkalis such as hydroxides, carbonates, phosphates, silicates, and borates of alkali metals, amines such as 2 - diethylaminoethanol, monoethanolamine, and diethanolamine, and alkaline developers such as aqueous solutions containing quaternary ammonium salts such as tetramethylammonium hydroxide and choline. After development, it is preferable to rinse with water. For the purpose of protecting the electrodes, it is preferable to leave the film after development at least around the bumps and the wiring electrodes. As a method, a method of dissolving the dry film from the upper layer and rinsing away the developer when the bottom of the substrate can be visually confirmed can be mentioned. The gap portion of the substrate having the LED element and the wiring electrode has a very small space and it is difficult for the developer to penetrate, so the dissolution of the dry film progresses more slowly compared to other portions. Therefore, it is possible to leave the film after development around the bumps and the wiring electrodes. Fig. 6 shows a schematic diagram of the coated film after development of the photosensitive resin composition formed on the LED mounting substrate. As shown in Fig. 6, it can be seen that the film after development remains in the gap portion.

[0017] <Step of converting the coated film after the development into a cured film> Examples of the step of converting the coated film after the development into a cured film include a thermal curing method of heating by applying heat using a hot plate, an oven, etc., and a photocuring method of irradiating light with an ultraviolet lamp, an LED lamp, etc. The thermal curing temperature is preferably 60 to 230 °C, and the thermal curing time is preferably about 15 minutes to 2 hours. For photocuring, the exposure intensity is 10 to 4000 J / m 2The degree (converted to the exposure amount at a wavelength of 365 nm) is preferable. As a method for curing the coating film after development, from the viewpoint of being able to efficiently cure the coating film after development regardless of the formation location, a thermal curing method is preferable. By making the coating film after development into a cured film, the cross-linking reaction of the resin proceeds, and the reliability of the cured film is improved. FIG. 7 shows a cross-sectional view of a state in which a cured film of the photosensitive resin composition is formed on the LED mounting substrate.

[0018] <Bump> The bump in the present invention is formed on the wiring electrode of the substrate. FIG. 8 shows an example of a substrate on which the bump 4 is formed. The bump in the present invention is preferably formed of a conductive material, and may be a metal such as solder, a mixture with a resin, or the like. The bump in the present invention is more preferably a bump made of a composite material of (A) an organic component and (B) conductive particles. Since the bump made of the composite material of (A) an organic component and (B) conductive particles has low rigidity, the mountability of the LED chip can be improved.

[0019] As a method for forming a bump made of a composite material of (A) an organic component and (B) conductive particles on the wiring electrode, there are a pattern printing method such as screen printing or gravure printing of a photosensitive conductive paste, a laser etching method for removing unnecessary parts after rough pattern printing, a photolithography method by exposing and developing the photosensitive conductive paste, and the like. Among them, since fine patterning is possible, a method of forming a pattern by an exposure and development process using a photosensitive conductive paste is preferable.

[0020] In the photolithography method, as the light source during exposure, an ultra-high pressure mercury lamp, a laser, the i-line (365 nm) or h-line (405 nm) of an LED is preferably used. In the photolithography method, examples of the developer include aqueous solutions of tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, or hexamethylenediamine.

[0021] The shape of the pattern is not particularly limited, and examples include a rectangular shape, a circular shape, an elliptical shape, a triangular shape, a polygonal shape, and combinations thereof. The shape of the pattern can be determined according to the shape of the electrode on the LED side.

[0022] The thickness B of the bump H is preferably 0.1 to 5.0 μm. In the case of the substrate on which the bumps shown in FIG. 8 are formed, the thickness of the bump is denoted by the symbol B H is represented. The thickness B of the bump H By setting the thickness of the bump B to 0.1 μm or more, the impact during LED mounting can be mitigated, and the mountability can be improved. The thickness B of the bump H is more preferably 1.0 μm or more, and even more preferably 1.5 μm or more. Here, "mountability" refers to a state in which the two electrodes of the LED and the two electrodes on the LED mounting substrate side can be electrically connected to each other, and it can be evaluated by applying a voltage to a plurality of fabricated LED mounting substrates and counting the number of lit LEDs. On the other hand, by setting the thickness B of the bump H to 5.0 μm or less, the spread of the bump during mounting can be suppressed, and the mountability can be enhanced by suppressing short-circuiting with the surrounding electrodes. The thickness B of the bump H is more preferably 3.5 μm or less. The thickness of the bump can be measured by non-contact measurement using a laser microscope.

[0023] (A) Organic component (A) The organic component includes those mainly composed of an acrylic copolymer, an epoxy resin, a silicone resin, a polyimide resin, a phenol resin, etc., and preferably contains an acrylic copolymer having a carboxyl group and an epoxy resin. By containing an acrylic copolymer having a carboxyl group and an epoxy resin in the organic component, the carboxyl group and the epoxy group undergo a thermosetting reaction with the organic component in the bump and the insulating layer, so that the adhesion between the LED electrode and the bump after thermocompression bonding can be improved, and the connection reliability can be further enhanced.

[0024] As the carboxyl group-containing acrylic copolymer, a copolymer of an acrylic monofunctional monomer and an unsaturated acid or its acid anhydride is preferred.

[0025] Examples of acrylic monofunctional monomers include methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, n-butyl acrylate, isobutyl acrylate, isopropane acrylate, glycidyl acrylate, butoxy triethylene glycol acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, 2-hydroxypropyl acrylate, isodecyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, octafluoropentyl acrylate, phenoxyethyl acrylate, stearyl acrylate, trifluoroethyl acrylate, aminoethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, thiophenol acrylate, benzyl mercaptan acrylate, acrylamide, N-methoxymethyl acrylamide, N-ethoxymethyl acrylamide, N-n-butoxymethyl acrylamide, N-isobutoxymethyl acrylamide, methacryl phenol, methacrylamide phenol, γ-acryloxypropyltrimethoxysilane, N-(2-hydroxyphenyl)acrylamide, N-(3-hydroxyphenyl)acrylamide, N-(4-hydroxyphenyl)acrylamide, o-hydroxyphenyl acrylate, m-hydroxyphenyl acrylate, p-hydroxyphenyl acrylate, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2-(2-hydroxyphenyl)ethyl acrylate, 2-(3-hydroxyphenyl)ethyl acrylate, 2-(4-hydroxyphenyl)ethyl acrylate, and the like. Two or more of these may be used. Among these, ethyl acrylate, 2-hydroxyethyl acrylate, and isobornyl acrylate are preferred.

[0026] Examples of the unsaturated acid or its acid anhydride include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetate, and acid anhydrides thereof. Two or more of these may be used. The acid value of the carboxyl group-containing acrylic copolymer can be adjusted by the copolymerization ratio of the unsaturated acid.

[0027] Examples of the epoxy resin include bisphenol A type, cresol novolak type, phenol novolak type, bisphenol A novolak type, dicyclopentadiene type, naphthalene type, etc. Among them, those having a softening point of 30°C or higher and 100°C or lower are preferable. If the softening point is 30°C or higher, the occurrence of short-circuit defects with adjacent bumps due to excessive flow during heat pressure bonding can be suppressed, and if it is 100°C or lower, component mounting at low temperature becomes possible. More specifically, EPICRON N-660, EPICRON N-670, EPICRON N-680, EPICRON N-770, EPICRON N-775, EPICLON 840, EPICRON N-865, EPICRON N-890, EPICRON HP-7200L, EPICRON HP-7200, EPICRON HP-7200H, EPICRON HP-4700 manufactured by DIC Corporation, KAYARAD NC-3000, NC-3000H manufactured by Nippon Kayaku Co., Ltd., etc. are included. Two or more of these may be used.

[0028] (B) Conductive particles (B) Examples of the conductive particles include particles such as silver, gold, copper, platinum, lead, tin, nickel, aluminum, tungsten, molybdenum, chromium, titanium, indium, magnesium, cobalt, zinc, potassium, lithium, iron, mercury, beryllium, cadmium, rhodium, ruthenium, iridium, and alloys thereof, and carbon black. Two or more of these may be contained. Among these, from the viewpoint of conductivity, metal particles selected from silver, gold, and copper are preferable, and silver particles are more preferable from the viewpoints of cost and stability. Further, the (B) conductive particles may be those having a surface coated with a resin, an inorganic oxide, or the like. Conductive particles having the surface of resin particles coated with a metal are preferable because of the elastic repulsion by the resin particles during transfer.

[0029] The aspect ratio, which is the value obtained by dividing the major axis length of the (B) conductive particles by the minor axis length, is preferably 1.1 to 2.0. Here, the aspect ratio of the (B) conductive particles can be calculated from the average values of the major axis lengths and minor axis lengths of 100 randomly selected primary particles of the (B) conductive particles observed at a magnification of 15,000 times using a scanning electron microscope (SEM) or a transmission electron microscope (TEM).

[0030] The average particle diameter of the (B) conductive particles is preferably 0.05 to 1.0 μm. When the average particle diameter is 0.05 μm or more, the number of conductive paths in the bump increases, and the electrical connection reliability can be further enhanced. On the other hand, when the average particle diameter is 1.0 μm or less, the surface smoothness, pattern accuracy, and dimensional accuracy of the obtained bump can be improved. Here, the average particle diameter of the (B) conductive particles can be measured using a laser irradiation type particle size distribution meter. The D50 value of the particle size distribution obtained by the measurement is taken as the average particle diameter (D50) of the conductive particles.

[0031] (A) It is preferable that the proportion of (B) conductive particles in the total weight of the bump made of the composite material of the organic component and (B) conductive particles is 50 to 90 wt%. When the proportion of (B) conductive particles is 50 wt% or more, the number of conductive paths formed in the bump increases, and the electrical connection reliability can be further improved. The proportion of (B) conductive particles is more preferably 60 wt% or more. Also, when the proportion of (B) conductive particles is 90 wt% or less, the rigidity of the bump decreases and the catching property increases, so that the positioning accuracy can be increased and the mountability can be further improved. In addition, by increasing the content of the organic component and improving the adhesion between the bump and the electrode of the LED, the connection reliability can be further improved. The proportion of (B) conductive particles is more preferably 80 wt% or less. The proportion of (B) conductive particles in the total weight of the bump can be calculated from the residual weight obtained by scraping off the bump on the substrate and burning off the organic component by thermogravimetric analysis.

[0032] <Photosensitive resin composition> The photosensitive resin composition of the present invention is a material whose solubility in a developer changes by the action of light. From the viewpoint of improving the reflectance and light-shielding property of the cured film, it is preferable that the photosensitive resin composition of the present invention contains (G) a coloring pigment. The photosensitive resin composition containing (G) a coloring pigment becomes a photosensitive colored resin composition. Further, as the photosensitive colored resin composition of the present invention, in addition to (G) a coloring pigment, it is preferable to contain (C) a resin, (D) a photopolymerization initiator, (E) a photopolymerizable compound, and (F) an organic solvent. The viscosity of the photosensitive colored resin composition of the present invention at 25°C is preferably 30 mPa·s or less, more preferably 10 mPa·s, from the viewpoint of filling the gap between the LED element and the wiring electrode on the substrate and the space between adjacent LED elements without defects such as bubbles. It is preferable because the reliability of the LED element can be improved by filling the gap between the LED element and the wiring electrode on the substrate and the space between adjacent LED elements without defects. On the other hand, from the viewpoint of suppressing fluidity and improving the film thickness uniformity of the coating film, it is preferably 1 mPa·s or more, more preferably 2 mPa·s or more. The viscosity is the value at 100 rpm measured by a cone plate type viscometer with the temperature set at 25.0 ± 0.2°C.

[0033] (C) Resin Examples of the (C) resin include siloxane, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, (meth)acrylic polymer, etc. Here, the (meth)acrylic polymer means a polymer of methacrylic acid ester and / or acrylic acid ester. Two or more of these may be contained. Among these, (C-1) siloxane resin is preferred because of its excellent transparency, heat resistance and light resistance.

[0034] (C-1) Siloxane resin is a hydrolyzed and dehydrated condensate of organosilane, and in the present invention, it contains at least a repeating unit represented by formula (1) and / or a repeating unit represented by formula (2).

[0035]

Chemical formula

[0036] In formula (1) and formula (2), R 2 represents a linear alkylene group having 1 to 6 carbon atoms, R 1 represents a hydrogen atom or a methyl group, and R 3 represents an alkyl group having 1 to 20 carbon atoms. * represents a bonding site.

[0037] By containing these repeating units, the (D) photoinitiator cleaves during exposure, and the side chain of the siloxane resin reacts with the generated radicals. As a result, the contrast in the degree of curing between the exposed part and the unexposed part is likely to occur, so that the resolution can be further improved and the development residue can be further suppressed.

[0038] (C-1) The siloxane resin is characterized by containing a total of 10 to 50 mol% of the repeating unit represented by formula (1) and the repeating unit represented by formula (2) in all the repeating units of the siloxane resin. By containing 10 mol% or more of the total content of the repeating unit represented by formula (1) and formula (2), the contrast in the degree of curing between the exposed part and the unexposed part is obtained, and the resolution can be improved. On the other hand, by containing these repeating units at 50 mol% or less, excessive curing of the exposed part can be suppressed, and the resolution can be further improved.

[0039] The content ratio of the organosilane unit containing the repeating unit represented by formula (1) and the repeating unit represented by formula (2) is 29 It can be determined by performing Si-NMR measurement and calculating the ratio of the integral value of Si derived from the organosilane unit having the repeating unit represented by formula (1) and the repeating unit represented by formula (2) to the integral value of the total Si derived from the organosilane. Further, the siloxane resin preferably contains a repeating unit represented by formula (3) and / or a repeating unit represented by formula (4).

[0040]

Chemical formula

[0041] In formula (3) and formula (4), R 4 represents a monovalent organic group having 1 to 20 carbon atoms with a carboxyl group and / or a carboxylic anhydride group. R 5 represents an alkyl group having 1 to 20 carbon atoms. * represents a bonding site. By containing the repeating unit represented by formula (3) and / or the repeating unit represented by formula (4), it has excellent developability solubility and can improve the resolution.

[0042] Further, the repeating unit represented by the formula (3) and the repeating unit represented by the formula (4) are preferably contained in an amount of 5 to 20 mol% in all the repeating units of the siloxane resin. By containing these repeating units in an amount of 5 mol% or more, development residues can be further suppressed. On the other hand, by containing these repeating units in an amount of 20 mol% or less, the resolution can be further improved.

[0043] The content ratio of the organosilane unit containing the repeating unit represented by the formula (3) and the repeating unit represented by the formula (4) is 29 It can be determined by performing Si-NMR measurement and calculating the ratio of the integral value of Si derived from the organosilane unit having the repeating unit represented by the formula (3) and the repeating unit represented by the formula (4) to the integral value of the total Si derived from the organosilane. In addition, the (C-1) siloxane resin may contain other repeating units. As the other repeating units, repeating units having non-aromatic functional groups are preferable, and by having these repeating units, the light resistance can be improved.

[0044] The repeating units represented by the formulas (1) to (4) are each derived from the organosilane compounds represented by the formulas (5) to (8). That is, the repeating unit represented by the formula (1) and / or the repeating unit represented by the formula (2) is derived from the organosilane compound represented by the formula (5) and / or the organosilane compound represented by the formula (6). The repeating unit represented by the formula (3) and / or the repeating unit represented by the formula (4) is derived from the organosilane compound represented by the formula (7) and / or the organosilane compound represented by the formula (8). The (C-1) polysiloxane resin having the repeating units represented by the formulas (1) to (4) can be obtained by hydrolyzing and polycondensing the corresponding organosilane compounds represented by the formulas (5) to (8). Further, other organosilane compounds may be used.

[0045]

Chemical formula

[0046] In the above formulas (5) and (6), R 1 , R 2 and R 3 represent the same groups as R 1 , R 2 and R 3 in formulas (1) and (2), respectively. R a may be the same or different and each represents a monovalent organic group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms. In the above formulas (7) and (8), R 4 and R 5 represent the same groups as R 4 and R 5 in formulas (3) and (4), respectively. R a represents the same group as R a in the above formulas (5) and (6).

[0047] Examples of the organosilane compound represented by formula (5) include γ-acryloylpropyltrimethoxysilane, γ-acryloylpropyltriethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-methacryloylpropyltriethoxysilane, etc. Two or more of these may be used. Examples of the organosilane compound represented by formula (6) include γ-acryloylpropylmethyldimethoxysilane, γ-acryloylpropylmethyldiethoxysilane, γ-methacryloylpropylmethyldimethoxysilane, γ-methacryloylpropylmethyldiethoxysilane, etc. Two or more of these may be used. Examples of the organosilane compound having the structure represented by the formula (7) include 3-trimethoxysilylpropionic acid, 3-triethoxysilylpropionic acid, 4-trimethoxysilylbutyric acid, 4-triethoxysilylbutyric acid, 5-trimethoxysilylvaleric acid, 5-triethoxysilylvaleric acid, 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, 3-trimethoxysilylpropyl cyclohexyl dicarboxylic anhydride, 3-triethoxysilylpropyl cyclohexyl dicarboxylic anhydride, 3-trimethoxysilylpropyl phthalic anhydride, 3-triethoxysilylpropyl phthalic anhydride, and the like. Two or more of these may be used. Examples of the organosilane compound having the structure represented by the formula (8) include 3-dimethylmethoxysilylpropionic acid, 3-dimethylethoxysilylpropionic acid, 4-dimethylmethoxysilylbutyric acid, 4-dimethylethoxysilylbutyric acid, 5-dimethylmethoxysilylvaleric acid, 5-dimethylethoxysilylvaleric acid, 3-dimethylmethoxysilylpropyl succinic anhydride, 3-dimethylethoxysilylpropyl succinic anhydride, 3-dimethylmethoxysilylpropyl cyclohexyl dicarboxylic anhydride, 3-dimethylethoxysilylpropyl cyclohexyl dicarboxylic anhydride, and the like. Two or more of these may be used. Examples of other organosilane compounds include organosilane compounds such as tetramethoxysilane, tetraethoxysilane, and Silicate 51 (tetraethoxysilane oligomer). Two or more of these may be used.

[0048] (C-1) From the viewpoint of coating properties, the weight average molecular weight (Mw) of the siloxane resin is preferably 1,000 or more, more preferably 2,000 or more. On the other hand, from the viewpoint of developability, the Mw of the (A) siloxane resin is preferably 50,000 or less, more preferably 20,000 or less. Here, the Mw of the siloxane resin in the present invention refers to the polystyrene conversion value measured by gel permeation chromatography (GPC).

[0049] In the photosensitive colored resin composition, the content of the (C) resin can be arbitrarily set according to the desired film thickness and application, but it is generally 10 to 50% by weight in the solid content of the photosensitive colored resin composition. Further, the content of the (C) resin is preferably 10% by weight or more, more preferably 20% by weight or more in the solid content of the photosensitive colored resin composition. On the other hand, the content of the (C) resin is preferably 50% by weight or less in the solid content of the photosensitive colored resin composition.

[0050] (C-1) The siloxane resin can be obtained by hydrolyzing the aforementioned organosilane compound and then subjecting the hydrolyzate to a dehydration condensation reaction in the presence of a solvent or without a solvent. Various conditions in the hydrolysis can be set according to the physical properties suitable for the intended application in consideration of the reaction scale, the size and shape of the reaction vessel, etc. Examples of the various conditions include acid concentration, reaction temperature, reaction time, etc.

[0051] For the hydrolysis reaction, acid catalysts such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polyvalent carboxylic acids and their anhydrides, and ion exchange resins can be used. Among these, an acidic aqueous solution containing formic acid, acetic acid and / or phosphoric acid is preferred. When an acid catalyst is used in the hydrolysis reaction, the addition amount of the acid catalyst is preferably 0.05 part by weight or more, more preferably 0.1 part by weight or more, based on 100 parts by weight of the total organosilane compounds used in the hydrolysis reaction, from the viewpoint of allowing the hydrolysis to proceed more rapidly. On the other hand, from the viewpoint of appropriately adjusting the progress of the hydrolysis reaction, the addition amount of the acid catalyst is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the total organosilane compounds. Here, the total amount of the organosilane compounds refers to the amount including all of the organosilane compound, its hydrolyzate and its condensate, and the same shall apply hereinafter.

[0052] The hydrolysis reaction can be carried out in an organic solvent. Considering the stability, wettability, volatility, etc. of the photosensitive coloring resin composition, the organic solvent can be appropriately selected. Examples of the organic solvent include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxy-1-butanol, diacetone alcohol; glycols such as ethylene glycol, propylene glycol; ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethyl ether; ketones such as methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, 2-heptanone; amides such as dimethylformamide, dimethylacetamide; acetates such as ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, butyl lactate; aromatic or aliphatic hydrocarbons such as toluene, xylene, hexane, cyclohexane; γ-butyrolactone, N-methyl-2-pyrrolidone, dimethyl sulfoxide, etc. Two or more of these may be used.

[0053] Among these, from the viewpoint of crack resistance of the cured film and the like, diacetone alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, γ-butyrolactone and the like are preferably used.

[0054] When an organic solvent is generated by the hydrolysis reaction, it is also possible to perform hydrolysis without a solvent. After completion of the hydrolysis reaction, it is also preferable to adjust to an appropriate concentration as a photosensitive coloring composition by further adding an organic solvent. Further, after hydrolysis, it is also possible to distill and remove all or part of the generated alcohol or the like under heating and / or reduced pressure, and then add a suitable organic solvent.

[0055] When an organic solvent is used in the hydrolysis reaction, the addition amount of the organic solvent is preferably 50 parts by weight or more, more preferably 80 parts by weight or more, based on 100 parts by weight of the total organosilane compound, from the viewpoint of suppressing the formation of gel. On the other hand, the addition amount of the organic solvent is preferably 500 parts by weight or less, more preferably 200 parts by weight or less, based on 100 parts by weight of the total organosilane compound, from the viewpoint of allowing the hydrolysis to proceed more rapidly.

[0056] Further, as the water used in the hydrolysis reaction, ion-exchanged water is preferable. The amount of water can be set arbitrarily, but is preferably 1.0 to 4.0 moles per 1 mole of the total organosilane compound.

[0057] Examples of the dehydration condensation reaction method include heating the silanol compound solution obtained by the hydrolysis reaction of an organosilane compound as it is. The heating temperature is preferably 50°C or higher and lower than the boiling point of the solvent, and the heating time is preferably 1 to 100 hours. Further, in order to increase the degree of polymerization of the siloxane resin, reheating or addition of a base catalyst may be performed. Further, depending on the purpose, after hydrolysis, an appropriate amount of the produced alcohol or the like may be distilled off and removed under heating and / or reduced pressure, and then a suitable solvent may be added.

[0058] From the viewpoint of the storage stability of the photosensitive colored resin composition, it is preferable that the siloxane resin solution after hydrolysis and dehydration condensation does not contain the catalyst, and the catalyst can be removed as necessary. As the catalyst removal method, from the viewpoints of simplicity of operation and removability, washing with water, treatment with an ion exchange resin, etc. are preferable. Washing with water is a method in which the siloxane resin solution is diluted with an appropriate hydrophobic solvent and then washed several times with water, and the obtained organic layer is concentrated with an evaporator or the like. Treatment with an ion exchange resin is a method in which the siloxane resin solution is brought into contact with an appropriate ion exchange resin.

[0059] (D) Photoinitiator (D) The photoinitiator may be any one that decomposes and / or reacts by light (including ultraviolet rays and electron beams) to generate radicals. For example, α-aminoalkylphenone compounds such as 2-methyl-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1; acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyl phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-phosphine oxide; oxime ester compounds such as 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], 1-phenyl-1,2-butadione-2-(O-methoxycarbonyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetoxyoxime); benzyl ketal compounds such as benzyldimethyl ketal; α-hydroxyketone compounds such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl-phenylketone; benzophenone compounds such as benzophenone, 4,4-bis(dimethylamino)benzophenone, 4,4-bis(diethylamino)benzophenone, methyl O-benzoylbenzoate, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, alkylated benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone;Acetophenone compounds such as 2,2 - diethoxyacetophenone, 2,3 - diethoxyacetophenone, 4 - t - butyldichloroacetophenone, benzalacetophenone, 4 - azidobenzalacetophenone; aromatic ketoester compounds such as methyl 2 - phenyl - 2 - oxyacetate; benzoic acid ester compounds such as ethyl 4 - dimethylaminobenzoate, (2 - ethyl)hexyl 4 - dimethylaminobenzoate, ethyl 4 - diethylaminobenzoate, methyl 2 - benzoylbenzoate, etc. These may contain two or more of them.;

[0060] In order to suppress the coloring by the (D) photoinitiator, the photosensitive colored resin composition preferably uses an acylphosphine oxide - based photoinitiator such as 2,4,6 - trimethylbenzoyl phenylphosphine oxide, bis(2,4,6 - trimethylbenzoyl)-phenylphosphine oxide, bis(2,6 - dimethoxybenzoyl)-(2,4,4 - trimethylpentyl)-phosphine oxide, etc.

[0061] From the viewpoint of effectively promoting radical curing, the content of the (D) photoinitiator in the photosensitive colored resin composition is preferably 0.01% by weight or more, more preferably 1% by weight or more in the solid content. On the other hand, from the viewpoint of suppressing the elution etc. of the remaining (D) photoinitiator, the content of the (D) photoinitiator is preferably 20% by weight or less, more preferably 10% by weight or less in the solid content.

[0062] (E) Photopolymerizable compound (E) The photopolymerizable compound refers to a compound having two or more ethylenically unsaturated double bonds in the molecule. Considering the ease of radical polymerization, the (E) photopolymerizable compound preferably has a (meth)acrylic group. Also, from the viewpoint of further improving the sensitivity in pattern processing, the double - bond equivalent of the (E) photopolymerizable compound is preferably 400 g / mol or less. On the other hand, from the viewpoint of further improving the resolution in pattern processing, the double - bond equivalent of the (E) photopolymerizable compound is preferably 80 g / mol or more.

[0063] Examples of the above (E) photopolymerizable compound include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,3 - butanediol diacrylate, 1,3 - butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4 - butanediol diacrylate, 1,4 - butanediol dimethacrylate, 1,6 - hexanediol diacrylate, 1,9 - nonanediol dimethacrylate, 1,10 - decanediol dimethacrylate, dimethylol - tricyclodecane diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, tetrapentaerythritol nonaacrylate, tetrapentaerythritol decaacrylate, pentapentaerythritol undecaacrylate, pentapentaerythritol dodecaacrylate, tripentaerythritol heptamethacrylate, tripentaerythritol octamethacrylate, tetrapentaerythritol nonamethacrylate, tetrapentaerythritol decamethacrylate, pentapentaerythritol undecamethacrylate, pentapentaerythritol dodecamethacrylate, dimethylol - tricyclodecane diacrylate. Two or more of these may be contained.

[0064] From the viewpoint of effectively promoting radical curing, the content of the (E) photopolymerizable compound in the photosensitive colored resin composition is preferably 1% by weight or more in the solid content of the photosensitive colored resin composition. On the other hand, from the viewpoint of suppressing the excessive reaction of radicals and further improving the resolution, the content of the (E) photopolymerizable compound is preferably 40% by weight or less in the solid content.

[0065] (F) Organic solvent The photosensitive colored resin composition of the present invention preferably contains an (F) organic solvent. As the organic solvent, it is preferable to combine an organic solvent having a boiling point of 150°C or higher and 250°C or lower under atmospheric pressure with an organic solvent having a boiling point of less than 150°C. By containing an organic solvent having a boiling point of 150°C or higher and 250°C or lower, the organic solvent volatilizes moderately during coating, and the drying of the coating film proceeds, so that coating unevenness can be suppressed and film thickness uniformity can be improved. Furthermore, by containing an organic solvent having a boiling point of less than 150°C under atmospheric pressure, the remaining of the organic solvent in the cured film of the present invention described later can be suppressed. From the viewpoint of suppressing the remaining of the organic solvent in the cured film and improving chemical resistance and adhesion for a longer period, it is preferable to contain an organic solvent having a boiling point of less than 150°C under atmospheric pressure in an amount of 50% by weight or more of the total organic solvent.

[0066] Examples of organic solvents having a boiling point of less than 150°C under atmospheric pressure include ethanol, isopropyl alcohol, 1-propyl alcohol, 1-butanol, 2-butanol, isopentyl alcohol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, methoxymethyl acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether, ethylene glycol monomethyl ether acetate, 1-methoxypropyl-2-acetate, acetol, acetylacetone, methyl isobutyl ketone, methyl ethyl ketone, methyl propyl ketone, methyl lactate, toluene, cyclopentanone, cyclohexane, normal heptane, benzene, methyl acetate, ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, and 5-hydroxy-2-pentanone. Two or more of these may be used.

[0067] Examples of the organic solvent having a boiling point of 150°C or higher and 250°C or lower under atmospheric pressure include ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-tert-butyl ether, propylene glycol mono n-butyl ether, propylene glycol mono t-butyl ether, 2-ethoxyethyl acetate, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether propionate, dipropylene glycol methyl ether, diisobutyl ketone, diacetone alcohol, ethyl lactate, butyl lactate, dimethylformamide, dimethylacetamide, γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, N-methylpyrrolidone, cyclohexanone, cycloheptanone, diethylene glycol monobutyl ether, and ethylene glycol dibutyl ether. Two or more of these may be used.

[0068] The content of the organic solvent can be arbitrarily set according to the coating method and the like. For example, when forming a film by spin coating, it is generally 50% by weight or more and 95% by weight or less in the photosensitive colored resin composition.

[0069] (G) Coloring pigment The photosensitive colored resin composition of the present invention preferably contains a (G) coloring pigment. By containing the (G) coloring pigment, the light-shielding property of the cured film can be improved. Further, it is more preferable to contain at least a (G-1) white pigment as the coloring pigment. By containing the (G-1) white pigment, it becomes possible to improve the reflectance of the cured film. Examples of the (G-1) white pigment include titanium dioxide, magnesium oxide, barium sulfate, zirconium oxide, zinc oxide, lead white, and the like. Two or more of these may be contained. Among these, it is preferable to contain at least one of titanium dioxide, zirconium oxide, zinc oxide, barium sulfate, and composite compounds thereof, and titanium dioxide having a high reflectance and being easily industrially used is more preferable.

[0070] The crystal structure of titanium dioxide is classified into anatase type, rutile type, and brookite type. Among these, rutile-type titanium dioxide is preferred because of its low photocatalytic activity. (G-1) The white pigment may be surface-treated. Surface treatment with Al, Si, and / or Zr is preferred, which can improve the dispersibility of the (G-1) white pigment in the photosensitive coloring resin composition and further improve the light resistance and heat resistance of the cured film. (G-1) From the viewpoint of further improving the reflectance, the average primary particle diameter of the white pigment is preferably 170 to 310 nm. Here, the average primary particle diameter of the (G-1) white pigment refers to the median diameter calculated from the particle size distribution measured by the laser diffraction method.

[0071] Examples of the titanium dioxide pigment preferably used as the (G-1) white pigment include R960; manufactured by DuPont (rutile type, SiO2 / Al2O3 treatment, average primary particle diameter 210 nm), CR-97; manufactured by Ishihara Sangyo Co., Ltd. (rutile type, Al2O3 / ZrO2 treatment, average primary particle diameter 250 nm), JR-301; manufactured by Teika Co., Ltd. (rutile type, Al2O3 treatment, average primary particle diameter 300 nm), JR-405; manufactured by Teika Co., Ltd. (rutile type, Al2O3 treatment, average primary particle diameter 210 nm), JR-600A; Teika Co., Ltd. (rutile type, Al2O3 treatment, average primary particle diameter 250 nm), JR-603; Teika Co., Ltd. (rutile type, Al2O3 / ZrO2 treatment, average primary particle diameter 280 nm), etc. Two or more of these may be contained.

[0072] (G-1) From the viewpoint of further improving the reflectance, the content of the white pigment is preferably 10% by weight or more, more preferably 20% by weight or more, based on the solid content of the photosensitive coloring resin composition. On the other hand, from the viewpoint of suppressing development residues and forming a higher-resolution pattern, the content of the (G-1) white pigment is preferably 80% by weight or less, more preferably 60% by weight or less, based on the solid content.

[0073] The photosensitive colored resin composition may contain a pigment dispersant together with the (G-1) white pigment, and the dispersibility of the (G-1) white pigment in the photosensitive colored resin composition can be improved. The pigment dispersant can be appropriately selected according to the type and surface state of the white pigment used. The pigment dispersant preferably contains an acidic group and / or a basic group. Examples of commercially available pigment dispersants include "Disperbyk" (registered trademark) 106, "Disperbyk" 108, "Disperbyk" 110, "Disperbyk" 180, "Disperbyk" 190, "Disperbyk" 2001, "Disperbyk" 2155, "Disperbyk" 140, "Disperbyk" 145 (all of the above are product names, manufactured by BYK-Chemie Co., Ltd.), etc. Two or more of these may be contained.

[0074] Further, the photosensitive coloring resin composition of the present invention may contain (H) a black pigment if necessary. By containing (H) a black pigment, the light-shielding property of the cured film can be improved. Examples of the (H) black pigment include black organic pigments, mixed-color organic pigments, black inorganic pigments, and the like. Examples of the black organic pigment include carbon black, perylene black, aniline black, benzofuranone-based pigments, and the like. These may be coated with a resin. Examples of the mixed-color organic pigment include those obtained by mixing two or more pigments such as red, blue, green, purple, yellow, magenta, and / or cyan to pseudo-blacken. Among these, from the viewpoint of achieving both an appropriately high OD value and pattern processability, a mixed pigment of a red pigment and a blue pigment is preferable. The weight ratio of the red pigment to the blue pigment is preferably 20 / 80 to 80 / 20, more preferably 30 / 70 to 70 / 30. Specific examples of representative pigments shown by Color Index (CI) numbers are as follows. Examples of the red pigment include Pigment Red (hereinafter abbreviated as PR) 9, PR48, PR97, PR122, PR123, PR144, PR149, PR166, PR168, PR177, PR179, PR180, PR192, PR209, PR215, PR216, PR217, PR220, PR223, PR224, PR226, PR227, PR228, PR240, PR254, and the like. Two or more of these may be contained. Examples of the blue pigment include Pigment Blue (hereinafter abbreviated as PB) 15, PB15:3, PB15:4, PB15:6, PB22, PB60, PB64, and the like. Two or more of these may be contained. Examples of the black inorganic pigment include graphite; fine particles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, gold, platinum, palladium; metal oxides; metal composite oxides; metal sulfides; metal nitrides; metal oxynitrides; metal carbides, and the like. Two or more of these may be contained.

[0075] Among the above black pigments, since they have high light-shielding properties, it is more preferable to contain at least one or more of titanium nitride, zirconium nitride, carbon black, and a mixed pigment of a red pigment and a blue pigment. From the viewpoint of adjusting the reflectance and OD to suppress the color mixing of light in adjacent pixels, the content of the black pigment is preferably 0.2% by weight or more, and more preferably 0.5% by weight or more. On the other hand, from the viewpoint of adjusting the reflectance and OD, the content of the black pigment is preferably 5% by weight or less, and more preferably 3% by weight or less.

[0076] In addition, the photosensitive colored resin composition of the present invention can contain (I) an organometallic compound as necessary. The (I) organometallic compound has a function of improving the light-shielding property by decomposing and aggregating to become a black pigment in the exposure step and / or the heating step during the pattern formation of the cured film. As the (I) organometallic compound, since it has high light-shielding properties, it is more preferable to contain at least one metal selected from the group consisting of silver, gold, platinum, and palladium. Examples of the metal compound selected from the group consisting of silver, gold, platinum, and palladium include organometallic compounds containing silver such as silver neodecanoate, silver octylate, and silver salicylate; organometallic compounds containing gold such as chloro(triphenylphosphine)gold and tetrachloroauric acid tetrahydrate; organometallic compounds containing platinum such as bis(acetylacetonato)platinum, dichlorobis(triphenylphosphine)platinum, and dichlorobis(benzonitrile)platinum; and organometallic compounds containing palladium such as bis(acetylacetonato)palladium, dichlorobis(triphenylphosphine)palladium, dichlorobis(benzonitrile)palladium, tetrakis(triphenylphosphine)palladium, and dibenzylideneacetone palladium. Two or more of these may be contained. Among these, from the viewpoint of further improving the light-shielding property, bis(acetylacetonato)palladium, dichlorobis(triphenylphosphine)palladium, dichlorobis(benzonitrile)palladium, and tetrakis(triphenylphosphine)palladium are more preferable.

[0077] The content of the organometallic compound (I) in the solid content of the photosensitive colored resin composition is preferably 0.2 to 5% by weight. By setting the content of the organometallic compound to 0.2% by weight or more, the OD value can be further improved. The content of the organometallic compound is more preferably 1.5% by weight or more. On the other hand, by setting the content of the organometallic compound to 5% by weight or less, the reflectance can be further improved.

[0078] In addition, the photosensitive colored resin composition of the present invention may further contain a crosslinking agent, an ultraviolet absorber, a polymerization inhibitor, a surfactant, etc., if necessary. When the photosensitive colored resin composition contains a crosslinking agent, the crosslinking of the siloxane resin is promoted during thermosetting, and the degree of crosslinking of the cured film becomes high. Therefore, a decrease in pattern resolution due to melting of the fine pattern during thermosetting is suppressed. Examples of the curing agent include nitrogen-containing organic substances, silicone resin curing agents, isocyanate compounds and their polymers, methylolated melamine derivatives, methylolated urea derivatives, various metal alcoholates, various metal chelate compounds, thermal acid generators, photoacid generators, and the like. Two or more of these may be contained. Among these, from the viewpoints of the stability of the curing agent and the processability of the coating film, methylolated melamine derivatives, methylolated urea derivatives, and photoacid generators are preferably used.

[0079] When the photosensitive colored resin composition contains an ultraviolet absorber, the light resistance of the cured film can be improved, and the resolution can be further improved. From the viewpoint of further suppressing color change due to heating, as the ultraviolet absorber, benzotriazole-based compounds such as 2-(2H-benzotriazol-2-yl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-tert-pentylphenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol, 2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole; benzophenone-based compounds such as 2-hydroxy-4-methoxybenzophenone; triazine-based compounds such as 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol are preferably used. Two or more of these may be contained.

[0080] When the photosensitive colored resin composition contains a polymerization inhibitor, the resolution can be improved. Examples of the polymerization inhibitor include di-t-butylhydroxytoluene, butylhydroxyanisole, hydroquinone, 4-methoxyphenol, 1,4-benzoquinone, and t-butylcatechol. Examples of commercially available polymerization inhibitors include "IRGANOX" (registered trademark) 1010, "IRGANOX" 1035, "IRGANOX" 1076, "IRGANOX" 1098, "IRGANOX" 1135, "IRGANOX" 1330, "IRGANOX" 1726, "IRGANOX" 1425, "IRGANOX" 1520, "IRGANOX" 245, "IRGANOX" 259, "IRGANOX" 3114, "IRGANOX" 565, "IRGANOX" 295 (above, trade names, manufactured by BASF Japan Ltd.). Two or more of these may be contained.

[0081] When the photosensitive colored resin composition contains a surfactant, the flowability during coating can be improved. Examples of the surfactant include fluorosurfactants such as "Megafac" (registered trademark) F142D, "Megafac" F172, "Megafac" F173, "Megafac" F183, "Megafac" F445, "Megafac" F470, "Megafac" F475, "Megafac" F477 (above are trade names, manufactured by DIC Corporation); silicone surfactants such as "BYK" (registered trademark)-333, "BYK"-301, "BYK"-331, "BYK"-345, "BYK"-307 (above are trade names, manufactured by BYK-Chemie Japan Co., Ltd.); polyalkylene oxide surfactants; poly(meth)acrylate surfactants, and the like. Two or more of these may be contained.

[0082] The solid content concentration of the photosensitive colored resin composition of the present invention can be arbitrarily set according to the coating method and the like. For example, when forming a film by spin coating as described later, it is general to set the solid content concentration to 5% by weight or more and 50% by weight or less. The solid content here means all the components in the photosensitive colored resin composition excluding volatile components such as solvents. The amount of the solid content can be determined by weighing the residue obtained by heating the photosensitive colored resin composition at 250 °C for 30 minutes to evaporate the volatile components.

[0083] Next, the manufacturing method of the photosensitive colored resin composition of the present invention will be described below. The photosensitive colored resin composition of the present invention can be obtained by mixing the above-mentioned components (C) to (G) and other components as necessary. More specifically, for example, it is preferable to stir and dissolve (C) resin, (D) photoinitiator, (E) photopolymerizable compound, (F) organic solvent, (G) coloring pigment and other components as necessary, and then filter.

[0084] Next, the LED mounting substrate with a cured film of the present invention will be described. The LED mounting substrate with a cured film of the present invention is composed of the aforementioned LED mounting substrate with a cured film formed from a cured product of the photosensitive resin composition of the present invention. The film thickness of the cured film is preferably 0.5 to 25 μm. By setting the film thickness of the cured film to 0.5 μm or more, the cured film can be sufficiently formed in the gap between the LED element and the substrate having the wiring electrode, which is preferable because the reliability of the LED element can be improved. Also, by setting the film thickness of the cured film to 25 μm or less, the film uniformity of the cured film can be improved, which is preferable.

[0085] Subsequently, the element including the LED mounting substrate with a cured film in the present invention will be described. The element including the LED mounting substrate with a cured film of the present invention is formed by forming bumps made of a composite material of an organic component and conductive particles on a substrate having electrodes, then mounting a plurality of LED elements on the bumps, and at least a part of the periphery of the bumps and the LED elements is covered with a cured film of the photosensitive resin composition of the present invention, and an LED mounting substrate having a cured film of the photosensitive resin composition is also provided between adjacent LD elements, and a driving IC driver or the like can be attached thereto. It is preferable that the cured film covering a part of the periphery of the bumps and the LED elements and the cured film between adjacent LD elements have the same composition. By using materials having the same composition for the cured film covering a part of the periphery of the bumps and the LED elements and the cured film between adjacent LD elements, they can be formed collectively, and the productivity can be improved.

Examples

[0086] Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Among the compounds used in the synthesis examples and examples, for those using abbreviations, the contents are shown below. PGMEA: Propylene glycol monomethyl ether acetate DAA: Diacetone alcohol.

[0087] The solid content concentrations of the polysiloxane solution and the acrylic resin solution in Synthesis Examples 1 to 2 were determined by the following method. 1.5 g of the polysiloxane solution or the acrylic resin solution was weighed into an aluminum cup and heated at 250 °C for 30 minutes using a hot plate to evaporate the liquid component. The weight of the solid content remaining in the aluminum cup after heating was weighed, and the solid content concentration of the polysiloxane solution or the acrylic resin solution was determined from the ratio to the weight before heating.

[0088] The weight average molecular weights of the polysiloxane and the acrylic resin in Synthesis Examples 1 to 2 were determined by the following method. Using a GPC analyzer (HLC - 8220; manufactured by Tosoh Corporation), GPC analysis was performed based on "JIS K7252 - 3 (date of promulgation = 2008 / 03 / 20)" using tetrahydrofuran as the mobile phase, and the weight average molecular weight in terms of polystyrene was measured.

[0089] The content ratio of each organosilane unit in the polysiloxane in Synthesis Example 1 was determined by the following method. The polysiloxane solution was injected into an NMR sample tube made of "Teflon" (registered trademark) with a diameter of 10 mm 29 and Si - NMR measurement was carried out. The content ratio of each organosilane unit was calculated from the ratio of the integral value of Si derived from a specific organosilane unit to the integral value of Si derived from all Si in the organosilane. 29 The Si - NMR measurement conditions are shown below. Apparatus: Nuclear magnetic resonance apparatus (JNM - GX270; manufactured by JEOL Ltd.) Measurement method: Gate - decoupling method Measurement nuclear frequency: 53.6693 MHz ( 29 Si nucleus) Spectral width: 20000 Hz Pulse width: 12 μs (45° pulse) Pulse repetition time: 30.0 seconds Solvent: Acetone - d6 Reference substance: Tetramethylsilane Measurement temperature: 23 °C Sample rotation speed: 0.0 Hz.

[0090] Synthesis Example 1: Solution of siloxane resin (c-1) Into a 500 ml three-necked flask, 59.15 g (0.400 mol) of propyltrimethoxysilane, 41.32 g (0.175 mol) of 3-trimethoxysilylpropyl succinic anhydride, 36.60 g (0.175 mol) of 3-methacryloxypropylmethyldimethoxysilane, 11.09 g (0.05 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 24.52 g (0.200 mol) of methyltrimethoxysilane, 0.561 g of BHT, and 122.34 g of PGMEA were charged. While stirring at room temperature, an aqueous phosphoric acid solution in which 1.727 g of phosphoric acid (1.0% by weight based on the charged monomers) was dissolved in 48.60 g of water was added over 30 minutes.

[0091] Thereafter, the flask was immersed in an oil bath at 70 °C and stirred for 90 minutes, and then the temperature of the oil bath was raised to 115 °C over 30 minutes. One hour after the start of heating, the solution temperature (internal temperature) reached 100 °C, and from there, heating and stirring were carried out for 1 hour and 30 minutes (internal temperature: 100 - 110 °C) to obtain a siloxane resin solution. During heating and heating and stirring, a mixed gas of 95% by volume of nitrogen and 5% by volume of oxygen was passed at a flow rate of 0.05 liter / min. A total of 110.70 g of methanol and water, which are by-products, distilled out during the reaction. To the obtained siloxane resin solution, PGMEA was added so that the solid content concentration became 40% by weight to obtain a siloxane resin (c-1) solution. The weight average molecular weight of the obtained siloxane resin (c-1) was 3,700 (in terms of polystyrene). Also, 29 From the measurement results of Si-NMR, the molar ratios of the repeating units derived from propyltrimethoxysilane, 3-trimethoxysilylpropyl succinic anhydride, 3-methacryloxypropylmethyldimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, and methyltrimethoxysilane in the siloxane resin (c-1) were 40 mol%, 17.5 mol%, 17.5 mol%, 5 mol%, and 20 mol%, respectively.

[0092] Synthesis Example 2: Solution of acrylic resin (d-1) 3 g of 2,2'-azobis(isobutyronitrile) and 50 g of PGMEA were charged into a 500 ml three-necked flask. Then, 30 g of methacrylic acid, 35 g of benzyl methacrylate, and 35 g of tricyclo[5.2.1.0 2,6 decane-8-yl methacrylate were charged, stirred at room temperature for a while, the inside of the flask was purged with nitrogen, and then heated and stirred at 70 °C for 5 hours to obtain an acrylic resin solution. PGMEA was added to the obtained acrylic resin solution so that the solid content concentration became 40% by weight, and an acrylic resin (d-1) solution was obtained. The weight average molecular weight of the acrylic resin (d-1) was 10,000 (in terms of polystyrene).

[0093] Synthesis Example 3 Carboxyl group-containing acrylic copolymer (J) having an unsaturated double bond 150 g of diethylene glycol monobutyl ether (hereinafter, "DGME") was charged into a reaction vessel under a nitrogen atmosphere, and the temperature was raised to 80 °C using an oil bath. To this, a mixture consisting of 20 g of ethyl acrylate (hereinafter, "EA"), 40 g of 2-ethylhexyl methacrylate (hereinafter, "2-EHMA"), 20 g of n-butyl acrylate (hereinafter, "BA"), 15 g of N-methylolacrylamide (hereinafter, "MAA"), 0.8 g of 2,2'-azobisisobutyronitrile, and 10 g of DGME was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was further heated at 80 °C for 6 hours to carry out a polymerization reaction. Then, 1 g of hydroquinone monomethyl ether was added to stop the polymerization reaction. Subsequently, a mixture consisting of 5 g of glycidyl methacrylate (hereinafter, "GMA"), 1 g of triethylbenzylammonium chloride, and 10 g of DGME was added dropwise over 0.5 hour. After completion of the dropwise addition, the mixture was further heated for 2 hours to carry out an addition reaction. The obtained reaction solution was purified with methanol to remove unreacted impurities, and further dried under vacuum for 24 hours to obtain a carboxyl group-containing acrylic copolymer (J) having an unsaturated double bond with a copolymerization ratio (by mass): EA / 2-EHMA / BA / GMA / AA = 20 / 40 / 20 / 5 / 15.

[0094] Preparation Example 1 Photosensitive resin composition (P-1) (G-1) As a white pigment, 5.00 g of titanium dioxide pigment (R-960; manufactured by BASF Japan Ltd.) was mixed with 5.00 g of a siloxane resin (c-1) solution as a (C) resin, and dispersed using a mill-type disperser filled with zirconia beads to obtain a pigment dispersion (MW-1).

[0095] Next, 6.400 g of the pigment dispersion (MW-1), 3.425 g of the siloxane resin (c-1) solution, 0.120 g of ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetoxime) (“Irgacure” (registered trademark) OXE-02 (trade name); manufactured by BASF Japan Ltd. (hereinafter referred to as “OXE-02”)) as a (D) photoinitiator, 0.240 g of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (“Irgacure” (registered trademark)-819 (trade name); manufactured by BASF Japan Ltd.), 3.20 g of a 50 wt% PGMEA diluted solution of pentaerythritol acrylate (“Light Acrylate” (registered trademark) PE-4A (trade name); manufactured by Kyoeisha Chemical Co., Ltd.) as a (E) photopolymerizable compound, 0.160 g of 3’,4’-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (“Celloxide” (registered trademark)-2021P (trade name); manufactured by Daicel Corporation), 0.024 g of ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] (“Irgafos” (registered trademark)-1010 (trade name); manufactured by BASF Japan Ltd.), and 0.060 g of a 10 wt% PGMEA diluted solution of an acrylic surfactant (trade name “BYK”-352; manufactured by Big Chemie Japan Ltd.) (corresponding to a concentration of 300 ppm) were dissolved in a mixed solvent of 1.200 g of DAA and 5.171 g of PGMEA and stirred. Then, filtration was performed through a 5.0 μm filter to obtain a photosensitive colored resin composition (P-1).

[0096] Preparation Example 2 Photosensitive Resin Composition (P-2) (H) As the black pigment, 5.00 g of titanium nitride (manufactured by Wako Pure Chemical Industries, Ltd.; particle size: 50 nm, titanium content: 74.3 wt%, nitrogen content: 20.3 wt%, oxygen content: 2.94 wt%) was mixed with 5.00 g of a siloxane resin (c-1) solution as the (C) resin, and dispersed using a mill-type disperser filled with zirconia beads to obtain a pigment dispersion (MW-2).

[0097] The photosensitive colored resin composition (P-2) was obtained in the same manner as in Preparation Example 1, except that the addition amount of the siloxane resin (c-1) solution was changed to 3.383 g, the PGMEA of the mixed solvent was changed to 5.189, and 0.24 g of the pigment dispersion (MW-2) was additionally added. Preparation Example 3 Photosensitive Colored Resin Composition (P-3) (I) As the organometallic compound, 2.00 g of bis(acetylacetonato)palladium was dissolved in 8.00 g of DAA to obtain an organometallic compound solution (OM-1).

[0098] The photosensitive colored resin composition (P-3) was obtained in the same manner as in Preparation Example 1, except that the addition amount of the siloxane resin (c-1) solution was changed to 3.065 g, the PGMEA of the mixed solvent was changed to 5.3870 g, the DAA was changed to 0.624 g, and 0.720 g of the organometallic compound solution (OM-1) was added.

[0099] Preparation Example 4 Photosensitive Colored Resin Composition (P-4) The photosensitive resin composition (P-4) was obtained in the same manner as in Preparation Example 1, except that the acrylic resin (d-1) solution was used instead of the siloxane resin (c-1) solution.

[0100] Preparation Example 5 Photosensitive Colored Resin Composition (P-5) The amount of the pigment dispersion (MW-1) was 7.520 g, the amount of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyloxime) (“Irgacure” (registered trademark) OXE-02 (trade name), manufactured by BASF Japan Ltd. (hereinafter referred to as “OXE-02”)) was 0.141 g, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (“Irgacure” (registered trademark)-819 (trade name), manufactured by BASF Japan Ltd.) was 0.282 g, a 50 wt% PGMEA diluted solution of pentaerythritol acrylate (“Light Acrylate” (registered trademark) PE-4A (trade name), manufactured by Kyoeisha Chemical Co., Ltd.) was 3.78 g, 3’,4’-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (“Celloxide” (registered trademark)-2021P (trade name), manufactured by Daicel Corporation) was 0.188 g, ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] (“Irganox” (registered trademark)-1010 (trade name), manufactured by BASF Japan Ltd.) was 0.028 g, DAA was 1.060 g and PGMEA was 2.934 g. A photosensitive colored resin composition (P-5) was obtained in the same manner as in Preparation Example 1, except that the addition amount of the siloxane resin (c-1) solution was changed to 4.027 g.

[0101] Preparation Example 6 Photosensitive Colored Resin Composition (P-6) The amount of the pigment dispersion (MW-1) was 8.800 g, the amount of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyloxime) ethanone (“Irgacure” (registered trademark) OXE-02 (trade name), manufactured by BASF Japan Ltd. (hereinafter referred to as “OXE-02”)) was 0.165 g, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (“Irgacure” (registered trademark)-819 (trade name), manufactured by BASF Japan Ltd.) was 0.330 g, a 50 wt% PGMEA diluted solution of pentaerythritol acrylate (“Light Acrylate” (registered trademark) PE-4A (trade name), manufactured by Kyoeisha Chemical Co., Ltd.) was 4.400 g, 3’,4’-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (“Celloxide” (registered trademark)-2021P (trade name), manufactured by Daicel Corporation) was 0.220 g, ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] (“Irgafos” (registered trademark)-1010 (trade name), manufactured by BASF Japan Ltd.) was 0.033 g, DAA was 0.900 g and PGMEA was 0.377 g. A photosensitive colored resin composition (P-6) was obtained in the same manner as in Preparation Example 1, except that the addition amount of the siloxane resin (c-1) solution was changed to 4.715 g.

[0102] Preparation Example 7 Photosensitive Colored Resin Composition (P-7) A photosensitive colored resin composition (P-7) was obtained in the same manner as in Preparation Example 1, except that the pigment dispersion (MW-1) was not added and the addition amount of the siloxane resin (c-1) solution was changed to 14.625 g, and PGMEA was 0.371 g.

[0103] The compositions of Preparation Examples 1 to 7 are summarized in Table 1.

[0104]

Table 1

[0105] Adjustment Example 8 Conductive Paste Into a 100 ml clean bottle, add 15.00 g of a carboxyl group-containing acrylic copolymer (J) having an unsaturated double bond, 0.66 g of (“IRGACURE (registered trademark)” OXE04 (trade name), manufactured by BASF Japan Ltd.) as a photoinitiator, 1.5 g of (“Light Acrylate (registered trademark)” BP-4EA (trade name), manufactured by Kyoeisha Chemical Co., Ltd.) as a compound having an unsaturated double bond, 3.82 g of (“EPICLON (registered trademark)” 840 (trade name), manufactured by DIC Corporation) as an epoxy resin, 2.17 g of H-4 ((trade name), manufactured by Meiwafosis Co., Ltd.) as a novolac phenol resin, and 5.78 g of DGME. Mix using a planetary centrifugal vacuum mixer “Avatori Rentaro (registered trademark)” ARE-310 (manufactured by Shinki Co., Ltd.) to obtain 28.94 g of a resin solution. Mix the obtained 28.94 g of the resin solution with 54.02 g of Ag particles having a particle size (D50) of 0.5 μm and an aspect ratio of 1.1, and knead using a three-roll mill (EXAKT M-50; manufactured by EXAKT) to obtain 82.96 g of a conductive paste.

[0106] <Bump formation substrate (K-1)> Apply the obtained conductive paste onto a glass substrate having an electrode with a substrate thickness of 0.7 mm, and heat in a drying oven at 100 °C for 5 minutes. Using a direct drawing exposure apparatus (MX-1201; manufactured by Dainippon Scientific Co., Ltd.), considering the line thickness of the exposed part, expose 200 bumps with a film thickness of 5 μm and a size of φ10 μm at an exposure dose of 300 mJ / cm 2 (converted to a wavelength of 375 nm) such that the distance between a pair of bumps is 10 μm. After exposure, spray develop for 20 seconds using a 0.1 wt% aqueous Na2CO3 solution, and perform a rinsing process with ultrapure water to fabricate a bump formation substrate (K-1).

[0107] <Bump formation substrate (K-2)> Perform indium plating on a circuit board having an electrode with a substrate thickness of 0.7 mm to obtain a bump formation substrate (K-2) having indium bumps with a thickness of 0.5 μm formed on the substrate electrode.

[0108] <Bump-Forming Substrate (K-3)> The bump-forming substrate (K-3) was fabricated by changing the film thickness of the bank to 2.5 μm in the same manner as the bump-forming substrate (K-1).

[0109] <Bump-Forming Substrate (K-4)> The bump-forming substrate (K-4) was fabricated by changing the film thickness of the bank to 1.0 μm in the same manner as the bump-forming substrate (K-1). <LED Mounting Substrate (L-1)> As shown in Fig. 9(a), a release layer 12 mainly composed of polyimide was formed on a transparent substrate 11 with a thickness of 5 μm. On the release layer 12, an LED transfer substrate 14 was fabricated in which the surface of the LED element 5 that does not have the LED electrode 4 of the LED light-emitting portion 13 was held by the adhesiveness of the release layer 12.

[0110] Next, as shown in Fig. 9(b), a laser 16 with a wavelength of 266 nm was irradiated onto the bump-forming substrate 15 from the transparent substrate 11 side of the LED transfer substrate 14 at 200 mJ / cm 2 to transfer the LED chip 14 onto the LED mounting substrate. Then, as shown in Fig. 9(c), thermocompression bonding was performed at 1 MPa, 120 °C, and 60 s using a diaphragm laminator to fabricate the LED mounting substrate (L-1) 17 as shown in Fig. 9(d). Also, for the fabricated LED mounting substrate (L-1), by using a focused ion beam apparatus (FIB) and a scanning electron microscope (SEM) to observe the cross-sectional shape of the LED, the distance S H between the bottom surface of the LED and the substrate having the wiring electrode was measured. In the case of the substrate on which the LED shown in Fig. 9 was mounted, the distance between the bottom surface of the LED and the substrate having the wiring electrode is represented by the symbol S H In the LED mounting substrate (L-1), the distance S H between the bottom surface of the LED and the substrate having the wiring electrode was 6.5 μm.

[0111] <LED Mounting Substrate (L-2)> In the same manner as the LED mounting substrate (L-1), the bump forming substrate (K-1) was changed to the bump forming substrate (K-2) to fabricate the LED mounting substrate (L-2). Regarding the fabricated LED mounting substrate (L-2), the distance S between the bottom surface of the LED and the substrate having the wiring electrodes H was 0.5 μm.

[0112] <LED mounting substrate (L-3)> In the same manner as the LED mounting substrate (L-1), the bump forming substrate (K-1) was changed to the bump forming substrate (K-3) to fabricate the LED mounting substrate (L-3). Regarding the fabricated LED mounting substrate (L-3), the distance S between the bottom surface of the LED and the substrate having the wiring electrodes H was 2.5 μm.

[0113] <LED mounting substrate (L-4)> In the same manner as the LED mounting substrate (L-1), the bump forming substrate (K-1) was changed to the bump forming substrate (K-4) to fabricate the LED mounting substrate (L-4). Regarding the fabricated LED mounting substrate (L-4), the distance S between the bottom surface of the LED and the substrate having the wiring electrodes H was 1.0 μm. The evaluation methods in each example and comparative example are shown below.

[0114] <Mountability evaluation> Regarding the LED mounting substrates used in the examples and comparative examples, a voltage was applied to 100 LEDs mounted thereon, and the number of lit LEDs was counted, and that number was taken as the mountability evaluation result.

[0115] <Connection reliability evaluation (continuous lighting test)> Regarding the LED mounting substrates with cured films obtained in the examples and comparative examples, a voltage was applied to count the number of lit LEDs. Then, the lighting state was continued for 3 hours, and the LED lighting rate was obtained by the following formula and taken as the connection reliability evaluation result.

[0116] Connection reliability evaluation = number of lit LEDs after the test / number of lit LEDs before the test × 100.

[0117] <Reflectance> The photosensitive colored resin compositions used in the examples and comparative examples were processed in the same manner as the conditions processed in the examples and comparative examples, except that the film thickness was changed, and a 10-μm cured film was formed on a flat glass substrate. The obtained cured film was used as a model of the cured film of the substrate with a cured film formed on the LED mounting substrate formed in each example and comparative example, and the reflectance at a wavelength of 550 nm in the SCI mode was measured from the cured film side using a spectrophotometer (trade name CM-2600d, manufactured by Konica Minolta, Inc.).

[0118] <Absorbance (OD value)> The photosensitive resin compositions used in the examples and comparative examples were processed in the same manner as the conditions processed in the examples and comparative examples, except that the film thickness was changed, and a 10-μm cured film was formed on a flat glass substrate. The obtained cured film was used as a model of the cured film of the substrate with a cured film formed on the substrate having an uneven structure formed in each example and comparative example, and the intensities of incident light and transmitted light were measured from above using an optical densitometer (U-4100 manufactured by Hitachi High-Technologies Corporation), and the absorbance (OD value) was calculated from the following formula (III).

[0119] OD value = log10(I0 / I) ··· Formula (III) I0: Incident light intensity I: Transmitted light intensity.

[0120] (Example 1) The photosensitive colored resin composition of Preparation Example 1 was spin-coated (trade name 1H-360S, manufactured by Mikasa Co., Ltd.) on the LED mounting substrate (L-1), and a coating film was formed using a hot plate (trade name SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.). Then, it was dried at a temperature of 100°C for 2 minutes to form a dried film. As the exposure machine in the step of exposing the substrate with the dried film, a parallel light mask aligner (trade name PLA-501F, manufactured by Canon Inc.) using an ultra-high pressure mercury lamp as a light source was used. For the mask pattern, a design with a gap of 5 μm between the mounted LED element and the coating film after development was used, and the stage was moved to a predetermined position using an alignment camera, and the exposure amount was 200 mJ / cm2 Exposure was performed with a gap of 100 μm using the (i-line). Subsequently, using an automatic developing apparatus (“AD-2000” (trade name) manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed for 100 seconds using a 0.045 wt% potassium hydroxide aqueous solution, and then rinsing was performed for 30 seconds using water. Thereafter, using an oven (trade name IHPS-222, manufactured by Espec Corporation), heating was performed in air at a temperature of 170° C. for 30 minutes to fabricate an LED mounting substrate with a cured film having a film thickness of 10 μm on the LED mounting substrate.

[0121] (Example 2) Processing was carried out in the same manner as in Example 1, except that the LED mounting substrate (L-2) was used instead of the LED mounting substrate (L-1).

[0122] (Example 3) Processing was carried out in the same manner as in Example 1, except that P-2 was used as the photosensitive resin composition and the exposure amount before development was set to 80 mJ.

[0123] (Example 4) Processing was carried out in the same manner as in Example 1, except that P-3 was used as the photosensitive resin composition and the exposure amount before development was set to 100 mJ.

[0124] (Example 5) Processing was carried out in the same manner as in Example 1, except that P-4 was used as the photosensitive resin composition and the exposure amount before development was set to 40 mJ.

[0125] (Example 6) Processing was carried out in the same manner as in Example 1, except that P-5 was used as the photosensitive resin composition.

[0126] (Example 7) Processing was carried out in the same manner as in Example 1, except that P-6 was used as the photosensitive resin composition.

[0127] (Example 8) Processing was carried out in the same manner as in Example 1, except that P-7 was used as the photosensitive resin composition.

[0128] (Example 9) Processing was carried out in the same manner as in Example 1, except that the LED mounting substrate (L-3) was used instead of the LED mounting substrate (L-1).

[0129] (Example 10) Processing was carried out in the same manner as in Example 1, except that the LED mounting substrate (L-3) was used instead of the LED mounting substrate (L-1).

[0130] (Comparative Example 1) Processing was carried out in the same manner as in Example 1, except that the photosensitive coloring resin composition P-1 was not applied to the LED mounting substrate (L-1).

[0131]

Table 2

Explanation of Signs

[0132] 1: Substrate 2: Wiring electrode 3: LED electrode 4: Bump 5: LED element 6: Coating film of photosensitive coloring resin composition 7: Dried film of photosensitive coloring resin composition 8: Coating film after exposure of photosensitive coloring resin composition 9: Coating film after development of photosensitive resin composition 10: Cured film of photosensitive resin composition 11: Transparent substrate 12: Release layer 13: LED light-emitting part 14: Substrate for LED transfer 15: Substrate for LED mounting 16: Laser 17: LED mounting substrate

Claims

1. A method for manufacturing an LED mounting substrate with a cured film, which sequentially performs the following processing steps (1) to (5) on an LED mounting substrate having a wiring electrode, bumps formed on the wiring electrode, and a plurality of LED elements mounted on the bumps. (1) A step of applying a photosensitive resin composition to the LED mounting substrate and filling the gap between the LED element and the substrate having the wiring electrode and the space between adjacent LED elements with a coating film. (2) A step of drying the coating film to form a dry film. (3) A step of exposing the dry film. (4) A step of developing and removing unnecessary portions in the dry film after exposure. (5) A step of forming a cured film from the film with unnecessary portions removed after development.

2. In the step (4) of developing and removing unnecessary portions in the dry film after exposure according to Claim 1, the method for manufacturing an LED mounting substrate with a cured film according to Claim 1, characterized in that a film after development is left at least around the bumps and the wiring electrodes.

3. The method for manufacturing an LED mounting substrate with a cured film according to Claim 1 or 2, wherein the bumps formed on the wiring electrode contain (A) an organic component and (B) conductive particles.

4. The method for manufacturing an LED mounting substrate with a cured film according to Claim 1 or 2, wherein the bumps contain (A) an acrylic copolymer having a carboxyl group as the organic component and an epoxy resin, and the ratio of the (B) conductive particles in the total weight of the bumps is 50 to 90 wt%.

5. The method for manufacturing an LED mounting substrate with a cured film according to Claim 1 or 2, wherein the bumps are formed by exposing and developing a conductive paste containing (A) an organic component and (B) conductive particles to form a pattern.

6. The method for manufacturing an LED mounting substrate with a cured film according to Claim 1 or 2, wherein the photosensitive resin composition contains (C) a resin, (D) a photopolymerization initiator, (E) a photopolymerizable compound, (F) an organic solvent, and (G) a coloring pigment.

7. The method for manufacturing an LED mounting substrate with a cured film according to Claim 6, characterized in that the (G) coloring pigment contains at least (G-1) a white pigment.

8. The method for manufacturing an LED mounting substrate with a cured film according to Claim 6, characterized in that the (C) resin is (C-1) a siloxane resin.

9. An LED mounting substrate with a cured film manufactured by the method according to Claim 6.

10. An element comprising the LED mounting substrate with a cured film according to Claim 9.

11. An LED mounting substrate including a substrate having electrodes, bumps made of a composite material of an organic component and conductive particles formed on the electrodes, and a plurality of LED elements mounted on the bumps, wherein at least a part of the periphery of at least the bumps and the LED elements is covered with a cured film of a photosensitive colored resin composition, and the cured film of the photosensitive colored resin composition is also provided between adjacent LED elements. The LED mounting substrate is characterized by this.

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