Dispersion composition, method for producing the dispersion composition, resin composition, film-coated substrate, and method for producing the film-coated substrate

Abstract

The present invention provides a dispersion composition that offers high stability as a composition, thereby improving film homogeneity and enabling the formation of films with excellent light transmission, dry etch resistance, and heat dissipation (thermal conductivity). [Solution] A dispersion composition for forming a diamond dispersion film is provided, comprising diamond particles, a dispersion medium, and a dispersant for dispersing the diamond particles in the dispersion medium, wherein the primary particles of the diamond particles have an average particle size D50, which is the cumulative 50% diameter in their volume-based particle size distribution, of 50 nm or more and 400 nm or less.

Description

[Technical Field]

[0001] The present disclosure relates to a dispersion composition, a method for producing the dispersion composition, a resin composition, a substrate with a film, and a method for producing the substrate with a film. [Background Art]

[0002] Conventionally, photosensitive resin compositions useful for manufacturing semiconductor devices and the like have been proposed (see, for example, Patent Document 1). This photosensitive resin composition contains nanodiamonds having a primary particle diameter of 30 nm or less. [Prior Art Literature] [Patent Literature]

[0003] [Patent Document 1] Japanese Unexamined Patent Application Publication No. 2005-234019 [Summary of the Invention] [Problem to be Solved by the Invention]

[0004] However, such nanodiamonds have an excessively small primary particle diameter, so particles tend to aggregate with each other, resulting in insufficient dispersion. As a result, it is difficult to ensure the homogeneity of the film. [Means for Solving the Problem]

[0005] According to one aspect of the present invention, there is provided a dispersion composition for forming a diamond-dispersed film, comprising diamond particles, a dispersion medium, and a dispersant that disperses the diamond particles in the dispersion medium, wherein an average particle diameter D50, which is a cumulative 50% diameter in the volume-based particle size distribution of primary particles of the diamond particles, is 50 nm or more and 400 nm or less.

[0006] According to this aspect, it is possible to provide a dispersion composition having high stability as a composition, which can improve the homogeneity of a film and form a film excellent in light transmittance, dry etching resistance and heat dissipation (thermal conductivity). [Brief Description of the Drawings]

[0007] [Figure 1] This figure shows an example of a film-coated substrate 1 according to one embodiment of the present disclosure. [Modes for carrying out the invention]

[0008] [Embodiment] The dispersion composition, method for producing the dispersion composition, liquid resin composition, film-coated substrate, and method for producing the film-coated substrate of this disclosure will be described in detail below based on preferred embodiments shown in the figures. The following description is illustrative of the present invention and does not limit its scope. It goes without saying that other embodiments may also fall within the scope of the present invention, as long as they are consistent with the spirit of the invention. For example, in this disclosure, “process” does not mean only processes that can be recognized as distinct from others, but also processes that are combined with other operations, distributed across multiple processes, include other process elements, and can perform the operations of multiple processes in a single process, as long as they are in line with the spirit of the invention.

[0009] [overview] First, I will explain the overview of this disclosure. <Membrane-coated substrate> Figure 1 shows an example of a film-coated substrate 1 according to one embodiment of the present disclosure. The film-coated substrate 1 comprises a substrate 2 and a diamond dispersion film 3 formed on the main surface 21 of the substrate 2. As will be described later, by using the diamond dispersion film 3, fine processing can be accurately performed on the main surface 21 of the substrate 2. The main surface 21 of the substrate 2 refers to any surface provided on the substrate 2. Therefore, the film-coated substrate 1 is suitable for use as a material for components mounted in precision equipment such as electronic devices and optical devices. In particular, the film-coated substrate 1 is preferably used as a material for semiconductor devices such as semiconductor integrated circuits.

[0010] <Base material> The constituent materials of the base material 2 are not particularly limited, but examples include oxides such as aluminum oxide (Al2O3), silicon oxide (SiO2), and boron oxide (B2O3), nitrides such as aluminum nitride (AlN) and gallium nitride (GaN), carbides such as silicon carbide (SiC), resins such as polycarbonate and polyimide, metals such as copper and aluminum, or combinations thereof. The base material 2 is not limited to a homogeneous structure as shown in Figure 1, and may, for example, have multiple layers made of different materials in the thickness direction.

[0011] <Diamond dispersion film> At least a portion of the main surface 21 of the substrate 2 is covered by a diamond dispersion film 3. The diamond dispersion film 3 may be a film that covers the entire main surface 21, or it may be a film that covers only a portion of the main surface 21. In this embodiment, the case in which the diamond dispersion film 3 covers only a portion of the main surface 21 will be described. That is, the case in which the diamond dispersion film 3 is patterned will be described. The diamond dispersion film 3 includes a resin matrix 31 and diamond particles 32 dispersed in the resin matrix 31. As the diamond particles 32 are dispersed in this manner, the diamond dispersion film 3 exhibits excellent light transmission, insulation, semiconductor properties (e.g., wide bandgap properties), and thermal conductivity.

[0012] The primary particles of the diamond particles 32 preferably have an average particle size D50, which is the cumulative 50% diameter in their volume-based particle size distribution, of about 50 nm to 400 nm, more preferably of about 90 nm to 350 nm, and even more preferably of about 100 nm to 300 nm. In the case of diamond particles with primary particles smaller than 50 nm (so-called nanodiamonds), light cannot be transmitted because it is scattered internally. Therefore, the light transmittance of a film in which diamond is dispersed is insufficient. In addition, because diamond particles tend to aggregate with each other, dispersion is insufficient, and it may be difficult to ensure the homogeneity of the film. On the other hand, as described above, the diamond particles 32 of this disclosure have a primary particle size that is not too small, which allows for sufficiently high light transmittance and homogeneity of the diamond dispersion film 3. Furthermore, because the primary particle size of the diamond particles 32 is not too large, the diamond dispersion film 3 can be easily processed into a desired fine shape. In addition, it is possible to prevent or suppress the detachment of the diamond particles 32 from the diamond dispersion film 3. In this specification, the upper and lower limits of the preferred numerical range can be combined as appropriate.

[0013] The average particle size D50 of the primary diamond particles 32 can be determined, for example, as follows: Three 1mm square regions are cut out from any three locations in the diamond dispersion film 3, and the resin matrix 31 and diamond particles 32 are separated. For the separated diamond particles 32, the cumulative 50% diameter in the volume-based particle size distribution is measured for each region using a particle size distribution analyzer and laser diffraction / scattering method. The arithmetic mean of the cumulative 50% diameters for each region is then calculated, and this value can be taken as the average particle size D50 of the primary diamond particles 32 in the diamond dispersion film 3.

[0014] The proportion of diamond particles 32 in the diamond dispersion film 3 is preferably between 10% and 80% by volume, and more preferably between 20% and 60% by volume. By including a large amount of diamond particles 32 in this way, the diamond dispersion film 3 can be given the excellent properties attributed to diamond as described above. Furthermore, by including a certain amount of resin matrix 31, appropriate adhesion can be ensured between the diamond particles 32 and between the diamond dispersion film 3 and the substrate 2. The proportion of diamond particles 32 in the diamond dispersion film 3 can be determined, for example, as follows: Three 1mm square regions are cut out from any three locations in the diamond dispersion film 3, and X-ray crystalline structure (XRD) analysis is performed on each region. The proportion of diamond in each region is then calculated by taking the arithmetic mean.

[0015] Further, when viewed from the diamond-dispersed film 3 side, the proportion of the area of regions where diamond particles 32 are present, among the regions where the diamond-dispersed film 3 is formed, is preferably about 60% or more, about 70% or more, or about 80% or more, more preferably about 90% or more, about 95% or more, and particularly preferably 100%. As described above, by relatively uniformly distributing (dispersing) the diamond particles 32 in the in-plane direction of the diamond-dispersed film 3, the above-mentioned excellent properties can be imparted to the diamond-dispersed film 3. In particular, since the mechanical and chemical strength and insulating properties of the diamond-dispersed film 3 are improved, the diamond-dispersed film 3 can suitably function as a protective film or an insulating film for the base material 2. The proportion of the area where diamond particles 32 are present can be determined, for example, by the following method. Specifically, 1 mm square regions at any three positions of the diamond-dispersed film 3 are observed using a scanning electron microscope (SEM)-electron backscatter diffraction (EBSD) method. Then, the proportion can be obtained by arithmetically averaging the proportion of the area occupied by diamond for each region.

[0016] The ratio of the thickness T of the diamond-dispersed film 3 to the average particle diameter D50 of the primary particles of the diamond particles 32 is preferably about 1.5 or more and 60 or less, and more preferably about 2 or more and 20 or less. As described above, when the thickness T is sufficiently large, a plurality of diamond particles 32 can be in a laminated state in the thickness direction of the diamond-dispersed film 3. That is, the excellent properties resulting from the diamond particles 32 can be more reliably imparted to the diamond-dispersed film 3. When the thickness T is moderately small, excessive use of diamond particles 32 can be prevented, and the diamond-dispersed film 3 can be provided at low cost. Further, since the thickness T is not excessively large, the diamond-dispersed film 3 can be removed relatively easily. For this reason, energy required for removing the diamond-dispersed film 3 can be saved. The thickness T of the diamond-dispersed film 3 can be obtained, for example, by analyzing the cross-section of the diamond-dispersed film 3 at any three positions using a SEM.

[0017] <Dispersion Composition> The dispersion composition according to an embodiment of the present disclosure is used for forming the above-described diamond-dispersed film 3. The dispersion composition is preferably liquid (or sol-like) under normal temperature and normal pressure conditions. The dispersion composition comprises diamond particles, a dispersion medium, and a dispersant. The dispersant has a function of dispersing the diamond particles in the dispersion medium.

[0018] In the dispersion composition, the diamond particles 32 are dispersed as dispersed particles in the dispersion medium. More specifically, the dispersed particles consist of one or more diamond particles 32, or consist of one or more diamond particles 32 and molecules constituting the dispersant. That is, the dispersed particles include at least the diamond particles 32. The average particle diameter D50, which is the 50% cumulative diameter by volume in the particle size distribution of the dispersed particles, is preferably approximately from 50 nm to 500 nm, more preferably approximately from 90 nm to 400 nm, still more preferably from 100 nm to 350 nm, further preferably approximately from 120 nm to 320 nm, and particularly preferably approximately from 150 nm to 300 nm. Since the dispersed particles are not excessively small as described above, light absorption by the dispersed particles can be reduced, and sufficient light transmittance can be imparted to the dispersion composition. Furthermore, since it is not necessary to use small-diameter diamond particles (such as so-called nanodiamonds), the cost of the dispersion composition and the environmental load associated with production can be reduced. In addition, since the dispersed particles are not excessively large, the mass of each individual dispersed particle is appropriately small, and the dispersed particles tend to be stably dispersed in the dispersion medium.

[0019] When the cumulative 10% diameter in the volume-based particle size distribution of dispersed particles is defined as D10 and the cumulative 90% diameter as D10, (D90-D10) / D50 is preferably between 0.5 and 2, and more preferably between 1 and 1.9. Thus, it is preferable for dispersed particles to have a relatively broad particle size distribution. That is, it is not necessary to strictly select the diamond particles 32 that constitute the dispersed particles, and the time and effort required to manufacture the dispersed composition can be reduced. Furthermore, the number of diamond particles 32 that are discarded due to selection can be reduced, so there is no waste of diamond particles 32. That is, the environmental burden during the manufacture of the dispersed composition can be reduced. In addition, if the dispersed particles have a somewhat sharp particle size distribution, the dispersed particles can be dispersed more reliably in the dispersion medium. In other words, variations in the quality of the dispersed composition can be suppressed.

[0020] The average particle size D50, cumulative 10% diameter D10, and cumulative 90% diameter D90 of dispersed particles can be determined as follows: A sample is prepared by diluting the dispersion composition with a solvent. Using a particle size distribution analyzer, the cumulative 50% diameter, cumulative 10% diameter, and cumulative 90% diameter in the volume-based particle size distribution are measured for this sample by laser diffraction and scattering. The arithmetic mean of the results of these three measurements is then taken, and these values ​​can be taken as the average particle size D50, cumulative 10% diameter D10, and cumulative 90% diameter D90 of the dispersed particles.

[0021] In the dispersion composition, the period during which the diamond particles can be maintained in a dispersed state is preferably about one day or more, and more preferably about 30 days or more. In this case, the dispersion composition can be judged to have excellent storage properties. Therefore, when using the dispersion composition, the process of redispersing the diamond particles can be omitted, and thus it has excellent handling properties. Furthermore, it can be expected that the diamond dispersion film 3 formed using the dispersion composition will have homogeneous properties. "A state in which diamond particles are dispersed" means, for example, that no precipitate has formed in a dispersed composition that has been left standing at room temperature and pressure.

[0022] The dispersion composition is light-transmitting. In particular, the dispersion composition can transmit ultraviolet light. Specifically, the transmittance of the dispersion composition to light with a wavelength of 365 nm (so-called i-ray) is preferably 10% or more, and more preferably 15% or more. Having this level of transmittance allows the dispersion composition to be used in applications where it is cured with active energy rays such as i-rays.

[0023] <Method for producing the dispersion composition> First, the diamond particles 32, a dispersant, and a dispersion medium are stirred and mixed to obtain a first mixture. At this time, a dispersion aid may also be stirred and mixed into the first mixture. Next, the diamond particles 32 are dispersed in this first mixture. Examples of dispersion methods for the diamond particles 32 include dry dispersion (kneading dispersion treatment) in which the particles are dispersed in a high viscosity state using a kneader or two-roll device, wet dispersion (fine dispersion treatment) in which the particles are dispersed in a relatively low viscosity state using a three-roll device, an ultrasonic device, a homogenizer or a bead mill, and methods that combine these dispersion methods. Preferably, a fine dispersion treatment is used as the dispersion method for the diamond particles 32. That is, a method for producing a dispersion composition according to one embodiment of the present disclosure is to obtain a dispersion composition by ultrasonic dispersion, homogenizer dispersion, or bead mill dispersion of diamond particles 32, a dispersion medium, and a dispersant for dispersing diamond particles in the dispersion medium.

[0024] Ultrasonic dispersion is a method of disintegrating and dispersing diamond particles 32 by using the force of cavitation generated when an ultrasonic-emitting tip is immersed in a dispersion medium. Examples of commercially available ultrasonic splitters include the UH-50, UH-50F, UH-300, UH-600, UH-600S, UH-600SH (all product names, manufactured by MST Corporation), PSF-600, PSF-1200, and RUS-600TCVP (all product names, manufactured by Nippon Seiki Seisakusho Co., Ltd.).

[0025] Homogenizer dispersion can be broadly classified into types such as agitated homogenizers and high-pressure homogenizers. A stirring homogenizer is a device that uses a stirring blade to rotate at high speed to entrain diamond particles 32 into the dispersion medium, while simultaneously dispersing the diamond particles 32 through the cutting action of the blade. Examples of commercially available agitated homogenizers include the M-Technique CreaMix W Motion CLM-1.7 / 5.5W and Crea SS5-100 (both product names), and the Primix Adihomomixer 2M and HV-M (product names).

[0026] A high-pressure homogenizer refers to a device that crushes and disperses the material to be crushed (aggregates of diamond particles 32) by applying high or ultra-high pressure and generating shear force as it passes through slits (gaps). This generally includes devices called high-pressure homogenizers and ultra-high-pressure homogenizers. Examples of high-pressure homogenizer devices include Starburst (product name, Sugino Machine Co., Ltd.), NanoVeida (product name, Yoshida Machinery Industry Co., Ltd.), and Microfluidizer M-110E / H (product name, Mizuho Industries Co., Ltd.).

[0027] Bead mill dispersion is a method of mixing various components (diamond particles 32, dispersants, etc.) in a dispersion medium, and crushing, refining, and dispersing coarse particles or aggregates (aggregated particles) through the collision force between the beads. In this process, the particle surface is coated with a dispersant or dispersion aid. This improves the stability of the dispersion composition and makes it easier to suppress precipitation over long periods. In this bead mill dispersion method, it is also effective to use high-hardness ceramic beads or beads with small particle sizes. For example, bead mill dispersion can be performed using zirconia beads with a particle size of approximately 0.1 mm to 1 mm (especially 0.1 mm to 0.5 mm) for approximately 0.1 to 20 hours.

[0028] Commercially available bead mills can be used. Examples of commercially available bead mills that can be used to prepare this dispersion composition include Star Mill Nano Getter, Star Mill ZRS, Star Mill LMZ, Agitator Mill LMK (all trade names, Ashizawa Finetech Co., Ltd.), Spike Mill, Mighty Mill, Mighty Mill Mark II, Key Mill (all trade names, Inoue Seisakusho Co., Ltd.), Apex Mill, Super Apex Mill, Ultra Apex Mill (all trade names, Hiroshima Metal & Machinery Co., Ltd.). Examples include the Sand Grinder (SLG), Ready Mill (RMV-03), Nano Ready Mill (RMV-03), Ultra Visco Mill (UVM), Ultra-X Visco Mill (UVX), New Visco Mill (NVM) (all product names, manufactured by AIMEX Co., Ltd.), SC Mill, MSC Mill, Attrita, Fine Mill (all product names, manufactured by Nippon Coke Industries Co., Ltd.), Annular Gap Bead Mill (product name, manufactured by Eurotech Co., Ltd.), Dyno Mill ECM, DYNO-MILL NPM-NANO Performance Mill (all product names, manufactured by Shinmaru Enterprise Co., Ltd.), MicroMediaX1 (product name, manufactured by Bühler Co., Ltd.), and others.

[0029] Subsequently, a dispersion composition is obtained by removing coarse particles from the first mixture in which the diamond particles 32 are dispersed. Coarse particles refer to large-diameter particles or impurities such as dust, having a particle size of approximately 5 μm or more, preferably 1 μm or more, and more preferably 0.5 μm or more. Methods for removing coarse particles include, for example, centrifugal separation at a gravitational acceleration of approximately 3000G to 25000G, filtration using filters such as sintered filters and membrane filters.

[0030] <Resin composition> A resin composition according to one embodiment of this disclosure is liquid and includes a dispersion composition. The resin composition is preferably liquid (or sol) under normal temperature and pressure conditions. The resin composition of this embodiment includes the dispersion composition described above and a curable compound. Examples of curable compounds include photocurable compounds (active energy ray curable compounds), thermosetting compounds, and anaerobic curable compounds. As will be described later, by curing the entire resin composition with the curable compound, a diamond dispersion film 3 can be formed and its shape stability can be maintained.

[0031] Furthermore, the resin composition according to one embodiment of this disclosure preferably further contains an alkali-soluble compound. This allows, for example, when forming a fine patterned diamond dispersion film 3 by photolithography, unwanted portions can be easily washed and removed with an alkaline solution. In other words, the developability of the diamond dispersion film 3, which is the cured product of the resin composition, is improved.

[0032] The viscosity of the liquid resin composition is preferably about 30 cps or less at room temperature (20°C), and more preferably about 20 cps or less. With such a low viscosity resin composition, when applied to a curing substrate or the like, it can be applied only to the area of ​​the desired shape with a sufficiently uniform thickness. For example, viscosity can be measured using an E-type viscometer at room temperature (20°C) under conditions of 50 rpm.

[0033] <Method for manufacturing a film-coated substrate> Next, an example of a method for manufacturing the film-coated substrate 1 will be described. [1] First, prepare the base material 2 and the resin composition. The base material 2 can be prepared by purchasing a commercially available product or by manufacturing it from scratch. On the other hand, the resin composition can be manufactured according to the method for producing the dispersion composition described above.

[0034] Next, the obtained dispersion composition, the curable compound, and the alkali-soluble compound are stirred and mixed to obtain a second mixture. In this embodiment, the case in which the curable compound is a photocurable compound will be described. Furthermore, polymerization initiators, solvents, etc., may be stirred and mixed into the second mixture. Next, the resin composition is obtained by removing coarse particles from this second mixture. The same method as for removing coarse particles from the first mixture can be used.

[0035] [2] Next, the resin composition is applied to the main surface 21 of the substrate 2 to form a liquid coating. Examples of methods for applying the resin composition include the dropping method, slit coating method, spray method, roll coating method, rotary coating method, casting method, droplet ejection method (inkjet method), flexographic printing method, screen printing method, gravure printing method, and offset printing method. Here, the resin composition may be applied so as to cover the entire main surface 21 of the substrate 2, or it may be applied so as to cover only a part of it. If necessary, pretreatment may be performed on the main surface 21 of the substrate 2 before applying the resin composition. Examples of pretreatment include forming a base layer on the main surface 21 of the substrate 2 (the surface to which the resin composition is to be applied) and increasing the surface roughness. These treatments are performed, for example, to improve the adhesion between the main surface 21 and the diamond dispersion film 3, to prevent the diffusion of the substance, and to flatten the surface of the film-coated substrate 1. The thickness of the resin composition (liquid film) is preferably greater than the thickness of the target diamond dispersion film 3, taking into account shrinkage due to curing. The thickness of the resin composition is preferably, for example, 0.05 μm to 20 μm, and more preferably 0.3 μm to 10 μm. By applying the resin composition with such a thickness, a diamond dispersion film 3 having the thickness T described above (see Figure 1) can be obtained.

[0036] [3] Next, at least a portion of the liquid components is removed from the resin composition to obtain a pre-cured film. That is, pre-baking is performed to volatilize at least a portion of the resin composition (liquid film). Pre-baking can be carried out, for example, by leaving it for 10 seconds to 1 hour in a temperature environment of room temperature or above 200°C. Since the thickness of the resin composition (liquid film) applied to the substrate 2 is relatively small, the pre-baking temperature can be lowered and the time shortened. Therefore, the environmental burden when manufacturing the film-coated substrate 1 can be reduced.

[0037] [4] Next, a mask is set up to restrict exposure to a portion of the pre-cured film. Here, the portion of the pre-cured film refers to the area where the diamond dispersion film 3 should not be formed. The mask may be created at this time or may be formed in advance.

[0038] [5] Next, the partially cured film (the resin composition after removing the liquid components) is exposed to active energy rays through a mask, thereby partially curing the film. As a result, only the exposed (i.e., exposed to active energy rays) portion of the partially cured film is cured. On the other hand, the portion whose exposure was restricted by the mask (i.e., not exposed to active energy rays) remains uncured and as a partially cured film. The pre-cured film can be exposed to active energy rays such as ultraviolet light, including, for example, g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), and i-rays (wavelength 365 nm). Light with a wavelength of 300 nm or less can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm) and ArF rays (wavelength 193 nm). However, it is preferable that the wavelength of the active energy rays be 365 nm or longer. Active energy rays with a wavelength of a certain length are less likely to be absorbed by the diamond particles 32 in the pre-cured film. Therefore, the active energy rays can sufficiently reach the substrate 2 (main surface 21). Exposure can be performed by continuously irradiating with active energy rays, or by repeatedly irradiating and pausing with light in short cycles (e.g., milliseconds or less) (pulsed exposure). Here, because the diamond particles 32 contained in the resin composition (dispersed composition) have the primary particle size described above, they can transmit active energy rays and cure the resin composition (semi-cured film). Furthermore, because the resin composition (liquid film) applied to the substrate 2 is not too thick as described above, it is possible to prevent or suppress a decrease in the intensity of the active energy rays reaching the substrate 2. Therefore, the total exposure time can be reduced, and thus the substrate 2 is less prone to deterioration, regardless of its constituent materials.

[0039] [6] Next, the partially cured film, which remains in an uncured state due to limited exposure, is removed. That is, it is washed with a developer solution, and a developing process is performed. This allows the diamond dispersion film 3 having the desired pattern shape to be developed. Examples of developing solutions include aqueous solutions of alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene. The developer concentration is preferably between 0.001% by mass and 10% by mass, and more preferably between 0.01% by mass and 1% by mass. The pH of the developer is preferably between 11 and 13, and more preferably between 11.5 and 12.5. By using a developer with such an appropriate pH, it is possible to suppress the roughening or peeling of the pattern shape of the diamond dispersion film 3. Examples of washing (developing) methods include the dip method, spray method, and paddle method. The developing temperature can be, for example, between 5°C and 40°C. In this embodiment, as described above, the resin composition contains an alkali-soluble resin, which allows the pre-cured film to dissolve quickly in an alkaline developer. Therefore, the development process can be easily carried out. After washing with the developing solution (developing), it is preferable to further wash with pure water. This prevents damage to the diamond dispersion film 3.

[0040] In this manner, a diamond dispersion film 3 is formed on the main surface 21 of the substrate 2 to obtain a substrate 1 with a film. However, the method for manufacturing the film-coated substrate 1 is not limited to the method described above, and various modifications are possible. For example, the manufacturing method may further include a step of ion doping the obtained film-coated substrate 1. In this step, by ion doping from the diamond dispersion film 3 side of the film-coated substrate 1, ions can be implanted only in areas on the main surface 21 where the diamond dispersion film 3 is not formed. In other words, the diamond dispersion film 3 can be used as a protective film to adjust the electrical properties of only a limited area of ​​the substrate 2. Ion doping methods include, for example, gas-phase diffusion, solid-phase diffusion, beamline ion implantation, ion shower implantation, plasma doping, laser doping, plasma ion implantation, and cluster ion implantation. The temperature during ion doping may be, for example, between room temperature and approximately 1500°C. Furthermore, since the diamond dispersion film 3 of this disclosure has diamond particles 32 dispersed at an appropriate density, it will not be completely lost by thermal decomposition even if ion doping is performed under high-temperature conditions. In other words, the diamond dispersion film 3 of this disclosure can function as a protective film during ion doping.

[0041] Furthermore, this manufacturing method may also include a step of etching the obtained film-coated substrate 1. In this step, etching is performed from the diamond dispersion film 3 side of the film-coated substrate 1, so that only the areas on the main surface 21 where the diamond dispersion film 3 is not formed can be removed. In other words, a fine three-dimensional structure can be formed on the main surface 21 of the substrate 2 using the diamond dispersion film 3 as a resist (mask). As for the etching method, either wet etching or dry etching can be employed. However, it is preferable to employ dry etching such as plasma etching, reactive ion etching, or ion beam etching. This allows for the precise formation of a more accurate three-dimensional structure of the substrate 2. The diamond dispersion film 3 of this disclosure has diamond particles 32 dispersed at an appropriate density, and therefore can exhibit resistance to dry etching even with a relatively small thickness T.

[0042] Furthermore, this manufacturing method may include both an ion doping step and an etching step. In this case, the manufacturing method further includes, after the ion doping step, a step of removing the diamond dispersion film 3 and a step of reforming the diamond dispersion film 3 (steps [2] to [6] described above). This makes it possible to manufacture a semiconductor device with desired characteristics.

[0043] In the ion doping or etching process, the film-coated substrate 1 may be exposed to high-temperature conditions exceeding 100°C (i.e., subjected to high-temperature treatment). As a result, after these processes, a large portion of the resin matrix 31 of the diamond dispersion film 3 covering the surface of the substrate 2 may be lost due to thermal decomposition. In other words, the thickness T of the diamond dispersion film 3 changes before and after high-temperature processing, such as the ion doping or etching process. Specifically, the ratio of the thickness of the diamond dispersion film 3 after high-temperature processing to the thickness T of the diamond dispersion film 3 before high-temperature processing is preferably between 0.2 and 0.9, and more preferably between 0.3 and 0.8. In this way, by maintaining a certain thickness of the diamond dispersion film 3 even after high-temperature processing, the reliability of the diamond dispersion film 3 as a protective film or resist is improved. Furthermore, by moderately reducing the thickness of the diamond dispersion film 3, that is, by losing the resin matrix 31, the energy required to remove the diamond dispersion film 3 can be reduced. In other words, the environmental burden associated with the manufacture of semiconductor devices, etc., using the film-coated substrate 1 can be reduced.

[0044] Furthermore, the proportion of diamond particles 32 in the diamond dispersion film 3 changes before and after high-temperature treatment. Specifically, the ratio of the proportion of diamond particles 32 (volume %) after high-temperature treatment to the proportion of diamond particles 32 (volume %) before high-temperature treatment is preferably between 1.5 and 10, and more preferably between 2 and 5. In this way, the proportion of diamond particles 32 does not become too high, that is, a certain amount of resin matrix 31 remains, which improves the reliability of the diamond dispersion film 3 as a protective film or resist. Also, a higher proportion of diamond particles 32 allows for the use of a method specifically designed to remove diamonds as the method for removing the diamond dispersion film 3. In other words, the energy required to remove the diamond dispersion film 3 is further reduced. Traditionally, thick polyimide films have been used as protective films or resists for high-temperature processes such as ion doping and etching. These thick polyimide films adhere strongly to the substrate during high-temperature processing. Therefore, conventionally, removing the protective film or resist required extensive and prolonged cleaning using large quantities of high-temperature concentrated sulfuric acid. This resulted in significant energy consumption for the production, distribution, cleaning of the protective film or resist, and neutralization of the sulfuric acid after use, leading to a high environmental impact and problems with the life cycle assessment (LCA) of semiconductor devices. On the other hand, methods for removing the diamond dispersion film 3 include physical polishing using other diamonds, and chemical polishing using a slurry containing fine diamond particles. Thus, it is not necessary to use high-temperature concentrated sulfuric acid when removing the diamond dispersion film 3. For this reason, even if the diamond dispersion film 3 is repeatedly formed and removed, that is, even if a semiconductor device with a fine structure (pattern) is manufactured using the film-coated substrate 1, the environmental impact is smaller compared to conventional methods. In other words, the life cycle assessment (LCA) of the semiconductor device can be improved.

[0045] [detail] The details of each material used in this disclosure are described below. <Dispersion composition> <<Diamond particles>> It is preferable to use diamond particles 32 having an appropriate particle size. Specifically, the primary particles of the diamond particles 32 preferably have an average particle size D50, which is the cumulative 50% diameter in their volume-based particle size distribution, of about 50 nm to 400 nm, more preferably 70 nm to 350 nm, even more preferably 100 nm to 300 nm, and particularly preferably 100 nm to 250 nm. By ensuring that the primary particles of the diamond particles 32 are not too small, it is possible to suppress the absorption of light within the diamond particles. Furthermore, since it is not necessary to use small-diameter diamond particles (so-called nanodiamonds, etc.), the cost of the dispersion composition and the environmental burden related to its manufacture can be reduced.

[0046] The primary particles of the diamond particles 32 preferably have a (D90-D10) / D50 of approximately 0.75 to 1, and more preferably 0.8 to 0.9, when the cumulative 10% diameter in the volume-based particle size distribution is D10 and the cumulative 90% diameter is D10. In this way, the primary particles of the diamond particles 32 have a relatively broad particle size distribution, eliminating the need for strict sorting of the diamond particles 32. Furthermore, since the amount of diamond particles 32 discarded due to sorting can be reduced, there is no need to produce or distribute excess diamond particles 32. In addition, the primary particles of the diamond particles 32 have a somewhat sharp particle size distribution, allowing for more reliable and uniform dispersion of the diamond particles 32 in the dispersion medium.

[0047] The average particle size D50, cumulative 10% diameter D10, and cumulative 90% diameter D90 of the diamond particles 32 as a material can be determined as follows. Specifically, for a sample in which diamond particles 32 are dispersed in a small amount of water, the cumulative 50% diameter, cumulative 10% diameter, and cumulative 90% diameter in the volume-based particle size distribution are measured using a particle size distribution analyzer by laser diffraction and scattering. Then, the arithmetic mean of the results of these three measurements is taken, and this value can be taken as the average particle size D50, cumulative 10% diameter D10, and cumulative 90% diameter D90 of the primary particles of the diamond particles 32 as a material.

[0048] Such diamond particles 32 can be obtained, for example, by crushing a diamond ingot. In this way, so-called crushed diamonds can be used, which reduces the cost and time required for the manufacture of diamond particles 32. Examples of diamond ingots include natural diamonds, synthetic diamonds, and diamond-like carbon. Of these, it is preferable to use single-crystal diamonds, including natural and synthetic diamonds. This improves the mechanical and chemical strength of the diamond dispersion film 3, such as wear resistance and chemical resistance.

[0049] <<Dispersant>> The dispersant is used to disperse the diamond particles 32 as described above. Examples of such dispersants include urethane compounds such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial)amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters and their modified products, oily dispersants such as amides and salts formed by the reaction of poly(lower alkyleneimines) with polyesters having free carboxyl groups, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide adduct compounds, and phosphate ester-based dispersants, which can be used individually or in combination of two or more.

[0050] The weight-average molecular weight (Mw) of the dispersant is preferably between 4600 and 60000, more preferably between 5000 and 50000, and even more preferably between 6000 and 40000. Thus, a moderately large molecular weight of the dispersant prevents or suppresses excessive aggregation of the diamond particles 32. Furthermore, a molecular weight that is not too large prevents or suppresses the precipitation of the dispersant itself or excessive aggregation of the diamond particles 32. In other words, the average particle size of the dispersed particles, consisting of one or more diamond particles 32, or one or more diamond particles 32 and molecules constituting the dispersant, can be set within the moderate range described above. Therefore, the diamond particles 32 can be sufficiently dispersed. The weight-average molecular weight is a polystyrene-based value measured by gel permeation chromatography (GPC).

[0051] The dispersant preferably has an acidic group or a basic group. If the dispersant has an acidic group, it is thought that at least a portion of the dispersant will be adsorbed onto the diamond particles 32. It is thought that the diamond particles 32 have hydroxyl groups in part, and it is thought that the acidic group will be adsorbed onto this hydrophilic portion having hydroxyl groups. This prevents or suppresses aggregation of the diamond particles 32 and allows the diamond particles 32 to be dispersed in the dispersant. When a dispersant has basic groups, it is thought that the dispersants repel each other. It is thought that at least some of the basic groups are cationized, which causes the basic groups to repel each other. Then, the diamond particles 32 are dispersed between the repelling dispersant molecules, allowing the diamond particles 32 to be dispersed in the dispersion composition.

[0052] • Dispersants containing acidic groups The acid value of the dispersant having an acidic group is preferably between 45 mg KOH / g and 100 mg KOH / g, and more preferably between 46 mg KOH / g and 98 mg KOH / g. Thus, a sufficiently high acid value of the dispersant allows for suitable adsorption to the diamond particles 32. Furthermore, by not having an excessively high acid value, the dispersant itself can maintain its affinity for the dispersion medium, thereby ensuring sufficient dispersion of the diamond particles 32. Examples of acidic groups include carboxyl groups, phosphate groups, and sulfonic acid groups.

[0053] Furthermore, it is particularly preferable to use a branched acidic resin as the dispersant having an acidic group. This prevents the polarity of each molecule constituting the dispersant from becoming excessively large. As a result, the dispersant is adsorbed appropriately onto the diamond particles 32, and the dispersion state of the dispersed particles is stabilized. In this specification, "branched" refers to a structure having a main chain and side chains branching from the main chain, with both the main chain and side chains having regions where monomers are polymerized. On the other hand, "linear" refers to a structure in which the carbon atoms and heteroatoms constituting the polymer are linked together in a single chain.

[0054] Preferred examples of dispersants having an acidic group are listed below. One of these dispersants may be used alone, or two or more may be used in combination. Furthermore, the dispersants listed below are merely examples, and various other dispersants can be used. (Resin having an aromatic carboxylic acid structure) First, a particularly preferred example of a dispersant having an acidic group is a resin having an aromatic carboxylic acid structure. These can be manufactured by methods described in WO2008 / 007776, JP 2008-029901, JP 2009-155406, JP 2010-185934, JP 2011-157416, JP 2009-251481, JP 2007-23195, JP 1996-143651, etc. By using a resin having an aromatic carboxylic acid structure, the polarity of the dispersant molecule is appropriately suppressed, resulting in an excellent balance between compatibility with the dispersion medium and adsorption to the diamond particles 32. That is, the diamond particles 32 can be sufficiently dispersed in the dispersion medium.

[0055] Furthermore, the following resins may be used as resins having an aromatic carboxylic acid structure. Specifically, a resin having a main chain containing an aromatic carboxylic acid ester moiety and side chains containing a vinyl polymer moiety. The main chain of this resin contains an aromatic carboxylic acid ester moiety having an ester bond, which is formed by esterifying an aromatic compound having two or more acid anhydride groups with a compound having two or more hydroxyl groups. In this resin, the amount of acid anhydride groups per mole of hydroxyl groups is approximately 0.9 moles to 1.5 moles, preferably approximately 1.0 mole to 1.3 moles. This allows for sufficient dispersion of the diamond particles 32. Furthermore, the main chain containing the aromatic carboxylic acid ester moiety has a structure having a encapsulation site derived from the monoalcohol described later. That is, the acid anhydride group remaining in the main chain is ring-opened with the monoalcohol, resulting in the presence of an alcohol ester group and a carboxyl group. In this disclosure, the side chains based on the vinyl polymer moiety can be formed, for example, by polymerization of ethylenically unsaturated monomers. The total monomer units constituting the vinyl polymer moiety refer to the substructures derived from each ethylenically unsaturated monomer after vinyl polymerization.

[0056] Aromatic compounds having two or more acid anhydride groups include, for example, pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride, propylene glycol ditrimellitic anhydride, butylene glycol ditrimellitic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, and 2,3,6,7-naphtha. 1,2,3,4,4'-lenetetracarboxylic acid dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic acid dianhydride, 3,3',4,4'-dimethyldiphenylsilanetetracarboxylic acid dianhydride, 3,3',4,4'-tetraphenylsilanetetracarboxylic acid dianhydride, 1,2,3,4-furantetracarboxylic acid dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone di Anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl A Examples include ter dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride, or 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic acid dianhydride.

[0057] As for compounds having two or more hydroxyl groups, compounds having a hydroxyl group and a thiol group in the molecule are preferred, and compounds having two hydroxyl groups and one thiol group in the molecule are more preferred. Examples of compounds having two hydroxyl groups and one thiol group in their molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, or 2-mercaptoethyl-2-ethyl-1,3-propanediol.

[0058] Examples of monoalcohols include methanol, ethanol, 1-butanol, 2-butanol, isobutanol, t-butanol, 1-pentanol, isopentyl alcohol, tert-pentyl alcohol, cyclopentanol, 1-hexanol, cyclohexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, isononyl alcohol, 1-nonyl alcohol, amyl alcohol, lauryl alcohol, n-butyl alcohol, isobutyl alcohol, cyclohexanol, benzyl alcohol, methylcyclohexanol, and other monoalcohols, as well as 3-methoxy-3-methyl-1-butanol, 3-methoxybutanol, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, and ethylene glycol monopropyl ether. Examples include monoalcohols having an ether group, such as ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol monophenyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, and propylene glycol monomethyl ether; and monoalcohols having a carbonyl group, such as methyl lactate, ethyl lactate, and diacetone alcohol. These can be used individually or in combination of two or more.

[0059] The monoalcohol is preferably a compound having an ether group or a carbonyl group. The dispersant can have an ether group or a carbonyl group at the end of its main chain, which improves the solubility of the dispersant in the dispersion medium. Among these, 3-methoxybutanol, propylene glycol monomethyl ether, and diacetone alcohol are preferred. The main chain, which is an aromatic carboxylic acid ester moiety, may have sealing sites derived from a monoalcohol, as well as sealing sites formed by reaction with water. Regarding the synthesis of the sealing site, the amount of monoalcohol used relative to the acid anhydride group is preferably between 1 molar equivalent and 30 molar equivalents, and more preferably between 1.5 molar equivalents and 20 molar equivalents, per 1 equivalent of acid anhydride group remaining in the main chain. If the amount is 1 molar equivalent or more, no acid anhydride group remains, resulting in good storage stability. If the amount is 30 molar equivalents or less, transesterification reactions due to ester bonding between the monoalcohol and the dispersant are less likely to occur, and a decrease in molecular weight is less likely to occur.

[0060] The side chains are obtained by polymerizing a vinyl polymerizable compound in the presence of a compound having a thiol group. When a compound containing a thiol group is used, specifically a compound having two hydroxyl groups and one thiol group in its molecule, the main chain is formed after the side chain is formed. Furthermore, when a compound containing thiol groups is used, specifically the main chain after the esterification reaction (which has multiple thiol groups derived from a compound containing two hydroxyl groups and one thiol group in its molecule), side chains are formed after the main chain is formed.

[0061] (Other resins containing acidic groups) The dispersants having acidic groups are not limited to the examples described above. For example, the dispersant may be a resin having a main chain with acidic groups other than aromatic carboxylic acids and side chains containing vinyl polymer moieties. The main chain of this resin is formed by radical polymerization of repeating resin units that do not contain aromatics, such as (meth)acrylic resin, polyester resin, polyurethane resin, polyurea resin, polyamide resin, and polyether resin, and repeating units that contain one or more acidic groups.

[0062] Examples of repeating units containing one or more acidic groups include (meth)acrylic acid, vinylbenzoic acid, maleic acid, maleic acid monoalkyl esters, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylate dimer, 2-acrylamido-2-methylpropanesulfonic acid, phosphate mono(2-acryloyloxyethyl ester), and phosphate mono(1-methyl-2-acryloyloxyethyl ester). Addition reaction products of monomers having hydroxyl groups, such as 2-hydroxyethyl (meth)acrylate, and cyclic anhydrides, such as maleic anhydride, phthalic anhydride, succinic anhydride, and cyclohexanedicarboxylic acid anhydride, can also be used. In this specification, when "(meth)acryloyl," "(meth)acrylic," "(meth)acrylic acid," "(meth)acrylate," or "(meth)acrylamide" is used, unless otherwise specified, it shall refer to "acryloyl and / or methacryloyl," "acrylic and / or methacrylic," "acrylic acid and / or methacrylic acid," "acrylate and / or methacrylate," or "acrylamide and / or methacrylamide," respectively.

[0063] Furthermore, the dispersant having an acidic group may contain a nitrogen atom in at least one of its main chain and side chains. For example, the main chain or side chain may contain poly(lower alkyleneimine) repeating units, polyallylamine repeating units, polydiallylamine repeating units, metaxylenediamine-epichlorohydrin polycondensate repeating units, and polyvinylamine repeating units.

[0064] • Dispersants containing basic groups The amine value of the dispersant having a basic group is preferably around 60 mg KOH / g to 75 mg KOH / g, and more preferably around 65 mg KOH / g to 73 mg KOH / g. A sufficiently high amine value of the dispersant allows the dispersant molecules to repel each other sufficiently. Furthermore, by keeping the amine value of the dispersant from being too high, the dispersant itself can maintain its affinity for the dispersion medium, allowing the diamond particles 32 to be sufficiently dispersed in the dispersion composition. Examples of basic groups include tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocyclic groups, and imino groups.

[0065] Furthermore, it is particularly preferable to use a linear basic resin as the dispersant having basic groups. This prevents or suppresses the aggregation of molecules constituting the dispersant into clumps, and makes it easier to hold diamond particles between dispersants that repel each other. Preferred examples of resin-type dispersants having basic groups include nitrogen atom-containing graft copolymers, or nitrogen atom-containing acrylic block copolymers or urethane polymer compounds having functional groups in their side chains, such as tertiary amino groups, quaternary ammonium bases, or nitrogen-containing heterocyclic groups. In particular, the dispersant having basic groups is preferably a block copolymer in which a first block, which is a vinyl polymer, and a second block having basic groups are bonded at their ends. With a dispersion resin having such a molecular structure, the solubility in the solvent due to the first block and the repulsion between the second blocks are exhibited in a well-balanced manner.

[0066] Furthermore, a dispersant having an acidic group and a dispersant having a basic group may be used in combination. In this case, for example, as disclosed in Japanese Patent Application Publication No. 2009-185277, a resin-type dispersant having an aromatic carboxyl group and a vinyl resin having a tertiary amino group (which functions as a resin-type dispersant) may be used in combination. It is not limited to this, and can be used in various combinations.

[0067] By using the dispersant described above, the diamond particles 32 can be suitably dispersed in the dispersion composition. Furthermore, regardless of the type of alkali-soluble resin described below, it can be suitably used as a photoresist or the like.

[0068] The dispersant is preferably used in an amount of 50 to 500 parts by mass, and more preferably 100 to 300 parts by mass, per 100 parts by mass of diamond particles 32. This allows the diamond particles 32 to be sufficiently dispersed in the dispersion medium.

[0069] <<Pigment derivative>> The dispersant may, if necessary, contain a pigment derivative as a dispersion aid. Pigment derivatives are compounds that have acidic groups, basic groups, neutral groups, etc., in their organic dye residues. Examples of pigment derivatives include compounds having acidic groups such as sulfo groups, carboxyl groups, and phosphate groups, or their amine salts, compounds having basic groups such as sulfonamide groups and tertiary amino groups at the terminal, and compounds having neutral groups such as phenyl groups and phthalimidoalkyl groups. When adding pigment derivatives, it is preferable to use pigment derivatives that have functional groups exhibiting the same liquid properties (acidic, basic) as the functional groups of the dispersant. This can be expected to enhance the behavior of the dispersant, i.e., improve the dispersibility of the diamond particles 32.

[0070] Examples of organic pigments include diketopyrrolopyrrole (hereinafter also referred to as DPP) pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiaidine indigo pigments, triazine pigments, benzimidazolon pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, surene pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo. Among these, DPP pigments, phthalocyanine pigments, triazine pigments, or quinophthalone pigments are preferred, phthalocyanine pigments or triazine pigments are more preferred, and triazine pigments are particularly preferred. In this case, excessive aggregation or precipitation in the dispersion composition can be more effectively prevented or suppressed. In particular, excessive aggregation or precipitation is less likely to occur when the average primary particle diameter of the diamond particles 32 is relatively large (for example, around 200 nm or more).

[0071] The pigment derivative may be used as a single compound or in combination of two or more compounds. When adding a pigment derivative, the amount used can be, for example, 0 to 100 parts by mass, 3 to 70 parts by mass, or 5 to 50 parts by mass per 100 parts by mass of diamond particles 32. However, the amount used when adding a pigment derivative is preferably 0 to 30 parts by mass, more preferably 0 to 20 parts by mass, and even more preferably 0 to 15 parts by mass per 100 parts by mass of diamond particles 32. In this case, the diamond particles can be dispersed well while maintaining sufficient permeability of the dispersant.

[0072] <<Dispersion medium>> The dispersion medium in which the diamond particles 32 are dispersed by the dispersant is preferably composed of, for example, at least one solvent. The solvent should preferably be selected considering factors such as the solubility of each component, the applicability of the resin composition, and safety. Examples of solvents include ketones, aromatic hydrocarbons, esters, and ethers. Examples of ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone. Examples of aromatic hydrocarbons include toluene and xylene.

[0073] Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropyl Examples include methyl ropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, and ethyl 2-oxobutanoate.

[0074] Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA), propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.

[0075] The dispersion medium is preferably used in an amount of 100 to 1000 parts by mass, and more preferably 200 to 500 parts by mass, per 100 parts by mass of diamond particles. This allows the diamond particles to be sufficiently dispersed in the dispersion medium.

[0076] <Resin composition> The resin composition includes the dispersion composition described above. Specifically, the resin composition of this embodiment includes the dispersion composition, a binder compound, and a curable compound. The content of the dispersion composition relative to the total amount of the resin composition is preferably 10% by mass or more and 80% by mass or less, and more preferably 20% by mass or more and 50 parts by mass or less. This makes it possible to produce a diamond dispersion film 3 that has dry etching resistance and low environmental impact when removed, as described above.

[0077] <<Binder Compound>> As the binder compound (binder resin), a resin with a transmittance of approximately 80% or more across the entire wavelength range from 400 nm to 700 nm can be used. Preferably, the transmittance across the entire wavelength range from 400 nm to 700 nm is approximately 95% or more. Furthermore, as mentioned above, the binder compound is preferably an alkali-soluble resin.

[0078] Binder resins can be used alone or in combination of two or more types. The binder resin content is preferably 20 to 400 parts by mass, and more preferably 50 to 250 parts by mass, per 100 parts by mass of diamond particles 32. This allows for the easy formation of a diamond dispersion film 3 in which the diamond particles 32 are dispersed.

[0079] (Alkali-soluble resin) In this disclosure, the weight-average molecular weight (Mw) of the binder resin (alkali-soluble resin) is preferably about 2,000 to 40,000, more preferably about 3,000 to 30,000, and even more preferably about 4,000 to 20,000. Furthermore, the Mw / Mn value is preferably about 10 or less. Having such a weight-average molecular weight allows for easy and accurate development of the diamond dispersion film 3. Specifically, a sufficiently large weight-average molecular weight (Mw) prevents or suppresses a decrease in adhesion to the substrate 2, regardless of the surface properties of the substrate 2. This makes it easier for the exposure pattern (the exposed and cured diamond dispersion film 3) to remain well on the main surface 21 of the substrate 2. Also, because the weight-average molecular weight (Mw) is not too large, the pre-cured film dissolves well in the alkaline developer, making it easier to prevent or suppress the generation of residue. That is, the edge shape of the pattern formed by the diamond dispersion film 3 is good. The acid value of the alkali-soluble resin in this disclosure is preferably 50 KOH mg / g to 200 KOH mg / g, more preferably 70 KOH mg / g to 180 KOH mg / g, and even more preferably 90 KOH mg / g to 170 KOH mg / g. Having a sufficiently high acid value in this way allows the pre-cured film to dissolve sufficiently in the alkaline developer, thereby preventing or suppressing the generation of residue. Furthermore, by not having an excessively high acid value, a decrease in adhesion to the substrate 2 can be prevented or suppressed regardless of the surface properties of the substrate 2. In other words, having an acid value of this degree allows the diamond dispersion film 3 to be developed easily and accurately.

[0080] Examples of alkali-soluble resins include thermoplastic resins, photosensitive resins, and non-photosensitive resins. Examples of thermoplastic resins as alkali-soluble resins include resins having acidic groups such as carboxyl groups and sulfone groups. Examples of such thermoplastic resins include acrylic resins having acidic groups, α-olefin / (anhydride) maleic acid copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, or isobutylene / (anhydride) maleic acid copolymers. Among these, acrylic resins having acidic groups and styrene / styrene sulfonic acid copolymers are preferred. This makes it easier to improve the developability, heat resistance, and transparency of the diamond dispersion film 3.

[0081] The photosensitive resin, as an alkali-soluble resin, preferably has an ethylenically unsaturated double bond. The ethylenically unsaturated double bond can be introduced, for example, by the method shown in (i) or (ii) below. This results in three-dimensional crosslinking of the diamond dispersion film 3, increasing the crosslinking density and improving chemical resistance.

[0082] [Method (i)] Method (i) involves, for example, adding a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond to the side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group with another monomer. Then, the resulting hydroxyl group is reacted with a polybasic acid anhydride to introduce an ethylenically unsaturated double bond and a carboxyl group.

[0083] Examples of ethylenically unsaturated monomers having an epoxy group include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred. This improves the reactivity with unsaturated monobasic acids.

[0084] Examples of unsaturated monobasic acids include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, and monocarboxylic acids such as α-haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted derivatives of (meth)acrylic acid.

[0085] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. Furthermore, if necessary, such as increasing the number of carboxyl groups, tricarboxylic acid anhydrides such as trimellitic anhydride or tetracarboxylic dianhydrides such as pyromellitic dianhydride may be used to hydrolyze the remaining anhydride groups.

[0086] Other monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropyl Examples include (meth)acrylates such as ethylene glycol (meth)acrylate or ethoxypolyethylene glycol (meth)acrylate, or (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acryloylmorpholine, as well as styrenes such as styrene or α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, and vinyl fatty acid compounds such as vinyl acetate or vinyl propionate.

[0087] Alternatively, for example, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidediphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3- Examples include maleimide benzoate, N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimide acridine, and other N-substituted maleimides; EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol.

[0088] A method similar to method (i) is, for example, a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with another monomer, to which an ethylenically unsaturated monomer having an epoxy group is added to some of the side chain carboxyl groups of the copolymer, thereby introducing an ethylenically unsaturated double bond and a carboxyl group.

[0089] [Method (ii)] Method (ii) involves reacting the isocyanate group of an ethylenically unsaturated monomer having an isocyanate group with the isocyanate group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group with another monomer.

[0090] Examples of ethylenically unsaturated monomers having hydroxyl groups include hydroxyalkyl methacrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate. Other examples include polyether mono(meth)acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to hydroxyalkyl (meth)acrylate, and polyester mono(meth)acrylate obtained by addition of polyγ-valerolactone, polyε-caprolactone, and / or poly12-hydroxystearic acid. Among these, it is preferable to use 2-hydroxyethyl methacrylate or glycerol mono(meth)acrylate, as this can prevent or suppress the contamination of the diamond dispersion film 3 with foreign matter. Furthermore, it is preferable to use a compound having two to six hydroxyl groups, and it is particularly preferable to use glycerol mono(meth)acrylate. In this case, sensitivity to light is improved.

[0091] Examples of ethylenically unsaturated monomers having an isocyanate group include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0092] Other monomers that can constitute alkali-soluble resins include, in addition to the other ethylenically unsaturated monomers already described, N-substituted maleimides, alkylene oxy group-containing monomers, phosphate ester group-containing ethylenically unsaturated monomers, carboxyl group-containing ethylenically unsaturated monomers, and the like. Examples of N-substituted maleimides include cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidediphenylmethane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N Examples include -(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-[4-(2-benzoimidazolyl)phenyl]maleimide, and 9-maleimide acridine. Examples of alkylene oxy group-containing monomers include EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol.

[0093] As carboxyl group-containing ethylenically unsaturated monomers, the monomers already described can be used. Examples of ethylenically unsaturated monomers containing phosphate ester groups include compounds obtained by reacting the hydroxyl group of the above-mentioned ethylenically unsaturated monomer containing a hydroxyl group with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphate.

[0094] Furthermore, the binder resin may also contain thermoplastic compounds other than alkali-soluble resins, thermosetting compounds, photosensitive resins, etc. Examples of thermoplastic compounds include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclorelated rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

[0095] The thermosetting compound may be a low-molecular-weight compound or a high-molecular-weight compound such as a resin. Examples of thermosetting compounds include, but are not limited to, epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenolic compounds. Each raw material used in the synthesis of the binder resin can be used individually or in combination of two or more types.

[0096] <<Curable compound>> As described above, the resin composition includes a curable compound. The curable compound is, for example, a polymerizable compound, and in this embodiment, it is preferable that it includes a monomer or oligomer that hardens with light (active energy rays) to produce a translucent resin. As curable compounds, polymerizable compounds having acidic groups, polymerizable compounds having urethane bonds, and polymerizable compounds modified with ethylene oxide (EO) or propylene oxide (PO) are particularly preferred, with polymerizable compounds modified with ethylene oxide (EO) or propylene oxide (PO) being more preferred. The curable compound is preferably one that has an ethylenically unsaturated double bond. As polymerizable compounds, polymerizable compounds having an acidic group, polymerizable compounds having a urethane bond, and polymerizable compounds modified with ethylene oxide (EO) or propylene oxide (PO) are particularly preferred, with polymerizable compounds modified with ethylene oxide (EO) or propylene oxide (PO) being especially preferred.

[0097] (Polymerizable compounds containing acidic groups) The polymerizable compounds in this disclosure may contain polymerizable compounds having acidic groups. Examples of acidic groups include sulfonic acid groups, carboxyl groups, and phosphate groups.

[0098] Examples of polymerizable compounds having acidic groups include esters of polyhydric alcohols and (meth)acrylic acid poly(meth)acrylates containing free hydroxyl groups and dicarboxylic acids, or esters of polyhydric acids and monohydroxyalkyl (meth)acrylates. Specific examples include monoesterified compounds containing free carboxyl groups of monohydroxyoligoacrylates or monohydroxyoligomethacrylates and dicarboxylic acids. Examples of monohydroxyoligoacrylates or monohydroxyoligomethacrylates include trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. Examples of dicarboxylic acids include malonic acid, succinic acid, glutaric acid, and phthalic acid. Another specific example is oligoesters containing free carboxyl groups of tricarboxylic acids and monohydroxymonoacrylates or monohydroxymonomethacrylates. Examples of tricarboxylic acids include propane-1,2,3-tricarboxylic acid (tricarbaryl acid), butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, and benzene-1,3,5-tricarboxylic acid. Examples of monohydroxymonoacrylates or monohydroxymonomethacrylates include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

[0099] (Polymerizable compound containing urethane bonds) The polymerizable compounds in this disclosure may include polymerizable compounds containing at least one ethylenically unsaturated bond and one urethane bond. Examples include polyfunctional urethane acrylates obtained by reacting a polyfunctional isocyanate with a hydroxyl group-containing (meth)acrylate, and polyfunctional urethane acrylates obtained by reacting an alcohol with a polyfunctional isocyanate and then reacting that with a hydroxyl group-containing (meth)acrylate.

[0100] Examples of (meth)acrylates containing hydroxyl groups include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction products of epoxy group-containing compounds and carboxy(meth)acrylate, and hydroxyl group-containing polyol polyacrylate.

[0101] Examples of polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanates.

[0102] Furthermore, it is preferable that the polymerizable compound contains one or more types of ethylene oxide (EO)-modified (meth)acrylate or propylene oxide (PO)-modified (meth)acrylate. When an (EO)-modified unit or a (PO)-modified unit is present, it is thought that using it in combination with an oxime ester-based photopolymerization initiator allows hydrogen bonds to be formed between the polymerizable compound and the photopolymerization initiator, bringing the radical generation site and the reaction site into close proximity, thereby promoting more efficient photocuring.

[0103] Examples of these include, preferably, the photopolymerizable compound contains at least one (meth)acrylate compound selected from the group consisting of (meth)acrylate compounds having a trimethylolpropane skeleton, (meth)acrylate compounds having a ditrimethylolpropane skeleton, (meth)acrylate compounds having a pentaerythritol skeleton, (meth)acrylate compounds having a dipentaerythritol skeleton, (meth)acrylate compounds having a glycerin skeleton, (meth)acrylate compounds having a diglycerin skeleton, and alkylene oxide modified compounds thereof. The above (meth)acrylate compound is preferably a bifunctional or more (meth)acrylate compound having two or more (meth)acryloyl groups, and more preferably a trifunctional or more (meth)acrylate compound having three or more (meth)acryloyl groups.

[0104] Here, (meth)acrylate compounds having a skeleton derived from ditrimethylolpropane can be obtained, for example, by esterifying ditrimethylolpropane with (meth)acrylic acid, or by transesterification using a neutral catalyst. These compounds also include compounds modified with alkylene oxy groups. Preferably, the above compounds have two or more ester bonds in a single molecule, and compounds with two to four ester bonds may be mixed.

[0105] Furthermore, (meth)acrylate compounds having a diglycerin-derived skeleton can be obtained, for example, by esterifying diglycerin with (meth)acrylic acid, or by transesterification using a neutral catalyst. These compounds also include compounds modified with alkylene oxy groups. Preferably, the above compounds have two or more ester bonds in a single molecule, and compounds with two to four ester bonds may be mixed.

[0106] The above-mentioned (meth)acrylate compounds having a skeleton derived from ditrimethylolpropane and (meth)acrylate compounds having a skeleton derived from diglycerin preferably include at least one compound selected from alkylene oxide-modified ditrimethylolpropane di(meth)acrylate compounds, alkylene oxide-modified ditrimethylolpropane tri(meth)acrylate compounds, alkylene oxide-modified ditrimethylolpropane tetra(meth)acrylate compounds, alkylene oxide-modified diglycerin di(meth)acrylate compounds, alkylene oxide-modified diglycerin tri(meth)acrylate compounds, and alkylene oxide-modified diglycerin tetra(meth)acrylate compounds, and more preferably include at least one compound selected from alkylene oxide-modified ditrimethylolpropane tetra(meth)acrylate compounds and alkylene oxide-modified diglycerin tetra(meth)acrylate compounds. This can further improve the ease of development.

[0107] Examples of (meth)acrylates having a dipentaerythritol-derived skeleton include dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and alkylene oxide-modified compounds thereof. Of these, dipentaerythritol hexa(meth)acrylate and alkylene oxide-modified dipentaerythritol hexa(meth)acrylate are preferred.

[0108] Examples of (meth)acrylate compounds having a trimethylolpropane-derived skeleton include trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and alkylene oxide-modified compounds thereof. Of these, trimethylolpropane tri(meth)acrylate and alkylene oxide-modified trimethylolpropane tri(meth)acrylate are preferred. Examples of (meth)acrylate compounds having a pentaerythritol-derived skeleton include pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and alkylene oxide-modified compounds thereof. Of these, pentaerythritol tetra(meth)acrylate and alkylene oxide-modified pentaerythritol tetra(meth)acrylate are preferred. Examples of (meth)acrylate compounds having a glycerin-derived skeleton include glycerin di(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide-modified compounds thereof. Of these, glycerin tri(meth)acrylate and alkylene oxide-modified glycerin tri(meth)acrylate are preferred.

[0109] (Other polymerizable compounds) Other polymerizable compounds include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate. Examples include (meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl(meth)acrylate, (meth)acrylic acid ester of methylolated melamine, epoxy(meth)acrylate, methacrylic acid ester, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, acrylonitrile, etc.

[0110] Additionally, photosensitive resins listed under the section on alkali-soluble resins can also be used. The polymerizable compounds described above can be used individually or mixed in any ratio of two or more as needed.

[0111] The amount of polymerizable compound added is preferably 1 to 50 parts by mass, and more preferably 2 to 40 parts by mass, based on 100 parts by mass of the total nonvolatile content of the resin composition. This enables efficient curing and desired development.

[0112] <<Photopolymerization initiator>> The resin composition may further contain a photopolymerization initiator. Examples of photopolymerization initiators include acetophenone compounds, benzoin compounds, thioxanthone compounds, triazine compounds, oxime ester compounds, phosphine compounds, quinone compounds, borate compounds, carbazole compounds, imidazole compounds, and titanocene compounds. Examples of acetophenone compounds include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone. Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyldimethyl ketal. Examples of benzophenone compounds include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylic benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone. Examples of thioxanthone compounds include thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone.Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine. Examples of oxime ester compounds include 1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyl oxime)], or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime). Examples of phosphine compounds include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, or diphenyl-2,4,6-trimethylbenzoylphosphine oxide. Examples of quinone compounds include 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone.

[0113] However, among these, the photopolymerization initiator is preferably an oxime ester compound. Oxime ester compounds undergo cleavage of the NO bond in the oxime upon absorption of ultraviolet light, generating iminyl radicals and alkyloxy radicals. These radicals can be further decomposed to generate highly active radicals, allowing patterns to be formed with a small amount of exposure. Therefore, even when the light transmittance of the resin composition is relatively low, a good pattern (shape of the diamond dispersion film 3) can be formed by using an oxime ester compound with high quantum efficiency as a photopolymerization initiator.

[0114] Examples of oxime ester compounds include oxime ester photopolymerization initiators described in Japanese Patent Publication No. 2007-210991, Japanese Patent Publication No. 2009-179619, Japanese Patent Publication No. 2010-037223, Japanese Patent Publication No. 2010-215575, Japanese Patent Publication No. 2011-020998, and the like.

[0115] Photopolymerization initiators can be used alone or in combination of two or more types. The amount of photopolymerization initiator is preferably 0.1 parts by mass to 20 parts by mass, and more preferably 0.2 parts by mass to 10 parts by mass, per 100 parts by mass of the nonvolatile content of the resin composition. This formulation improves photocurability and developer resistance, and makes it easier to achieve a smooth surface on the diamond dispersion film 3.

[0116] <<Sensitizer>> Furthermore, the resin composition of this disclosure may contain a sensitizer. Examples of sensitizers include unsaturated ketones such as chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiaidine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyradinoporphyrazine derivatives. Examples include conductors, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxaliloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrillium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospilopyran derivatives, metal arene complexes, organoruthenium complexes, or Michler ketone derivatives, α-acyloxyesters, acylphosphine oxides, methylphenylglyoxylates, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, and the like.

[0117] Among the sensitizers mentioned above, thioxanthone derivatives, Michler ketone derivatives, and carbazole derivatives are particularly suitable for sensitizing. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl-N-ethylcarbazole, etc., can be used.

[0118] More specifically, examples of sensitizers include, but are not limited to, those described in "Pigment Handbook" (1986, Kodansha) edited by Shin Okawara et al., "Chemistry of Functional Pigments" (1981, CMC) edited by Shin Okawara et al., and "Special Functional Materials" (1986, CMC). In addition, sensitizers that exhibit absorption in the ultraviolet to near-infrared region can also be included. Sensitizers can be used alone or in combination of two or more types. The sensitizer content is preferably 3 to 60 parts by mass, and more preferably 5 to 50 parts by mass, per 100 parts by mass of the photopolymerization initiator. Including an appropriate amount further improves curability and developability.

[0119] <<Thiol-based chain transfer agent>> The resin composition may further contain a chain transfer agent. Examples of such chain transfer agents include thiol-based chain transfer agents.

[0120] The thiol-based chain transfer agent is preferably a polyfunctional aliphatic thiol, which has two or more thiol groups bonded to aliphatic groups such as methylene or ethylene groups. More preferably, it is a polyfunctional aliphatic thiol with four or more thiol groups. Increasing the number of functional groups improves the polymerization initiation function, allowing curing from the surface of the diamond dispersion film 3 to the substrate 2 (main surface 21).

[0121] Examples of polyfunctional thiols include hexanedithiol and decanedithiol. Examples include 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, etc., with ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate being preferred.

[0122] Thiol-based chain transfer agents can be used alone or in combination of two or more types. The content of the thiol-based chain transfer agent is preferably 0.1% to 10% by mass, and more preferably 0.1% to 3% by mass, based on 100% by mass of the nonvolatile content of the resin composition. When an appropriate amount is included, the light sensitivity is improved and wrinkles are less likely to occur on the surface of the diamond dispersion film 3.

[0123] <<Polymerization inhibitor>> The resin composition may further contain a polymerization inhibitor. In this case, photosensitivity due to diffracted light from the mask can be suppressed during photolithography exposure. This makes it easier to obtain a diamond dispersion film 3 with the desired shape.

[0124] Examples of polymerization inhibitors include alkylcatechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, 3,5-di-tert-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, and 2-n Examples include alkylresorcinol compounds such as -butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, and 4-tert-butylresorcinol; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, and 2,5-di-tert-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tripenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphine and trisnonylphenylphosphine; pyrogallol and phloroglucin.

[0125] The polymerization inhibitor content is preferably 0.01% to 0.4% by mass of the non-volatile content of the resin composition. By keeping the content within this range, the effect of the polymerization inhibitor is enhanced, resulting in improved wrinkle and pattern resolution of the diamond dispersion film 3.

[0126] <<UV absorber>> The resin composition may further contain an ultraviolet absorber. An ultraviolet absorber is an organic compound that has the function of absorbing ultraviolet light such as i-rays, and examples include benzotriazole compounds, triazine compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, and salicylate compounds.

[0127] Examples of benzotriazole compounds include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, and 5% A mixture of 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazole2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side chain and linear alkyl ester, 2-(2H-benzotriazole2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazole2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl Reaction product of 3-(3-(2H-benzotriazole2-yl)-5-t-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300, 2-(2H-benzotriazole2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazole2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazole2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazole2-yl)-6-t-butyl Examples include 4-methylphenol, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole2-yl)phenyl]propionate, and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole2-yl)phenyl]propionate.

[0128] Examples of triazine compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, and the reaction of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with (2-ethylhexyl)-glycidic acid ester. Examples of the resulting products include 2,4-bis"2-hydroxy-4-butoxyphenyl"-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine. Other oligomeric and polymeric compounds having a triazine structure can also be used.

[0129] Examples of benzophenone compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone. Other oligomeric and polymeric compounds having a benzophenone structure can also be used.

[0130] Examples of salicylic acid ester compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tertbutylphenyl salicylate. Other oligomer and polymer type compounds having a salicylic acid ester structure can also be used.

[0131] The amount of UV absorber is preferably 5% to 70% by mass of the total 100% by mass of the photopolymerization initiator and UV absorber. Including an appropriate amount further improves developability.

[0132] Furthermore, the total content of the photopolymerization initiator and ultraviolet absorber is preferably about 1% to 20% by mass of the non-volatile content of the resin composition. When an appropriate amount is included, the adhesion between the substrate 2 and the diamond dispersion film 3 is further improved, and good developability is obtained.

[0133] <<Antioxidant>> The resin composition may further contain an antioxidant. The antioxidant prevents the photopolymerization initiator and thermosetting compounds contained in the resin composition from oxidizing and yellowing due to high-temperature processing. This improves the light transmittance of the diamond dispersion film 3. Examples of high-temperature processing include ITO annealing when manufacturing semiconductor devices from the film-coated substrate 1.

[0134] Examples of antioxidants include hindered phenol compounds, hindered amine compounds, phosphorus compounds, sulfur compounds, and hydroxylamine compounds. In this specification, it is preferable that the antioxidant is a compound that does not contain halogen atoms.

[0135] Among these, hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants, and sulfur antioxidants are preferred. In this case, the light transmittance of the diamond dispersion film 3 is easily improved.

[0136] Antioxidants can be used alone or in combination of two or more types. Furthermore, the antioxidant content is preferably 0.5% to 5.0% by mass of the non-volatile content of the resin composition, which makes it easier to improve the light transmittance of the diamond dispersion film 3.

[0137] <<Leveling agent>> The resin composition may further contain a leveling agent. When a leveling agent is included, the wettability of the diamond dispersion film 3 to the substrate 2 is improved. In addition, the diamond dispersion film 3 can be applied with a relatively uniform thickness. Examples of leveling agents include various surfactants such as silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants.

[0138] Examples of silicone-based surfactants include linear polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals. More specifically, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345 / 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 3570 from BIC Chemie, and FZ-7002, 2110, 2 from Toray Dow Corning Co., Ltd. Products such as 122, 2123, 2191, 5609, and Shin-Etsu Chemical Co., Ltd.'s X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341, etc. can be used.

[0139] Examples of fluorine-based surfactants include surfactants or leveling agents having fluorocarbon chains. More specifically, the following products can be used: Surflon S-242, S-243, S-420, S-611, S-651, S-386 from AGC Seimi Chemical Co., Ltd., Megafac F-253, F-477, F-551, F-552, F-555, F-558, F-560, F-570, F-575, F-576, R-40-LM, R-41, RS-72-K, DS-21 from DIC Corporation, FC-4430, FC-4432 from Sumitomo 3M Limited, EF-PP31N09, EF-PP33G1, EF-PP32C1 from Mitsubishi Materials Electronic Chemicals Co., Ltd., and Futergent 602A from Neos Co., Ltd.

[0140] Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristelle ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, and sorbitan tristearate. Examples include sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitan tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanolamide, alkylimidazoline, etc. More specifically, Kao Corporation's Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, LS -110, LS-114, MS-110, A-60, A-90, B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD450, Leodor SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW-L106 TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60(K), Amito 102, 105, 105 A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA Pluronic (registered trademark) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R manufactured by ADEKA Corporation, and (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 90, No. 95 manufactured by Kyoeisha Chemical Co., Ltd. can be used.

[0141] Examples of cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and their ethylene oxide adducts. More specifically, products such as Acetamine 24, Cortamin 24P, 60W, and 86P Concentrate manufactured by Kao Corporation can be used.

[0142] Examples of anionic surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate esters. More specifically, products such as Neos Co., Ltd.'s Futergent 100 and 150, and ADEKA Corporation's Adeka Hope YES-25, Adeka Call TS-230E, PS-440E, EC-8600, etc. can be used.

[0143] Examples of amphoteric surfactants include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyldimethylaminoacetic acid betaine, and alkylamine oxides such as lauryldimethylamine oxide. More specifically, Kao Corporation's Anchitol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, ​​20N, etc., can be used.

[0144] The amount of surfactant added is preferably 0.001% to 2.0% by mass, and more preferably 0.005% to 1.0% by mass, based on 100% by mass of the non-volatile content of the resin composition. Within this range, a good balance is achieved between the wettability and pattern adhesion of the resin composition to the substrate 2 and the light transmittance. The resin composition may contain only one type of surfactant, or it may contain two or more types. If it contains two or more types, it is preferable that the total amount is within the above range.

[0145] <<Adhesion enhancer>> The resin composition may further contain adhesion-enhancing agents such as silane coupling agents. The inclusion of adhesion-enhancing agents improves the adhesion between the diamond dispersion film 3 and the substrate 2. This allows for the creation of finer patterns.

[0146] Examples of adhesion enhancers include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, (meth)acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane, epoxysilanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane, and N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane. Examples of silane coupling agents include aminosilanes such as 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and hydrochloride salts of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; mercaptos such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryls such as p-styryltrimethoxysilane; ureidos such as 3-ureidopropyltriethoxysilane; sulfides such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanates such as 3-isocyanatetopropyltriethoxysilane. The adhesion enhancer can be added in an amount of approximately 0.001 parts by mass to 10 parts by mass per 100 parts by mass of the resin composition, and is preferably added in an amount of approximately 0.005 parts by mass to 5 parts by mass. Within this range, the effect is greater and good adhesion is achieved.

[0147] <<Solvent>> The resin composition further contains a solvent. This allows for the adjustment of the non-volatile content concentration of the resin composition to form a relatively thin diamond dispersion film 3 on the substrate 2. The solvent is selected considering its good ability to transfer the resin composition to the substrate 2, as well as the solubility of each component of the resin composition and safety.

[0148] Various solvents can be used as solvents, and their properties such as boiling point, SP value, evaporation rate, and viscosity are taken into consideration, and they are used individually or in mixtures as appropriate according to the application conditions (e.g., application rate, drying conditions, etc.).

[0149] Examples of solvents include ester solvents (solvents containing -COO- but not -O-), ether solvents (solvents containing -O- but not -COO-), ether ester solvents (solvents containing both -COO- and -O-), ketone solvents (solvents containing -CO- but not -COO-), alcohol solvents (solvents containing OH but not -O-, -CO-, and -COO-), aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxides.

[0150] It is preferable to include an organic solvent among the above solvents, whose boiling point at 1 atm is approximately 120°C to 180°C. This makes it easier to apply the resin composition to the main surface 21 of the substrate 2 and allows it to dry in a suitable amount of time. Among these, PGMEA, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, N-methylpyrrolidone, etc. are preferred, and PGMEA, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, etc. are more preferred.

[0151] [Differentiation] The following describes modifications of the embodiments described above. The embodiments described above and the following descriptions are interchangeable.

[0152] In the embodiments described above, the case in which the diamond dispersion film 3 forms a pattern covering a part of the main surface 21 was explained, but the invention is not limited to this. That is, the diamond dispersion film 3 may cover the entire main surface 21. In this case, the steps of setting the mask [4] and developing the film [6] in the manufacturing method of the film-coated substrate 1 can be omitted. Furthermore, in the curing step [5], the diamond dispersion film 3 can be formed by exposing the entire pre-cured film without using a mask. Such a diamond dispersion film 3 can be used, for example, as an insulating film. Furthermore, in this case, the binder compound does not need to contain an alkali-soluble compound. For example, it may contain a thermoplastic resin, a thermosetting resin, etc.

[0153] In the embodiments described above, the pattern of the diamond dispersion film 3 was formed by partial exposure using a mask, but the invention is not limited to this. In this case, in the step of forming a liquid coating in the manufacturing method of the film-coated substrate 1 [2], the resin composition is applied only to the area on the main surface 21 where the diamond dispersion film 3 is to be formed. That is, for example, a liquid coating is formed in a pattern by a droplet ejection method (inkjet method), flexographic printing method, screen printing method, gravure printing method, offset printing method, etc. Then, in the curing step [5], the patterned diamond dispersion film 3 can be formed by exposing the entire pre-cured coating without using a mask. In this case, too, the steps of setting the mask [4] and developing the image [6] can naturally be omitted.

[0154] In the embodiments described above, the case in which the curable compound is a photocurable compound (active energy ray curable compound) was explained, but the invention is not limited to this. The curable compound may be, for example, a thermosetting compound or an anaerobic curable compound. In this case as well, the steps of setting the mask [4] and developing the product [6] are naturally unnecessary. If the diamond dispersion film 3 is to be formed in a pattern, the liquid film can be formed in a pattern beforehand in the step of forming the liquid film [2].

[0155] In the case of thermosetting compounds, in the manufacturing method of the film-coated substrate 1, in the step of obtaining a pre-cured film [3], instead of pre-baking, a low-temperature heat treatment is performed so that the curable compound reaches a semi-cured state (so-called B-stage state of thermosetting resin). This heat treatment can be carried out, for example, by leaving it for 0.1 seconds to 1 hour in a temperature environment of about 60°C to 150°C. Then, in the curing step [5], instead of exposure, a high-temperature heat treatment is performed so that the curable compound reaches a fully cured state (so-called C-stage state of thermosetting resin). This heat treatment can be carried out, for example, by leaving it for 0.1 seconds to 1 hour in a temperature environment of about 100°C to 300°C. Alternatively, the low-temperature heat treatment in the step of obtaining the pre-cured film [3] may be omitted, and only the high-temperature heat treatment may be performed. As thermosetting compounds, for example, thermosetting resins exemplified in the section on binder compounds can be used.

[0156] If the curable compound is an anaerobic curable compound, in the curing step [5], instead of exposure, the pre-cured film can be left standing with metal ions applied to it. This standing can be carried out, for example, by leaving it for 0.1 seconds to 1 hour.

[0157] Next, other embodiments of this disclosure will be described. The following describes other embodiments, focusing on the differences from the above embodiments, and omits explanations of similar matters. <Method for manufacturing a film-coated substrate> Next, an example of a method for manufacturing the film-coated substrate 1 of this embodiment will be described.

[0158] [1'] First, prepare the base material 2 and the resin composition in the same manner as in the above step [1]. In this embodiment, the curable compound is preferably a thermosetting compound, and the alkali-soluble compound may or may not be mixed. As the thermosetting compound, for example, the thermosetting resin exemplified in the section on binder compounds in the above embodiment can be used. In this case, the resin composition preferably contains a thermal polymerization initiator. Examples of thermal polymerization initiators include compounds that generate radicals by the action of heat to initiate or promote radical polymerization reactions, and azo compounds, organic peroxides, and oximesulfonate compounds are preferably used.

[0159] Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane1-carbonitride), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-hydroxymethylpropionitrile), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane].

[0160] Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl) peroxydicarbonate, t-butyl peroxydecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. Examples of oxime sulfonate compounds include those described in Japanese Patent Publication No. 5955339 and Japanese Patent Publication No. 6664383.

[0161] [2'] Next, the resin composition is applied to the main surface 21 of the substrate 2 in the same manner as in step [2] above to form a liquid coating. In this embodiment, the application of the resin composition to the main surface 21 of the substrate 2 is preferably carried out by a coating method such as a roll coating method, a rotary coating method, or a casting coating method. [3'] Next, in step [3] above, instead of pre-baking, a low-temperature heat treatment is performed so that the thermosetting compound reaches a semi-cured state (the so-called B-stage state of the thermosetting resin). This heat treatment can be carried out, for example, by leaving it for 0.1 seconds to 1 hour in a temperature environment of approximately 60°C to 150°C.

[0162] [4'] Next, in step [5] above, instead of exposure, the thermosetting compound is subjected to high-temperature heat treatment to reach the fully cured state (the so-called C-stage state of the thermosetting resin). This heat treatment can be carried out, for example, by leaving it for 0.1 seconds to 1 hour in a temperature environment of approximately 100°C to 300°C. Furthermore, the low-temperature heat treatment in step [3'] above may be omitted, and only the high-temperature heat treatment in step [4'] may be performed. In this manner, a diamond dispersion film 3 is formed on the main surface 21 of the substrate 2 to obtain a substrate 1 with a film.

[0163] The diamond particles 32 used in this disclosure have an appropriate primary particle size, making them less prone to aggregation in the resin composition. Therefore, the homogeneity of the diamond dispersion film 3 can be sufficiently enhanced. Because the diamond particles 32 have high thermal conductivity, the diamond dispersion film 3 can exhibit excellent heat dissipation (thermal conductivity). In recent years, with the growth of the AI ​​market, heat generation in electronic components such as semiconductor devices due to the increasing carrier transfer speed has become a significant problem. The film-coated substrate 1 of this embodiment is particularly suitable for application to such electronic components.

[0164] Furthermore, from the viewpoint of further improving the heat dissipation performance of the diamond dispersion film 3, it is important to increase the proportion of diamond particles 32 in the diamond dispersion film 3, and increasing the content of diamond particles 32 in the resin composition is effective in achieving this. Through diligent research by the inventors, it has become clear that the content of diamond particles 32 in the resin composition can be sufficiently increased by using a relatively high molecular weight dispersant. The weight-average molecular weight (Mw) of such dispersant is preferably between 34,000 and 60,000, more preferably between 36,000 and 50,000, and even more preferably between 38,000 and 40,000.

[0165] Furthermore, it is preferable that the dispersant contains structures or hydroxyl groups that contribute to thermosetting. This makes it possible to further increase the content of diamond particles 32 in the resin composition. The dispersibility of diamond particles 32 in the resin composition is also easily improved. The dispersant content is preferably, for example, about 25 parts by mass or more, and more preferably about 27.5 parts by mass or more and 50 parts by mass or less, per 100 parts by mass of diamond particles 32. When adding a pigment derivative, the amount of dispersant can be, for example, 50 to 100 parts by mass per 100 parts by mass of the total amount of pigment derivative and dispersant. If the amount of dispersant is too low, the pigment derivative will be in excess, which disrupts the adsorption balance of the dispersant to the diamond particles 32 and tends to reduce the dispersion stability of the resin composition.

[0166] The resin composition of this embodiment tends to have a low viscosity despite having a high content of diamond particles 32, making it easy to form a liquid coating with a uniform thickness, and thus a diamond dispersion film 3, by various coating methods. For this reason, using such a resin composition, a diamond dispersion film 3 can be formed well not only in large areas but also in relatively small fine areas. In this case, the viscosity of the resin composition is preferably about 30 cps or less at room temperature (20°C), and more preferably about 20 cps or less.

[0167] Suitable substrates 2 in this embodiment include, for example, multilayer wiring boards capable of mounting HBM (high bandwidth memory). In this case, the diamond dispersion film 3 can be formed directly on the main surface 21 of the substrate 2, or via a solder resist layer. Furthermore, the diamond dispersion film 3 is formed to avoid bumps for connecting HBM provided on the multilayer wiring board, etc. As described above, since the resin composition of this embodiment has a relatively low viscosity, the diamond dispersion film 3 can be formed uniformly and homogeneously while avoiding the bumps. Although each embodiment of this disclosure has been described above, the embodiments described in each embodiment can be combined with each other. Furthermore, the product may be provided in the following embodiments.

[0168] (1) A dispersion composition for forming a diamond dispersion film, comprising diamond particles, a dispersion medium, and a dispersant for dispersing the diamond particles in the dispersion medium, wherein the primary particles of the diamond particles have an average particle size D50, which is the cumulative 50% diameter in their volume-based particle size distribution, of 50 nm or more and 400 nm or less.

[0169] (2) The dispersion composition described in (1) above, wherein the primary particles of the diamond particles have an average particle size D50 of 100 nm or more and 300 nm or less.

[0170] (3) The dispersion composition according to (1) or (2) above, wherein the primary diamond particles have a volume-based particle size distribution where D10 is the cumulative 10% diameter and D10 is the cumulative 90% diameter, and (D90-D10) / D50 is 0.75 or more and 1 or less.

[0171] (4) A dispersion composition according to any one of (1) to (3) above, wherein the diamond particles are obtained by crushing a diamond mass.

[0172] (5) A dispersion composition according to any one of (1) to (4) above, wherein the weight-average molecular weight of the dispersant is 4600 or more and 60000 or less.

[0173] (6) The dispersion composition described in (5) above, wherein the dispersant is a branched acidic resin.

[0174] (7) A dispersion composition according to (6) above, wherein the acid value of the dispersant is 45 mg KOH / g or more and 100 mg KOH / g or less.

[0175] (8) The dispersion composition described in (5) above, wherein the dispersant is a linear basic resin.

[0176] (9) The dispersion composition described in (8) above, wherein the amine value of the dispersant is 60 mg KOH / g or more and 75 mg KOH / g or less.

[0177] (10) A method for producing a dispersion composition, comprising ultrasonic dispersion, homogenizer dispersion, or bead mill dispersion of diamond particles, a dispersion medium, and a dispersant for dispersing the diamond particles in the dispersion medium to obtain the dispersion composition.

[0178] (11) A liquid resin composition comprising the dispersion composition described in any one of (1) to (9) above.

[0179] (12) A resin composition according to (11) above, further comprising a curable compound.

[0180] (13) A resin composition according to (12) above, wherein the curable compound is a photocurable compound or a thermosetting compound.

[0181] (14) A resin composition according to any one of (11) to (13) above, further comprising an alkali-soluble compound.

[0182] (15) A film-coated substrate comprising a substrate and a diamond dispersion film, wherein the diamond dispersion film comprises a resin matrix and diamond particles dispersed in the resin matrix, and the primary particles of the diamond particles have an average particle size D50, which is the cumulative 50% diameter in their volume-based particle size distribution, of 50 nm or more and 400 nm or less.

[0183] (16) A method for manufacturing a film-coated substrate, comprising the steps of: preparing a substrate and a resin composition according to any one of (11) to (14) above; applying the resin composition to the substrate; removing at least a portion of the liquid components from the resin composition; and curing the resin composition after the removal of the liquid components to form a diamond dispersion film and obtain a film-coated substrate. Of course, this is not always the case.

[0184] Finally, while various embodiments relating to this disclosure have been described, these are presented as examples only and are not intended to limit the scope of the invention. These novel embodiments can be implemented in a variety of other forms, and various omissions, substitutions, and modifications can be made without departing from the spirit of the invention. These embodiments and their variations are included in the scope and spirit of the invention, as well as in the claims and their equivalents.

[0185] [Examples] The present invention will be described below with reference to examples. In the examples, "parts" and "%" refer to "parts by mass" and "mass%", respectively. Also, propylene glycol monomethyl ether acetate may be represented as PGMEA and cyclohexanone as CHA. First, we will explain the methods for measuring particle size distribution, weight-average molecular weight (Mw) of the dispersant, acid value / amine value of the dispersant, and non-volatile content of the dispersant.

[0186] 1.Measurement method (Particle size distribution of inorganic fillers) The particle size distribution of the inorganic filler was measured using a particle size distribution analyzer ("MicrotracUPA," manufactured by Nikkiso Co., Ltd.) by laser diffraction and scattering. For the measurement, 10 mg of inorganic filler was dispersed in 4 mL of water to prepare the sample. Based on the measurement results, the primary particle size D10 at which the cumulative volume reached 10%, the primary particle size D50 (average particle size) at which the cumulative volume reached 50%, and the primary particle size D90 at which the cumulative volume reached 90% were determined, starting from the smallest particle size.

[0187] (Particle size distribution of dispersed particles) The particle size distribution of the dispersed particles was measured using a particle size distribution analyzer ("MicrotracUPA," manufactured by Nikkiso Co., Ltd.) by laser diffraction and scattering. When measuring the dispersed particles, 0.1 mL of the dispersion composition was diluted in 4.9 mL of PGMEA to prepare the sample. Based on the measurement results, the particle sizes were defined as follows, from smallest to largest: D10, where the cumulative volume reached 10%; D50 (average particle size), where the cumulative volume reached 50%; and D90, where the cumulative volume reached 90%.

[0188] (Average molecular weight of dispersant) The mass-average molecular weight (Mw) of the dispersant was measured using a gel permeation chromatography (GPC) instrument ("HLC-8220GPC," manufactured by Tosoh Corporation) equipped with an RI detector. Two separation columns ("TSK-GEL SUPER HZM-N," manufactured by Tosoh Corporation) were connected in series, and the measurement was performed at an oven temperature of 40°C, using THF solution as the eluent and a flow rate of 0.35 mL / min. The sample was dissolved in a solvent consisting of 1% by mass of the above eluent, and 20 microliters were injected. All molecular weights are polystyrene equivalents.

[0189] (Acid value of dispersant) 0.5 g to 1 g of the dispersant solution was mixed with 80 mL of acetone and 10 mL of water and stirred to dissolve uniformly. A 0.1 mol / L aqueous KOH solution was used as the titrant, and the solution was titrated using an automatic titrator ("COM-555," manufactured by HIRANUMA Corporation) to measure the acid value (mgKOH / g) of the dispersant solution. The acid value per unit of non-volatile content of the dispersant was then calculated from the acid value of the dispersant solution and the concentration of non-volatile content of the dispersant solution.

[0190] The acid value (mgKOH / g) of the dispersant in its dry state was calculated using the following formula. Acid value (mgKOH / g) = {(5.611 × α × F) / S} / (non-volatile content concentration / 100) however, S: Sample volume (g) α: Consumption volume (mL) of 0.1 mol / L potassium hydroxide-ethanol solution F: Potency of 0.1 mol / L potassium hydroxide-ethanol solution

[0191] (Amine value of dispersant) 0.5 g to 1 g of the dispersant solution was mixed with 80 mL of acetone and 10 mL of water and stirred to dissolve uniformly. A 0.1 mol / L perchloric acid aqueous solution was used as the titrant, and the solution was titrated using an automatic titrator ("COM-555", manufactured by HIRANUMA) to measure the amine value (mgKOH / g) of the dispersant solution. The amine value per unit of non-volatile matter of the dispersant was then calculated from the amine value of the dispersant solution and the concentration of non-volatile matter of the dispersant solution.

[0192] The amine value (mgKOH / g) of the dispersant in its dry state was calculated using the following formula. Amine value (mgKOH / g) = {(5.611 × a) / S} / (non-volatile content concentration / 100) however, S: Sample volume (g) a: Consumption volume (mL) of 0.1 mol / L perchloric acid solution

[0193] (Non-volatile content of dispersant) The conditions for determining the non-volatile content of the dispersant were as follows: sample mass of approximately 1 g, drying conditions of 200°C, and drying time of 10 minutes.

[0194] 2. Manufacturing of resin compositions 2-1. Preparation of inorganic fillers As shown in Table 1, inorganic filler A was prepared. [Table 1]

[0195] More specifically, the following products were used as inorganic fillers. A-1: "MD100" manufactured by Tomei Diamond Co., Ltd. A-2: "MD300" manufactured by Tomei Diamond Co., Ltd. A-3: "FRM0-0.25" Manufactured by Global Diamond Co., Ltd. A-4: "FRM0-0.5" Manufactured by Global Diamond Co., Ltd. A-5: "FRM0-1" manufactured by Global Diamond Co., Ltd. A-6: "MD500" manufactured by Tomei Diamond Co., Ltd. A-7: "AMS-90B" manufactured by Sumitomo Chemical Co., Ltd. A-8: "SPF-20M" manufactured by Denka Co., Ltd. A-9: "DND-R" Manufactured by Beijing Guozuishu Science and Technology Co., Ltd.

[0196] 2-2. Preparation of Dispersant Solution (Preparation of dispersant B1-1 solution) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 80 parts n-butyl acrylate, 60 parts methyl methacrylate, 20 parts methacrylic acid, 20 parts 2-[0-(1'-methylpropyleneamino)carboxyamino]ethyl methacrylate ("Karenz MOI-BM" CAS: 78279-10-4, manufactured by Resonaq Corporation), 20 parts (3-ethyloxetan-3-yl)methyl methacrylate ("ETERNACOLLOXMA" CAS: 37674-57-0, manufactured by UBE Corporation), and 100 parts PGMEA were charged, and the mixture was purged with nitrogen gas. The reaction vessel was heated to 80°C and stirred. A solution of 14 parts 2-mercapto-2-methyl-1,3-propanediol and 0.1 parts 2,2'-azobisisobutyronitrile was added, and the mixture was reacted for 10 hours. Non-volatile content measurement confirmed that 95% of the mixture had reacted.

[0197] Next, 39 parts of 9,9-bis(3,4-dicarboxyphenyl)fluorendioate anhydride (manufactured by JFE Chemical Corporation), 106 parts of a bifunctional polycarbonate polyol with a hydroxyl value of 112 mgKOH / g ("Kuraray Polyol C-1015N," manufactured by Kuraray Co., Ltd.), 33 parts of trimellitic anhydride, 238 parts of PGMEA, and 0.40 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted at 100°C for 7 hours. The reaction was terminated after confirming that more than 98% of the acid anhydride had undergone half-esterification by measuring the acid value. The resulting dispersant B1-1 had an acid value of 94 mgKOH / g and a weight-average molecular weight (Mw) of 7000. PGMEA was added to adjust the non-volatile content to 40% by mass to obtain dispersant B1-1 solution.

[0198] (Preparation of dispersant B1-2 solution) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 10 parts methacrylic acid, 20 parts methyl methacrylate, 90 parts 2-methoxyethyl methacrylate, 40 parts tert-butyl methacrylate, 20 parts n-butyl acrylate, 20 parts tert-butyl acrylate, and 50 parts PGMEA were charged, and the mixture was purged with nitrogen gas. The reaction vessel was heated to 50°C and stirred, and 12 parts of 3-mercapto-1,2-propanediol were added. The temperature was raised to 90°C, and a solution of 90 parts of PGMEA and 0.1 parts of 2,2'-azobisisobutyronitrile was added, and the mixture was reacted for 7 hours. Non-volatile content measurement confirmed that 95% of the reaction had occurred.

[0199] Next, 19 parts of pyromellitic anhydride, 100 parts of PGMEA, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted at 100°C for 7 hours. The reaction was terminated after confirming that more than 98% of the acid anhydride had undergone half-esterification by measuring the acid value. The resulting dispersant B1-2 had an acid value of 77 mgKOH / g and a weight-average molecular weight (Mw) of 8500. PGMEA was added to adjust the non-volatile content to 40% by mass to obtain dispersant B1-2 solution.

[0200] (Preparation of dispersant B1-3 solution) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 6 parts of 3-mercapto-1,2-propanediol, 9.7 parts of pyromellitic dianhydride, 23.6 parts of PGMEA, and 0.01 parts of mono-n-butyltin(IV) oxide were charged, and the mixture was purged with nitrogen gas. The reaction vessel was heated to 100°C and stirred, and the reaction was allowed to proceed for 7 hours.

[0201] After confirming that more than 97% of the acid anhydride had been half-esterified by measuring the acid value, the temperature in the system was cooled to 70°C, 80 parts of methyl methacrylate and 20 parts of hydroxyethyl methacrylate were charged, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile dissolved in 26.2 parts of PGMEA was added, and the reaction was carried out for 10 hours. The reaction was terminated after confirming that 95% of the polymerization had progressed by measuring the non-volatile content. The acid value of the obtained dispersant B1-3 was 70 mg KOH / g, and the weight-average molecular weight (Mw) was 9500. PGMEA was added to adjust the non-volatile content to 40% by mass to obtain the dispersant B1-3 solution.

[0202] (Preparation of dispersant B1-4 solution) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 62.6 parts of 1-dodecanol, 325.4 parts of ε-caprolactone, and 0.1 parts of monobutyltin(IV) oxide as a catalyst were charged, and the mixture was purged with nitrogen gas. The reaction vessel was heated to 120°C and stirred, and the reaction was allowed to proceed for 4 hours. Next, the reaction vessel was heated to 100°C and stirred, and 36.6 parts of pyromellitic dianhydride were added to the reaction product and the mixture was allowed to react for 5 hours.

[0203] The reaction was terminated after confirming that more than 97% of the acid anhydride had undergone half-esterification by measuring the acid value. The resulting dispersant B1-4 had an acid value of 49 mgKOH / g and a weight-average molecular weight (Mw) of 5010. PGMEA was added to adjust the non-volatile content to 40% by mass to obtain the dispersant B1-4 solution.

[0204] (Preparation of dispersant B1-5 solution) In a reaction vessel equipped with a nitrogen gas inlet tube, thermometer, condenser, and stirrer, 186 parts of isostearyl alcohol, 1712 parts of ε-caprolactone, and 1.7 parts of tetrabutyl titanate were charged, and the mixture was purged with nitrogen gas. The reaction vessel was heated to 120°C and stirred, and the reaction was allowed to proceed for 5 hours. Next, the reaction vessel was cooled to below 40°C, and 84.5 parts of polyphosphate with an orthophosphate equivalent content of 116% were added. The temperature inside the reaction vessel was gradually raised, and the reaction was carried out at 80°C for 6 hours before being terminated.

[0205] The resulting dispersant B1-5 had an acid value of 59 mgKOH / g and a weight-average molecular weight (Mw) of 5030. PGMEA was added to adjust the non-volatile content to 40% by mass, and a dispersant B1-5 solution was obtained.

[0206] (Preparation of dispersant B1-6 solution) Dispersant B1-6 was obtained as a copolymer consisting of repeating units derived from a compound represented by the following formula (1) and repeating units derived from a compound represented by the following formula (2). The acid value of dispersant B1-6 was 51.7 mgKOH / g, and the weight-average molecular weight (Mw) was 13000. PGMEA was added to adjust the non-volatile content to 40% by mass, and a dispersant B1-6 solution was obtained. In equations (1) and (2), the numerical values ​​listed alongside the repeating units of the main chain are molar ratios, and the numerical values ​​listed alongside the repeating units of the side chain are the number of repeats in the repeating region.

[0207] ·Formula (1): [ka]

[0208] ·Formula (2):

Chem.

[0209] (Preparation of Dispersant B1-7 Solution) Dispersant B1-7, which is a copolymer consisting of a repeating unit derived from a compound represented by the following formula (3) and a repeating unit derived from a compound represented by the following formula (4), was obtained. Dispersant B1-7 had an acid value of 58.2 mgKOH / g and a weight average molecular weight (Mw) of 10000. PGMEA was added thereto to adjust the non-volatile content to 40% by mass, whereby a Dispersant B1-7 solution was obtained. In formulas (3) and (4), the numerical values indicated together with the repeating units in the main chain are molar ratios, and the numerical values indicated together with the repeating units in the side chains are the number of repetitions of the repeating moiety.

[0210] ·Formula (3):

Chem.

[0211] ·Formula (4):

Chem.

[0212] (Preparation of Dispersant B1-8 Solution) A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 40 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst, and the atmosphere was replaced with nitrogen gas. 9.3 parts of ethyl bromoisobutyrate as an initiator, 5.6 parts of cuprous chloride as a catalyst, and 133 parts of methoxypropyl acetate were charged, the temperature was raised to 110°C under a nitrogen stream, and polymerization of the first block was initiated. After 4 hours of polymerization, it was confirmed by non-volatile content measurement that the polymerization conversion rate was 98% or more.

[0213] Next, 61 parts of methoxypropyl acetate, 25 parts of dimethylaminoethyl methacrylate as the second block monomer, and 25 parts of methacryloyloxyethyltrimethylammonium chloride were added to the reaction vessel, and the reaction was continued by stirring while maintaining a nitrogen atmosphere at 110°C. Two hours after the addition of dimethylaminoethyl methacrylate, the polymerization conversion rate of the second block was confirmed to be 98% or higher by measuring the non-volatile content, and the reaction was terminated. The obtained dispersant B1-8 had an amine value of 62.5 mg KOH / g and a weight-average molecular weight (Mw) of 16000. PGMEA was added to adjust the non-volatile content to 40% by mass, and a dispersant B1-8 solution was obtained.

[0214] (Preparation of dispersant B1-9 solution) In a reaction vessel equipped with a thermometer and a stirrer, 41 parts of N,N-dimethylpropanediamine and 120 parts of chloroform were charged and stirred at room temperature. 50 parts of methacrylate chloride were then added dropwise over 1 hour. After stirring at room temperature for 3 hours, the reaction was confirmed to be complete by 1H-NMR. The reaction solution was then washed sequentially with 300 parts of deionized water and 200 parts of saturated brine. 20 g of magnesium sulfate was added to the organic layer, stirred, and then filtered. The solvent in the resulting solution was removed using a rotary evaporator to obtain 58 parts of compound [A] represented by formula (5) as a pale yellow transparent liquid (yield 85%). The obtained compound was identified by 1H-NMR.

[0215] ·Formula (5) [ka]

[0216] In a reaction vessel equipped with a gas inlet pipe, thermometer, condenser, and stirrer, 15.7 parts of methyl methacrylate, 47.2 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged, and the vessel was purged with nitrogen gas. Next, 2.6 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 100 parts of PGMEA were added, and the temperature was raised to 110°C under a nitrogen atmosphere to start polymerization of the first block. After 4 hours of polymerization, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or higher based on the non-volatile content.

[0217] Next, 25 parts of PGMEA and 30.3 parts of compound [A] as the second block monomer were added to this reaction vessel, and the reaction was continued while stirring at 110°C under a nitrogen atmosphere. Two hours after adding compound [A] represented by formula (5) above, the polymerization conversion rate of the second block was confirmed to be 98% or higher by measuring the non-volatile content. Furthermore, 6.8 parts of benzyl chloride were added to this reaction vessel, and the mixture was stirred for 3 hours while maintaining a temperature of 110°C and a nitrogen atmosphere, after which it was cooled. The obtained dispersant B1-9 had an amine value of 70 mgKOH / g, a quaternary ammonium salt value of 30 mgKOH / g, and a weight-average molecular weight (Mw) of 9800. PGMEA was added to adjust the non-volatile content to 40% by mass to obtain a dispersant B1-9 solution.

[0218] (Preparation of dispersant B1-10 solution) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 80 parts n-butyl acrylate, 60 parts methyl methacrylate, 20 parts methacrylic acid, 20 parts 2-[0-(1'-methylpropyleneamino)carboxyamino]ethyl methacrylate ("Kalenz MOI-BM" CAS: 78279-10-4, manufactured by Resonaq Corporation), and 20 parts ETERNACOLL OXMA (manufactured by UBE Corporation) were charged, and the mixture was purged with nitrogen gas. The reaction vessel was heated to 80°C, and a solution of 14 parts 2-mercapto-2-methyl-1,3-propanediol and 0.03 parts 2,2'-azobisisobutyronitrile was added, and the mixture was reacted for 10 hours. Non-volatile content measurement confirmed that 95% of the mixture had reacted.

[0219] Next, 39 parts of BPAF:9,9-bis(3,4-dicarboxyphenyl)fluorendioate anhydride (manufactured by JFE Chemical Corporation), 106 parts of a bifunctional polycarbonate polyol with a hydroxyl value of 112 mgKOH / g ("Kuraray Polyol C-1015N," manufactured by Kuraray Co., Ltd.), 33 parts of trimellitic anhydride, 392 parts of cyclohexanone, and 0.40 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted at 100°C for 7 hours. The reaction was terminated after confirming that more than 98% of the acid anhydride had undergone half-esterification by measuring the acid value. The resulting dispersant B1-10 had an acid value of 73 mgKOH / g and a weight-average molecular weight (Mw) of 45,000. The dispersant B1-10 solution was obtained by adjusting the non-volatile content to 40% by mass using PGMEA.

[0220] (Preparation of dispersant B1-11 solution) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 50 parts methyl methacrylate, 30 parts n-butyl methacrylate, 20 parts (3-ethyl-3-oxetanyl)methyl methacrylate, and 45.4 parts PGMAc were charged, and the mixture was purged with nitrogen gas. The reaction vessel was heated to 70°C, 6 parts of 3-mercapto-1,2-propanediol were added, followed by 0.06 parts of AIBN (azobisisobutyronitrile), and the mixture was reacted for 12 hours. Solid content measurement confirmed that 95% of the mixture had reacted. Next, 9.7 parts of pyromellitic anhydride, 70.3 parts of PGMAc, and 0.20 parts of DBU (1,8-diazabicyclo-[5.4.0]-7-undecene) as a catalyst were added, and the mixture was reacted at 120°C for 7 hours. The reaction was terminated after confirming that more than 98% of the acid anhydride had undergone half-esterification by measuring the acid value. PGMAc was added to adjust the non-volatile content to 40%, and a dispersant B1-11 solution with an acid value of 64 mgKOH / g and a weight-average molecular weight of 18000 was obtained.

[0221] (Preparation of dispersant B1-12 solution) A reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 40 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst. The mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the inside of the system was purged with nitrogen. Next, 4.5 parts of ethyl bromoisobutyrate as an initiator, 5.6 parts of cuprous chloride as a catalyst, and 133 parts of methoxypropyl acetate were charged. The temperature was raised to 110°C under a nitrogen stream to initiate polymerization of the first block (B block). After 4 hours of polymerization, the polymerization solution was sampled to measure the solid content, and it was confirmed that the polymerization conversion rate was 98% or more when calculated from the non-volatile content. Next, 61 parts of methoxypropyl acetate, 25 parts of dimethylaminoethyl methacrylate as a second block (A block) monomer, and 25 parts of methacryloyloxyethyltrimethylammonium chloride were added to the reactor. The reaction was continued by stirring while maintaining 110°C under a nitrogen atmosphere.

[0222] Two hours after the addition of dimethylaminoethyl methacrylate, the polymerization solution was sampled to measure the solid content, and it was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more when calculated from the non-volatile content. The reaction solution was cooled to room temperature to terminate the polymerization. As a result of GPC measurement, the polymer had an Mw of 42,000, a molecular weight distribution Mw / Mn of 1.3, and a reaction conversion rate of 98.5%. In this way, a resin having an amine value per solid content of 62.5 mgKOH / g was obtained. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether acetate was added to the previously synthesized resin solution so that the non-volatile content was 40% by mass, thereby preparing a dispersant B1-12 solution.

[0223] (Preparation of Dispersant B1-13 Solution) In a reaction vessel equipped with a stirrer and thermometer, 41 parts of N,N-dimethylpropanediamine and 120 parts of chloroform were charged and stirred at room temperature. 50 parts of methacrylate chloride were then added dropwise over 1 hour. After stirring at room temperature for 3 hours, the reaction was confirmed to be complete by 1H-NMR. The reaction solution was then washed sequentially with 300 parts of deionized water and 200 parts of saturated brine. 20 g of magnesium sulfate was added to the organic layer, stirred, and then filtered. The solvent in the obtained solution was removed by distillation using a rotary evaporator, and 58 parts of compound [A] represented by formula (5) above were obtained as a pale yellow transparent liquid (yield 85%). The obtained compound was identified by 1H-NMR.

[0224] In a reaction vessel equipped with a gas inlet pipe, condenser, stirring blades, and thermometer, 15.7 parts of methyl methacrylate, 47.2 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged. The mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the system was then purged with nitrogen. Next, 1.2 parts of ethyl bromoisobutyrate were added as an initiator, 3.7 parts of cuprous chloride and 100 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc) as catalysts. The mixture was heated to 110°C under a nitrogen atmosphere to begin polymerization of the first block. After 4 hours of polymerization, the polymerization solution was sampled and the solid content was measured. Based on the non-volatile content, it was confirmed that the polymerization conversion rate was 98% or higher.

[0225] Next, 25 parts of PGMAc and 30.3 parts of compound [A] represented by formula (5) above were added to the reaction vessel as the second block monomer. The reaction was continued while stirring was maintained at 110°C under a nitrogen atmosphere. Two hours after adding compound [B] represented by formula (18) above, the polymerization solution was sampled and the solid content was measured. Based on the non-volatile content, it was confirmed that the polymerization conversion rate of the second block was 98% or higher. Furthermore, 4.5 parts of benzyl chloride were added to this reaction apparatus, and the mixture was stirred for 3 hours while maintaining a temperature of 110°C and a nitrogen atmosphere, after which it was cooled. PGMAc was added to the previously synthesized block copolymer solution so that the non-volatile content was 40% by weight. In this way, a basic dispersant B1-13 solution was obtained with an amine value of 60 mgKOH / g per solid content, a quaternary ammonium salt value of 20 mgKOH / g, a weight-average molecular weight (Mw) of 38,500, and a non-volatile content of 40% by weight.

[0226] (Preparation of dispersant B1-14 solution) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 108 parts of 3-mercapto-1,2-propanediol, 174 parts of pyromellitic dianhydride, 650 parts of propylene glycol monomethyl ether acetate, and 0.2 parts of monobutyltin oxide as a catalyst were charged. After purging with nitrogen gas, the reaction was carried out at 120°C for 5 hours (first step). Acid value measurement confirmed that more than 95% of the acid anhydride had undergone half-esterification. Next, 160 parts of the compound obtained in the first step (based on solid content), 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl methacrylate, 50 parts of methacrylic acid, and 663 parts of propylene glycol monomethyl ether acetate were charged into the reaction vessel. The reaction vessel was heated to 80°C, and 1.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) were added, and the mixture was reacted for 12 hours (second step). Solid content measurement confirmed that 95% had reacted.

[0227] Finally, 500 parts of a 50% propylene glycol monomethyl ether acetate solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 parts of hydroquinone were charged, and the reaction was carried out by IR until the disappearance of the 2270 cm-1 peak based on the isocyanate group was confirmed (third step). After confirming the disappearance of the peak, the reaction solution was cooled, and the solid content was adjusted with propylene glycol monomethyl ether acetate to obtain a dispersant B1-14 solution with a solid content of 40%. The acid value of the obtained dispersant was 68 mg KOH / g, the unsaturated double bond equivalent was 1593, and the weight-average molecular weight was 13000.

[0228] (Preparation of dispersant B1-15 solution) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 50 parts methyl methacrylate, 30 parts n-butyl methacrylate, 20 parts (3-ethyl-3-oxetanyl)methyl methacrylate, and 45.4 parts PGMAc were charged, and the mixture was purged with nitrogen gas. The reaction vessel was heated to 70°C, 6 parts of 3-mercapto-1,2-propanediol were added, followed by 0.12 parts of AIBN (azobisisobutyronitrile), and the mixture was reacted for 12 hours. Solid content measurement confirmed that 95% of the mixture had reacted.

[0229] Next, 9.7 parts of pyromellitic anhydride, 70.3 parts of PGMAc, and 0.20 parts of DBU (1,8-diazabicyclo-[5.4.0]-7-undecene) as a catalyst were added, and the reaction was carried out at 120°C for 7 hours. The reaction was terminated after confirming that more than 98% of the acid anhydride had been half-esterified by measuring the acid value. PGMAc was added to adjust the non-volatile content to 40%, obtaining a dispersant B1-15 solution with an acid value of 43 mg KOH / g and a weight-average molecular weight of 9000.

[0230] (Preparation of dispersant B1-16 solution) In a reaction vessel equipped with a gas inlet tube, temperature control, condenser, and stirrer, 10 parts methacrylic acid, 90 parts methyl methacrylate, 50 parts ethyl acrylate, 50 parts tert-butyl acrylate, and 50 parts propylene glycol monomethyl ether acetate were charged, and the mixture was purged with nitrogen gas. The reaction vessel was heated to 50°C and stirred, and 12 parts of 3-mercapto-1,2-propanediol were added. The temperature was raised to 90°C, and the reaction was carried out for 7 hours while adding a solution of 0.1 parts of 2,2'-azobisisobutyronitrile added to 90 parts of propylene glycol monomethyl ether acetate. Non-volatile content measurement confirmed that 95% had reacted.

[0231] 19 parts of pyromellitic dianhydride, 50 parts of propylene glycol monomethyl ether acetate, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added and the mixture was reacted at 100°C for 7 hours. The reaction was terminated after confirming that more than 98% of the acid anhydride had been half-esterified by measuring the acid value. Next, propylene glycol monomethyl ether acetate was added to dilute the solution to a non-volatile content of 40% to obtain a dispersant B1-16 solution with an acid value of 70 mg KOH / g and a weight-average molecular weight of 8500.

[0232] (Preparation of dispersant B1-17 solution) In a reaction vessel equipped with a gas inlet tube, temperature control, condenser, and stirrer, 170 parts of methyl methacrylate, 20 parts of tert-butyl methacrylate, 10 parts of cyclohexyl acrylate, and 50 parts of propylene glycol monomethyl ether acetate were charged, and the mixture was purged with nitrogen gas. The reaction vessel was heated to 50°C and stirred, and 12 parts of 3-mercapto-1,2-propanediol were added. The temperature was raised to 90°C, and the reaction was carried out for 7 hours while adding a solution of 0.1 parts of 2,2'-azobisisobutyronitrile added to 90 parts of propylene glycol monomethyl ether acetate. Non-volatile content measurement confirmed that 95% had reacted.

[0233] 19 parts of pyromellitic dianhydride, 50 parts of propylene glycol monomethyl ether acetate, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added and the mixture was reacted at 100°C for 7 hours. The reaction was terminated after confirming that more than 98% of the acid anhydride had been half-esterified by measuring the acid value. Next, propylene glycol monomethyl ether acetate was added to dilute the solution to a non-volatile content of 40% to obtain a dispersant B1-17 solution having aromatic carboxyl groups with an acid value of 42 mg KOH / g and a weight-average molecular weight of 8500.

[0234] (Preparation of dispersant B1-18 solution) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 50.0 parts of tert-butyl acrylate, 50.0 parts of methyl methacrylate, and 25.0 parts of propylene glycol monomethyl ether acetate were charged, and the vessel was purged with nitrogen gas. The reaction vessel was heated to 50°C, and 6.0 parts of 3-mercapto-1,2-propanediol were added. The temperature was raised to 90°C, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile dissolved in 45.7 parts of propylene glycol monomethyl ether acetate was added, and the reaction was carried out for 10 hours. Non-volatile content measurement confirmed that 95% of the reaction had occurred.

[0235] Next, 14.5 parts of pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.), 38.0 parts of PGMAc, and 0.2 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted at 120°C for 5 hours. Subsequently, 12.1 g of 3-methoxybutanol was added, and the reaction was carried out at 120°C for 3 hours. The reaction was terminated after confirming that more than 98% of the acid anhydride had undergone half-esterification by measuring the acid value. After the reaction was complete, propylene glycol monomethyl ether acetate was added to adjust the non-volatile content to 40% by mass, and a dispersant B1-18 solution with an acid value of 95 mg KOH / g and a weight-average molecular weight of 9500 was obtained.

[0236] (Preparation of dispersant B2-1 solution) In a four-necked separable flask equipped with a thermometer, stirrer, distillation tube, and condenser, 50.0 parts of PGMEA and 100.0 parts of methyl methacrylate were charged and heated to 90°C under a nitrogen stream. 4.0 parts of mercaptoacetic acid and 1.0 part of 2,2'-azobisisobutyronitrile were added, and the mixture was reacted for 10 hours before being cooled. GPC measurements confirmed that over 98% of the reaction occurred. The resulting dispersant B2-1 had an acid value of 30 mg KOH / g and a weight-average molecular weight (Mw) of 2500. The dispersant B2-1 solution was obtained by adjusting the non-volatile content to 40% by mass using PGMEA.

[0237] (Preparation of dispersant B2-2 solution) In a four-necked separable flask equipped with a thermometer, stirrer, distillation tube, and condenser, 50.0 parts of PGMEA and 97.0 parts of methyl methacrylate were charged and heated to 90°C under a nitrogen stream. 4.0 parts of thiomalic acid and 1.0 part of 2,2'-azobisisobutyronitrile were added, and the mixture was reacted for 10 hours before being cooled. GPC measurements confirmed that over 98% of the reaction occurred. The resulting dispersant B2-2 had an acid value of 45 mg KOH / g and a weight-average molecular weight (Mw) of 4500. The dispersant B2-2 solution was obtained by adjusting the non-volatile content to 40% by mass using PGMEA.

[0238] (Preparation of dispersant B2-3 solution) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 10 parts methacrylic acid, 20 parts methyl methacrylate, 90 parts 2-methoxyethyl methacrylate, 40 parts tert-butyl methacrylate, 20 parts n-butyl acrylate, 20 parts tert-butyl acrylate, and 50 parts PGMEA were charged, and the mixture was purged with nitrogen gas. The reaction vessel was heated to 50°C and stirred, and 0.8 parts of thioglycerol were added. The temperature was raised to 90°C, and the reaction was carried out for 7 hours while adding a solution of 0.1 parts of 2,2'-azobisisobutyronitrile added to 90 parts of PGMEA. Non-volatile content measurement confirmed that 95% had reacted.

[0239] 1.2 parts of pyromellitic anhydride, 100 parts of PGMEA, and 0.2 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene were added as a catalyst, and the mixture was reacted at 100°C for 7 hours. The reaction was terminated after confirming that more than 98% of the acid anhydride had undergone half-esterification by measuring the acid value. The resulting dispersant B2-3 had an acid value of 35 mg KOH / g and a weight-average molecular weight (Mw) of 65,000. PGMEA was added to adjust the non-volatile content to 40% by mass to obtain the dispersant B2-3 solution.

[0240] (Preparation of dispersant B2-4 solution) In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, and thermometer, 80.0 g of biphenyltetracarboxylic dianhydride (manufactured by Mitsubishi Chemical Corporation), 250.0 g of pentaerythritol triacrylate ("Viscote #300," manufactured by Osaka Organic Chemical Industry Co., Ltd.), 0.16 g of hydroquinone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 141.2 g of cyclohexanone were charged, and the mixture was heated to 85°C. Next, 1.65 g of 1,8-diazabicyclo[5.4.0]-7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, and the mixture was stirred at 85°C for 8 hours. Then, 77.3 g of glycidyl methacrylate (manufactured by Dow Chemical Japan Ltd.) and 33.9 g of cyclohexanone were added, and then 2.65 g of dimethylbenzylamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added as a catalyst, and the mixture was stirred at 85°C for 6 hours. The reaction was then cooled to room temperature to complete the reaction. The resulting dispersant B2-4 had an acid value of 15 mg KOH / g and a weight-average molecular weight (Mw) of 2830. PGMEA was added to adjust the non-volatile content to 40% by mass, and a dispersant B2-4 solution was obtained.

[0241] 2-3. Preparation of the Dispersion Composition (Manufacturing Example 1) The following mixture was stirred and mixed until homogeneous, then placed together with 0.5 mm diameter zirconia beads in a bead mill ("Mini Model M-250 MKII," manufactured by Eiger Japan Co., Ltd.) and dispersed for 3 hours. After that, it was filtered through a 5 μm pore size filter to obtain dispersion composition D-1 with a non-volatile content of 20% by mass. Inorganic filler A-1: ​​13 parts by mass Dispersant B1-1 solution: 17.5 parts by mass Dispersion medium (PGMEA): 69.5 parts by mass

[0242] (Manufacturing examples 2-50, 54-74, and 78-81) Dispersed compositions D-2 to D-50, 54 to 74, and 78 to 81 were produced by mixing, dispersing, and filtering in the same manner as in Production Example 1, except that the type and amount of each material were changed as shown in Tables 2 to 5. When pigment derivatives were included, the pigment derivatives were stirred and mixed together with the other materials and dispersed in a bead mill.

[0243] (Manufacturing example 51) Dispersion composition D-51 was manufactured in the same manner as in Manufacturing Example 12, except that the above bead mill was replaced with an ultrasonic device (manufactured by Yamato Scientific Co., Ltd., product name: "LUH150") and ultrasonic irradiation was performed for 2 hours. (Manufacturing example 52) Dispersion composition D-52 was prepared in the same manner as in Production Example 12, except that the above bead mill was replaced with a stirring homogenizer (M-Technique Co., Ltd., product name: "Cleamix CLM-0.8S") and the homogenization process was carried out for 2 hours.

[0244] (Manufacturing example 53) Dispersion composition D-53 was produced in the same manner as in Production Example 12, except that the above bead mill was replaced with a high-pressure homogenizer (manufactured by Sugino Machine Co., Ltd., product name: "Starburst Mini") and high-pressure homogenization treatment at 100 MPa was performed 10 times.

[0245] (Manufacturing example 75) Dispersion composition D-75 was manufactured in the same manner as in manufacturing example 61, except that the above bead mill was replaced with an ultrasonic device (manufactured by Yamato Scientific Co., Ltd., product name: "LUH150") and ultrasonic irradiation was performed for 2 hours. (Manufacturing example 76) Dispersion composition D-76 was prepared in the same manner as in production example 61, except that the above bead mill was replaced with a stirring homogenizer (manufactured by M-Technique, product name: "Cleamix CLM-0.8S") and the homogenization treatment was performed for 2 hours.

[0246] (Manufacturing example 77) Dispersion composition D-77 was produced in the same manner as in production example 61, except that the above bead mill was replaced with a high-pressure homogenizer (manufactured by Sugino Machine Co., Ltd., product name: "Starburst Mini") and high-pressure homogenization treatment at 100 MPa was performed 10 times. In the table, the symbols for pigment derivatives refer to the pigment derivatives shown below.

[0247] • Pigment derivative (1)-1: A basic triazine having the following structure. [ka]

[0248] • Pigment derivative (1)-2: A basic triazine having the following structure. [ka]

[0249] • Pigment derivative (2)-1: A basic phthalocyanine having the following structure. [ka]

[0250] • Pigment derivative (2)-2: A basic phthalocyanine having the following structure. [ka]

[0251] • Pigment derivative (3)-1: Basic DPP having the following structure. [ka]

[0252] • Pigment derivative (3)-2: Basic DPP having the following structure. [ka]

[0253] • Pigment derivative (4): Basic quinophthalone having the following structure. [ka]

[0254] • Pigment derivative (5): Acidic triazine having the following structure. [ka]

[0255] [Table 2]

[0256] [Table 3]

[0257] [Table 4]

[0258] [Table 5]

[0259] 2-4. Manufacturing of Binder Resin Solution 370 parts of cyclohexanone were placed in a separable four-neck flask equipped with a gas inlet tube, thermometer, condenser, dropping tube, and stirrer. The flask was heated to 80°C, and the inside of the flask was replaced with nitrogen gas. Next, a mixture of 18 parts of paracumylphenol ethylene oxide-modified acrylate ("Aronics M110," manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2.0 parts of 2,2'-azobisisobutyronitrile was added dropwise from a dropping tube over 2 hours. After addition, the mixture was reacted at 100°C for a further 3 hours.

[0260] A solution of 1.0 part azobisisobutyronitrile dissolved in 50 parts cyclohexanone was added, and the mixture was reacted at 100°C for 1 hour. The flask was purged with air, and a solution of 9.3 parts acrylic acid (equivalent to 100 mol% of glycidyl groups), 0.5 parts trisdimethylaminophenol, and 0.1 parts hydroquinone was added. The mixture was then reacted at 120°C for 6 hours. The reaction was terminated when the acid value of the non-volatile components reached 0.5 mg KOH / g. Subsequently, 19.5 parts of tetrahydrophthalic anhydride (equivalent to 100 mol% of the hydroxyl groups produced) and 0.5 parts of triethylamine were added, and the mixture was reacted at 120°C for 3.5 hours, after which it was cooled to room temperature.

[0261] The weight-average molecular weight (Mw) of the obtained binder resin was 19,000. Approximately 2 g of the binder resin solution in the flask was sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. Then, PGMEA was added to adjust the non-volatile content to 40% by mass to obtain the binder resin solution.

[0262] 2-5. Production of resin compositions (Example 1A) The following mixture was stirred and mixed until homogeneous, then filtered through a 1.0 μm pore size filter to obtain resin composition X-1 with a non-volatile content of 18% by mass. Dispersion composition D-1: 50 parts by mass Binder resin solution: 10.5 parts by mass Photopolymerizable compound: 3.5 parts by mass Photopolymerization initiator: 0.4 parts by mass Solvent (PGMEA): 35.6 parts by mass The dispersion composition had a non-volatile content of 20% by mass, and the binder resin solution had a non-volatile content of 40% by mass. A polyfunctional methacrylate ("Aronics M-402," manufactured by Toagosei Co., Ltd.) was used as the photopolymerizable compound. An oxime ester polymerization initiator ("Irgacure OXE-02," manufactured by BASF Japan Ltd.) was used as the photopolymerization initiator.

[0263] (Examples 2A to 53A, Comparative Examples 1A to 6A, Examples 1B to 18B, Comparative Examples 1B to 4B) Resin compositions X-2 to X-81 were prepared by mixing, dispersing, and filtering in the same manner as in Example 1A, except that the type and amount of each material were changed as shown in Tables 6 to 10. Furthermore, a polyfunctional methacrylate ("Aronics M-402," manufactured by Toagosei Co., Ltd.) was used as the thermally polymerizable compound. A benzoyl peroxide-based polymerization initiator ("Perbutyl O," manufactured by NOF Corporation) was used as the thermal polymerization initiator.

[0264] [Table 6]

[0265] [Table 7]

[0266] [Table 8]

[0267] [Table 9]

[0268] [Table 10]

[0269] 3. Evaluation Each test was conducted using the following method. <Viscosity> The viscosity of the obtained resin compositions (X-1 to X-81) was measured using an E-type viscometer ("ELD-type viscometer," manufactured by Toki Sangyo Co., Ltd.) at 25°C and a rotation speed of 50 rpm. The viscosity values ​​were then evaluated according to the following criteria. [Evaluation Criteria] 5:20cps or less (good) 4: More than 20cps and less than 40cps (normal) 3: Over 40 cps and under 60 cps (usable) 2: Over 60cps (defect) 1: Unmeasurable "Unmeasurable" refers to cases where the inorganic filler has clearly settled or gelled within the resin composition. In other words, it is a case where the viscosity value of the entire resin composition cannot be obtained because the inorganic filler is not dispersed.

[0270] <Storage stability> The storage stability of the obtained resin compositions (X-1 to X-81) was determined as follows. After preparation (manufacturing), the viscosity of the resin composition and the average particle size D50 of the dispersed particles were measured after being left at room temperature (20°C) and atmospheric pressure for 12 to 24 hours and after being left for 7 days. The rate of change of viscosity and the rate of change of average particle size D50 were calculated, and the obtained results were evaluated according to the following criteria. The viscosity was measured using the method described in <Viscosity>, and the average particle size D50 was measured using the method described in (Particle size distribution of dispersed particles). [Evaluation Criteria] 5: Viscosity change rate of 10% or less and average particle size D50 change rate of 20% or less (good) 4: Either a viscosity change rate of 10% or less, or a change rate of average particle size D50 of 20% or less (normal) 3: Viscosity change rate is between 10% and 20%, and average particle size D50 change rate is between 20% and 30% (practical). 2: Viscosity change rate exceeds 20% and average particle size D50 change rate exceeds 30% (defective) 1: Unmeasurable "Unmeasurable" refers to cases where gel-like sedimentation occurs in the resin composition, making it difficult to measure viscosity or average particle size D50 (particle size distribution).

[0271] <Storage stability (2)> The storage stability of the obtained resin compositions (X-1 to X-81) was determined as follows. After preparation (manufacturing), the viscosity of the resin composition and the average particle size D50 of the dispersed particles were measured after being left at room temperature (20°C) and atmospheric pressure for 12 to 24 hours and after being left for 1 month. The rate of change of viscosity and the rate of change of average particle size D50 were calculated, and the obtained results were evaluated according to the following criteria. The viscosity was measured using the method described in <Viscosity>, and the average particle size D50 was measured using the method described in (Particle size distribution of dispersed particles). [Evaluation Criteria] 5: Viscosity change rate of 10% or less and average particle size D50 change rate of 20% or less (good) 4: Either a viscosity change rate of 10% or less, or a change rate of average particle size D50 of 20% or less (normal) 3: Viscosity change rate is between 10% and 20%, and average particle size D50 change rate is between 20% and 30% (practical). 2: Viscosity change rate exceeds 20% and average particle size D50 change rate exceeds 30% (defective) 1: Unmeasurable "Unmeasurable" refers to cases where gel-like sedimentation occurs in the resin composition, making it difficult to measure viscosity or average particle size D50 (particle size distribution).

[0272] <Filterability> Each of the obtained resin compositions (X-1 to X-81) was subjected to a pressure of 0.1 mN / m for a certain period of time using a 1.5 μm disc filter ("Titan3PTFEFILTER," manufactured by Tomsic Co., Ltd.), and the amount of liquid that passed through the disc filter during that time was evaluated. A larger amount of liquid indicates better filterability (i.e., less precipitation or excessive aggregation).

[0273] The filtration performance was then evaluated according to the following evaluation criteria. [Evaluation Criteria] 5: The amount of liquid that passed through the filter was 15 mL or more (good). 4: The amount of liquid that passed through the filter was 11.25 mL or more but less than 15 mL (normal). 3: The amount of liquid that passes through the filter is 7.5 mL or more but less than 11.25 mL (practical). 2: The amount of liquid that passed through the filter was 3.75 mL or more but less than 7.5 mL (defective) 1: The amount of liquid that passes through the filter is less than 3.75 mL (no filtration).

[0274] <Evaluation of coating film properties> The coating properties of the obtained resin compositions were evaluated using the following method. <<Spectroscopic Shape Evaluation>> A substrate with a liquid coating was obtained by spin-coating resin compositions (X-1 to X-59) onto a 100 mm x 100 mm, 0.7 mm thick glass substrate, such that the dried film thickness was 1.5 μm. Next, the substrate with the liquid coating was dried in a 70°C oven for 20 minutes to obtain a substrate with a pre-cured coating. An ultra-high pressure mercury lamp was used to achieve an integrated exposure dose of 150 mJ / cm². 2 The pre-cured coating was exposed to ultraviolet light to achieve the desired result. The transmittance of the i-line (365 nm) during this exposure was measured using a UV-Vis-Near-Infrared spectrophotometer ("UH4150," manufactured by Hitachi High-Tech Science Corporation). A higher transmittance indicates a better spectral shape.

[0275] The transmittance was then evaluated according to the following evaluation criteria. [Evaluation Criteria] 5: i-line transmittance is 40% or higher (good) 4: i-line transmittance 30% to less than 40% (normal) 3: i-line transmittance is 20% or more but less than 30% (practical). 2: i-line transmittance is 10% or more but less than 20% (poor) 1: i-line transmittance is less than 10% (no transmittance)

[0276] <<Photolithography Evaluation>> A resist solution for planarization films ("HL-18s," manufactured by Nippon Steel Chemical & Material Co., Ltd.) was applied to a 6-inch silicon wafer by spin coating. The wafer was heated on a 100°C hot plate for 6 minutes, then heated in a 230°C oven for 1 hour to cure the coating and obtain a substrate with a planarization film. Next, resin compositions (X-1 to X-59) were each applied to the planarization film by spin coating so that the film thickness after drying was 10 μm, thereby obtaining a substrate with a liquid coating. Subsequently, the substrate with the liquid coating was pre-baked on a 100°C hot plate for 1 minute to obtain a substrate with a partially cured coating. An i-line stepper exposure system ("FPA-3000i5+," manufactured by Canon Inc.) was used with an integrated exposure dose of 200 mJ / cm². 2 To achieve this, the pre-cured film was exposed to ultraviolet light through a photomask designed to form 1.0 μm square pixels. After exposure, the substrate with the cured film was paddle-developed with an organic alkaline developer. After paddle development, the substrate was washed with pure water using a 20-second spin shower, any remaining water droplets on the wafer were removed with high-pressure air, and the substrate was allowed to air dry to attempt the formation of a square pixel pattern. This resulted in obtaining a film-coated substrate. For the film-coated substrates, the surface of the unexposed areas washed away by development was observed at 200x magnification using an optical microscope, and the photolithographic properties ("Photolithographic Properties" in the table) were observed based on the presence or absence of residue.

[0277] Then, the photolithographic properties were evaluated according to the following evaluation criteria. [Evaluation Criteria] 5: No residue after 1 minute of development (good) 4: A slight residue is visible after a 1-minute development time (normal). 3: A small amount of residue is visible after a 1-minute development time (usable). 2: A large amount of residue is visible after a development time of 1 minute (poor quality). 1: Severe residue is visible after a development time of 1 minute (no photolithography properties).

[0278] <<Evaluation of film-forming properties>> The developed test substrates were heat-treated at 500°C for 180 minutes. The presence or absence of the film after heat treatment was checked. The results were evaluated according to the following criteria. [Evaluation Criteria] 5: Film remains 1: No membrane residue

[0279] <<Heat Resistance Evaluation>> The cross-section of the film before and after heat treatment was observed at 200x magnification using a non-contact surface and layer cross-sectional shape measurement system ("Vertscan3.0 R4300C," manufactured by Ryoka Systems Co., Ltd.), and the film thickness (film thickness) on the substrate was measured. Measurements were taken at three arbitrary points 100 μm apart, and the film thickness was determined by arithmetic mean of the measurement results. The film loss was then calculated using the following formula. The obtained results were evaluated according to the following criteria. [Film loss] = ([Film thickness before heat treatment] - [Film thickness after heat treatment]) / [Film thickness before heat treatment] × 100 [Evaluation Criteria] 5: Membrane loss 10% or less (good) 4: Membrane loss more than 10% and less than 20% (normal) 3: Film loss between 20% and 30% (practical) 2: Membrane loss over 30% (defective) -: Unmeasurable (no film formation)

[0280] < <haze>> The obtained resin compositions (X-60 to X-81) were coated onto a 100 mm x 100 mm, 0.7 mm thick glass substrate ("Glass Eagle 2000," manufactured by Corning) using a spin coater to obtain a substrate (coated substrate) with a finished film thickness of 2.0 μm after heating at 150°C for 20 minutes. Next, after vacuum drying, an illuminance of 20 mW / cm² was used with an ultra-high pressure mercury lamp. 2 Exposure dose: 50 mJ / cm² 2 Ultraviolet exposure was performed. The coated substrate was heated at 150°C for 20 minutes, and after cooling, the haze value was measured using a haze meter ("NDH-2000," manufactured by Tokyo Denshoku Co., Ltd.). The measured haze values ​​were evaluated according to the following criteria. [Evaluation Criteria] 5:3 or less (good) 4:3 over 5 (normal) 3:5 or better, 10 or less (usable) 2: More than 10 and less than 20 (defective) 1:20 or higher (no light transmission)

[0281] <<Surface foreign matter>> The presence or absence of foreign matter on the surface of the coated substrate after measuring the haze value was observed using an optical microscope at 200x magnification. The presence or absence of foreign matter was then evaluated according to the following criteria. [Evaluation Criteria] 5: No foreign objects found 1: Foreign object present

[0282] <<Evaluation of film-forming properties (2)>> The surface of the coated substrate was visually inspected to determine if any abnormalities were present after measuring the haze value. The presence or absence of abnormalities was then evaluated according to the following criteria. [Evaluation Criteria] 5: No visual abnormalities found. 1: Fracture present

[0283] <Dry etching resistance evaluation> Dry etching resistance was tested on films whose heat resistance had been confirmed. First, the film-coated substrate was placed on the stage of the dry etching apparatus. SF6 was circulated as the etching gas at a total flow rate of 30 sccm. Etching was performed by applying a bias power of 400 W and an antenna power of 20 W to plasmaize the etching gas. The chamber pressure was set to 0.5 Pa and the temperature to 20°C, and etching was performed for 5 minutes at an etching rate of 200 nm / min.

[0284] The cross-section of the film before and after dry etching was observed at 200x magnification using a non-contact surface and layer cross-sectional shape measurement system ("Vertscan3.0 R4300C," manufactured by Ryoka Systems Co., Ltd.), and the film thickness (film thickness) on the substrate was measured. Measurements were taken at three arbitrary points 100 μm apart, and the film thickness was determined by arithmetic mean of the measurement results. The dry etching film loss was then calculated using the following formula. The obtained results were evaluated according to the following criteria. [Dry etching film loss] = ([Film thickness before dry etching] - [Film thickness after dry etching]) / [Film thickness before dry etching] × 100 [Evaluation Criteria] 5: Dry etching film loss of 10% or less (good) 4: Dry etching film loss of over 10% but less than or equal to 20% (normal) 3: Dry etching film loss of over 20% but less than or equal to 30% (practical) 2: Dry etching film loss exceeding 30% (defective) -: Unmeasurable (not heat resistant)

[0285] <Heat dissipation> First, the obtained resin compositions (X-60 to X-81) were coated onto a release sheet and dried to produce two sheets 1, each with a 100 μm thick resin composition layer, one side of which was covered by the release sheet. Then, these two sheets 1 were stacked so that the resin composition layers were joined together, and bonded under conditions of 100°C, 0.3 MPa, and 1 m / min to form sheet 2. In other words, sheet 2 is a laminate in which the resin composition layer is sandwiched between two release sheets. The thickness of the resin composition layer was 190 μm after the above bonding process. Subsequently, sheet 2 (10 cm x 10 cm in size) was pressed at 180°C and 3.0 MPa for 60 minutes, after which the release sheets on both sides were peeled off to obtain a cured product (hereinafter also referred to as "measurement sample").

[0286] The thermal conductivity was determined for the sample used for measurement from its thermal diffusivity, specific heat, and density, according to the following formula. Thermal conductivity (W / (m·K)) = Density (g / cm³) 3 ) × Specific heat (J / kg·K) × Thermal diffusivity (mm 2 / s) The thermal diffusivity was determined as follows: A sample was cut into 20 mm squares, gold was deposited onto the surface of the sample, and then carbon was coated with carbon spray. The thermal diffusivity was then measured using a xenon flash analyzer ("LFA447 NanoFlash," manufactured by NETZSCH). The measurement environment was 25 ± 1 °C, measurement voltage 202 kV, Amplitude 2520, and pulse width 14 ms. Furthermore, specific heat was measured using a high-sensitivity differential scanning calorimeter ("DSC220C," manufactured by SII Nanotechnology Co., Ltd.). The heating rate was 5°C / min in the range of -50°C to 200°C, and the specific heat at 25°C was read. Furthermore, the density was calculated using the water displacement method.

[0287] The calculated thermal conductivity was evaluated according to the following criteria. 5: 3.5W / mK or more (good) 4: 1.5 W / mK or more and less than 3.5 W / mK (normal) 3: 1.0 W / mK or more and less than 1.5 W / mK (practical) 2: 0.5W / mK or higher, less than 1.0W / mK (defective) 1: Less than 0.5W / mK (no heat dissipation) The evaluation results are summarized in Tables 11 to 15 below.

[0288] [Table 11]

[0289] [Table 12]

[0290] [Table 13]

[0291] [Table 14]

[0292] [Table 15] [Explanation of symbols]

[0293] 1: Film-coated substrate 2: Base material 21: Main surface 3: Diamond dispersion film 31: Resin Matrix 32: Diamond particles< / haze>

Claims

1. A dispersion composition for forming a diamond dispersion film, Diamond particles and Dispersion medium and The dispersion medium comprises a dispersant for dispersing the diamond particles, The primary particles of the diamond particles have an average particle size D50, which is the cumulative 50% diameter in their volume-based particle size distribution, that is between 50 nm and 400 nm. Dispersion composition.

2. In the dispersion composition according to claim 1, The primary particles of the diamond particles have an average particle size D50 of 100 nm or more and 300 nm or less. Dispersion composition.

3. In the dispersion composition according to claim 1, The primary particles of the diamond particles have a volume-based particle size distribution where the cumulative 10% diameter is D10 and the cumulative 90% diameter is D10, and (D90 - D10) / D50 is between 0.75 and 1. Dispersion composition.

4. In the dispersion composition according to claim 1, The diamond particles are obtained by crushing a diamond mass. Dispersion composition.

5. In the dispersion composition according to claim 1, The weight-average molecular weight of the dispersant is between 4600 and 60000. Dispersion composition.

6. In the dispersion composition according to claim 5, The aforementioned dispersant is a branched acidic resin. Dispersion composition.

7. In the dispersion composition according to claim 6, The acid value of the dispersant is 45 mg KOH / g or more and 100 mg KOH / g or less. Dispersion composition.

8. In the dispersion composition according to claim 5, The dispersant is a linear basic resin. Dispersion composition.

9. In the dispersion composition according to claim 8, The amine value of the dispersant is 60 mg KOH / g or more and 75 mg KOH / g or less. Dispersion composition.

10. A method for producing a dispersion composition, The dispersion composition is obtained by ultrasonic dispersion, homogenizer dispersion, or bead mill dispersion of diamond particles, a dispersion medium, and a dispersant for dispersing the diamond particles in the dispersion medium. A method for producing a dispersed composition.

11. A liquid resin composition, A dispersion composition comprising the one described in claim 1, Resin composition.

12. In the resin composition according to claim 11, Furthermore, containing a curable compound, Resin composition.

13. In the resin composition according to claim 12, The curable compound is a photocurable compound or a thermocurable compound. Resin composition.

14. In the resin composition according to claim 11, Furthermore, containing alkali-soluble compounds, Resin composition.

15. A film-coated substrate, The system comprises a substrate and a diamond dispersion film. The diamond dispersion film is resin matrix and The resin matrix contains diamond particles dispersed in the resin matrix, The primary particles of the diamond particles have an average particle size D50, which is the cumulative 50% diameter in their volume-based particle size distribution, that is between 50 nm and 400 nm. Film-coated substrate.

16. A method for manufacturing a film-coated substrate, A step of preparing a base material and a resin composition according to any one of claims 11 to 14, A step of applying the resin composition to the substrate, A step of removing at least a portion of the liquid component from the resin composition, The process includes a step of curing the resin composition after removing the liquid component to form a diamond dispersion film and obtain a film-coated substrate. A method for manufacturing a film-coated substrate.

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