Reaction-curable composition

Abstract

The present disclosure addresses the problem of providing a reaction curable composition that makes it possible to suppress reflection of light on the surface of a cured product by producing the cured product by curing the reaction curable composition. A reaction curable composition according to one aspect of the present disclosure contains a reactive component (A) and a filler (B). The filler (B) contains an antireflection filler (B1). The antireflection filler (B1) has an average particle diameter of 0.8-10 μm, and the antireflection filler (B1) has a plurality of protrusions on the surface of particles thereof. The protrusions have an average diameter of 100-500 nm.

Description

Technical Field

[0001] The present disclosure relates to a reaction-curable composition, and more particularly to a reaction-curable composition containing a reactive component and a filler.

Background Art

[0002] Patent Document 1 discloses a curable one-component epoxy resin composition containing (a) an epoxy component containing at least one epoxy compound having two or more groups per molecule, a latent curing agent component, a thixotropy-imparting component, a polythiol component containing a polythiol having at least one secondary or tertiary thiol group per molecule, and a stabilizing component containing a solid organic acid, and optionally including a pigment, a filler, etc.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

[0004] An object of the present disclosure is to provide a reaction-curable composition capable of suppressing light reflection on the surface of a cured product by curing to produce the cured product.

[0005] The reaction-curable composition according to one aspect of the present disclosure contains a reactive component (A) and a filler (B). The filler (B) contains an antireflection filler (B1). The average particle diameter of the antireflection filler (B1) is 0.8 μm or more and 10 μm or less, and the antireflection filler (B1) has a plurality of protrusions on the surface of its particles. The average diameter of the protrusions is 100 nm or more and 500 nm or less.

Brief Description of the Drawings

[0006] [Figure 1]Figure 1 is a schematic cross-sectional view of an example of a cured product of a reaction-curable composition in one embodiment of the present disclosure. [Figure 2] Figure 2 is a graph showing the frequency of protrusion diameters on particles of filler #1 (manufactured by Nikko Rica Co., Ltd., product name Silcrusta MKN03). [Figure 3] Figure 3 is a graph showing the specular reflectance spectra for each of the cured products of several compositions with different concentrations of filler #1 (manufactured by Nikko Rica Co., Ltd., product name Silcrusta MKN03). [Figure 4] Figure 4 is a graph showing the diffuse reflectance spectra for each of the cured products of several compositions with different concentrations of filler #1 (manufactured by Nikko Rica Co., Ltd., product name Silcrusta MKN03). [Figure 5] Figure 5 is a graph showing the total light reflectance spectra for each of the cured products of several compositions with different concentrations of filler #1 (manufactured by Nikko Rica Co., Ltd., product name Silcrusta MKN03). [Figure 6] Figure 6 shows an image obtained by photographing the surface of a cured product of a composition in which filler #1 (manufactured by Nikko Rica Co., Ltd., product name Silcrusta MKN03) is 30% by volume, using a differential scanning electron microscope. [Figure 7] Figure 7 shows images obtained by photographing particles of filler #1 (manufactured by Nikko Rica Co., Ltd., product name Silcrusta MKN03) using a differential scanning electron microscope. [Modes for carrying out the invention]

[0007] First, the inventor will explain the circumstances that led to the completion of this disclosure.

[0008] Reactively curable compounds containing reactive components and fillers are sometimes used as adhesives, sealants, etc. For example, Patent Document 1 (JP 2014-500895) discloses a curable one-component epoxy resin composition comprising (a) an epoxy component containing at least one epoxy compound having two or more groups per molecule, a latent curing agent component, a thixotropy-imparting component, a polythiol component containing a polythiol having at least one secondary or tertiary thiol group per molecule, and a stabilizing component containing a solid organic acid, and optionally including pigments, fillers, etc.

[0009] The inventors noticed that when adhesives are used in the manufacture of optical equipment such as camera modules, and when encapsulants are used as underfills, sidefills, or coatings for optical elements such as image sensors, the adhesives and encapsulants can cause noise by specularly reflecting light.

[0010] Therefore, the inventor investigated anti-glare methods and anti-reflection methods as methods for suppressing specular reflection of light on the surface of a cured product obtained by curing the composition.

[0011] However, according to the inventor's research, the anti-glare method has the following problems:

[0012] (1) In the case of anti-glare methods that utilize fillers, if specular reflection of light is to be suppressed using only fine fillers, or a combination of large-diameter and fine fillers, the composition tends to thicken due to the presence of fillers. In particular, with solvent-free methods, the amount of filler must be limited to prevent excessive thickening. Therefore, it is difficult to obtain a large reflection suppression effect.

[0013] (2) In the anti-glare method that utilizes the phase separation method, controlling the surface irregularities of the cured product is extremely difficult.

[0014] (3) In the antiglare method using shape transfer, post-processing of the cured product is required. Therefore, just curing the composition cannot suppress specular reflection of light, and in particular, post-processing is difficult in the case of adhesives for camera modules.

[0015] In addition, according to the inventor's investigation, the antireflection method has the following problems.

[0016] (1) In the antireflection method using optical interference, it is essential to impart a laminated structure to the cured product, so complicated processes are required, and this method is particularly difficult to apply to adhesive applications.

[0017] (2) In the antireflection method by reducing the refractive index of the cured product, the refractive index of the cured product obtained by curing a composition containing a reactive compound such as an epoxy compound or an acrylic compound, which is particularly used for adhesives and sealants, is at least 1.4 even at the lowest, and since the refractive index difference from air is large, it is difficult to sufficiently suppress reflection.

[0018] (3) In the antireflection method using pseudo-refractive index continuity, it is conceivable to form irregularities on the surface of the cured product by fine fillers having a wavelength below the visible light region, such as a moth-eye structure. However, if only fine fillers or a combination of large-diameter fillers and fine fillers are used to suppress specular reflection of light, the composition tends to thicken because it contains fillers. Especially in the case of solvent-free, the filler amount must be limited to suppress excessive thickening. Therefore, it is difficult to obtain a large reflection suppression effect.

[0019] Therefore, the inventor has conducted intensive research and development to provide a reaction-curable composition that can suppress specular reflection of light on the surface of the cured product by curing to produce a cured product without additional processes such as post-processing, and has completed the present disclosure. However, the process of completing the present disclosure does not limit the content of the present disclosure. That is, for example, the use of the reaction-curable composition is not limited only to adhesives and sealants, nor is it limited only to applications that require suppression of specular reflection of light.

[0020] Hereinafter, an embodiment of the present disclosure will be described. Note that the following embodiment is only one of various embodiments of the present disclosure. The following embodiment can be variously modified according to the design as long as the object of the present disclosure can be achieved.

[0021] The reaction-curable composition according to this embodiment (hereinafter also referred to as composition (X)) contains a reactive component (A) and a filler (B). The filler (B) contains an antireflection filler (B1). The average particle diameter of the antireflection filler (B1) is 0.8 μm or more and 10 μm or less. The antireflection filler (B1) has a plurality of protrusions on the surface of its particles. The average diameter of the protrusions is 100 nm or more and 500 nm or less.

[0022] Note that the antireflection filler (B1) may be a filler that satisfies the above particle diameter conditions and has the above protrusions. The name "antireflection filler (B1)" is set only for distinguishing the antireflection filler (B1) from other fillers (B2), and the phrase "antireflection" in this name does not define the characteristics of the antireflection filler (B1).

[0023] According to this embodiment, the composition (X) is cured by reacting the reactive component (A) to obtain a cured product. This cured product contains the antireflection filler (B1), and since this antireflection filler (B1) is likely to scatter light, specular reflection of light on the surface of the cured product is effectively suppressed. Therefore, in this embodiment, by producing a cured product from the composition (X), specular reflection of light on the surface of the cured product can be suppressed.

[0024] In addition, since the antireflection filler (B1) is very likely to scatter light, specular reflection of light on the surface of the cured product can be suppressed without excessively increasing the amount of the filler (B) in the composition (X). Therefore, the amount of the filler (B) in the composition (X) can be appropriately suppressed to suppress thickening of the composition (X) due to the filler (B). Also, for this reason, for example, even if the composition (X) does not contain a solvent or the solvent content in the composition (X) is small, the composition (X) can have good fluidity.

[0025] Furthermore, by appropriately controlling the amount of filler (B) in composition (X), it is possible to achieve a lower modulus of elasticity and a higher elongation rate in the cured product. This can improve the impact resistance of the cured product.

[0026] Preferably, composition (X) is a one-component type and solvent-free, and its cured product has sufficiently excellent anti-reflective properties for light in the visible light region. Preferably, the cured product of composition (X) also has sufficiently excellent anti-reflective properties for light in the near-infrared region (from 800 nm to 1000 nm). If the cured product has anti-reflective properties for light in the visible light region, for example, when composition (X) is used as an adhesive in a camera module, the reflection of visible light within the camera module is suppressed, which can suppress noise such as flare noise in images output by the image sensor, etc. Furthermore, if the cured product has anti-reflective properties for light in the near-infrared region, discoloration of images output by the image sensor, etc. is suppressed. For this reason, it is particularly desirable that light in the visible light region and infrared light not be reflected in the optical path inside the camera module, etc. Anti-reflective properties refer to the property of being able to suppress specular reflection of light.

[0027] Further details about the components of composition (X) will be explained.

[0028] As described above, in one embodiment of the present disclosure, composition (X) contains a reactive component (A) and a filler (B). Filler (B) contains an anti-reflective filler (B1). The average particle diameter of the anti-reflective filler (B1) is 0.8 μm or more and 10 μm or less. Preferably, 10% or more of the surface area of ​​the anti-reflective filler (B1) particles has protrusions with an average diameter of 100 nm or more and 500 nm or less. The average diameter of the protrusions is the average value of the protrusion diameters. The protrusion diameter is the average value of the vertical diameter (dimension of the major axis) and the horizontal diameter (dimension in the direction perpendicular to the major axis) of the protrusions.

[0029] Reactive component (A) is a component that polymerizes upon reaction. Reactive component (A) may, for example, contain a reactive compound (A1), or contain a reactive compound (A1) and a curing agent (A2) that reacts with the reactive compound (A1).

[0030] The reactive compound (A1) contains, for example, at least one of an epoxy compound and an acrylic compound.

[0031] The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy compound contains at least one selected from the group consisting of, for example, biphenyl-type epoxy resins; bisphenol-type epoxy resins such as bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, and bisphenol S-type epoxy resins; hydrogenated bisphenol-type epoxy resins such as hydrogenated bisphenol A-type epoxy resins, hydrogenated bisphenol F-type epoxy resins, and hydrogenated bisphenol S-type epoxy resins; naphthalene ring-containing epoxy resins; anthracene ring-containing epoxy resins; alicyclic epoxy resins; dicyclopentadiene-type epoxy resins; phenol novolac-type epoxy resins; cresol novolac-type epoxy resins; triphenylmethane-type epoxy resins; brome-containing epoxy resins; aliphatic epoxy resins; aliphatic polyether-type epoxy resins; triglycidyl isocyanurate; glycidyl group-containing silicone resins; and glycidylamine-type epoxy resins.

[0032] The epoxy compound preferably contains a bisphenol-type epoxy resin, and more preferably contains at least one of a bisphenol A-type epoxy resin and a bisphenol F-type epoxy resin.

[0033] Acrylic compounds are compounds having at least one of an acryloyl group and a methacryloyl group in their molecule. Acrylic compounds include, for example, at least one selected from the group consisting of trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, dimethylol-tricyclodecane diacrylate, acryloylmorpholine, tetrahydrofurfuryl acrylate, 4-hydroxybutyl acrylate, 9,9-bis(4-(2-(meth)acryloyloxyethoxy)phenyl)-9H-fluorene, tris-(2-acryloxyethyl) isocyanurate, bis-(2-acryloxyethyl) isocyanurate, caprolactone-modified tris-(2-acryloxyethyl) isocyanurate, isocyanurate EO-modified diacrylate, and isocyanurate EO-modified triacrylate.

[0034] The reactive compound (A1) is preferably liquid at 25°C. In this case, the thickening of composition (X) is further suppressed.

[0035] The compounds that reactive compound (A1) may contain are not limited to epoxy compounds and acrylic compounds. For example, reactive compound (A1) may contain oxetane compounds, which are compounds having an oxetane group in their molecule, vinyl compounds, which are compounds having a vinyl group in their molecule, and so on.

[0036] This section explains the case where the reactive component (A) contains a hardening agent (A2).

[0037] The curing agent (A2) contains a compound that can react with the reactive compound (A1). The curing agent (A2) includes, for example, at least one selected from the group consisting of amine compounds, acid anhydrides, phenol compounds, thiol compounds, and imidazole compounds. It is preferable that the reactive compound (A1) contains an epoxy compound and the curing agent (A2) contains at least one selected from the group consisting of amine compounds, acid anhydrides, phenol compounds, thiol compounds, and imidazole compounds. It is also preferable that the reactive compound (A1) contains at least one of an epoxy compound and an acrylic compound and the curing agent (A2) contains a thiol compound.

[0038] Amine compounds are compounds that have an amino group in their molecule. Examples of amine compounds include 4,4'-diamino-3,3'-diethyldiphenylmethane.

[0039] The acid anhydride contains one or more selected from the group consisting of, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, benzophenonetetracarboxylic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and polyazelaic anhydride.

[0040] A phenol compound is a compound having a phenolic hydroxyl group in its molecule. Preferably, a phenol compound has two or more phenolic hydroxyl groups in one molecule. The phenol compound may include one or more selected from the group consisting of, for example, phenol novolac resin, cresol novolac resin, biphenyl-type novolac resin, triphenylmethane-type resin, naphthol novolac resin, phenol aralkyl resin, and biphenyl aralkyl resin.

[0041] Thiol compounds are compounds that have a thiol group in their molecule. Examples of thiol compounds include pentaerythritol tetra(3-mercaptopropionate) (e.g., product name Epomate QX40 manufactured by Mitsubishi Chemical Corporation).

[0042] The imidazole compound contains at least one selected from the group consisting of, for example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole.

[0043] Furthermore, even if the reactive compound (A1) contains compounds other than epoxy compounds, the curing agent (A2) may contain appropriate compounds depending on the type of compound contained in the reactive compound (A1).

[0044] The content of the curing agent (A2) is, for example, 0.3 equivalents or more and 1.5 equivalents or less per equivalent of the reactive compound (A1).

[0045] Composition (X) may contain a curing catalyst. In this case, heating of composition (X) facilitates the curing reaction of composition (X). The curing catalyst contains at least one component selected from the group consisting of, for example, imidazoles, cycloamidines, tertiary amines, organophosphines, tetrasubstituted phosphonium / tetrasubstituted borates, quaternary phosphonium salts having counteranions other than borates, and tetraphenylboron salts. The curing catalyst may also contain a latent curing catalyst. In this case, the reaction of composition (X) in an unheated state can be suppressed, and the storage stability of composition (X) can be improved. The latent curing catalyst may contain at least one of a liquid latent curing accelerator and a solid-disperse latent curing accelerator. The latent curing catalyst may also contain a microencapsulated latent curing catalyst. The microencapsulated latent curing catalyst contains, for example, a microencapsulated imidazole containing imidazoles as a catalytically active compound. The proportion of the curing catalyst is, for example, 0.1% to 20% relative to the epoxy resin.

[0046] Composition (X) may contain an initiator (C). Initiator (C) is a compound that initiates the reaction of reactive component (A). For example, if reactive component (A) contains an acrylic compound, initiator (C) may contain a radical polymerization initiator. Radical polymerization initiators include, for example, at least one compound selected from the group consisting of aromatic ketones, acyl phosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having carbon-halogen bonds, and alkylamine compounds. The proportion of initiator (C) is, for example, 0.1% by mass or more and 10% by mass or less relative to the acrylic compound.

[0047] Examples of combinations of a reactive compound (A1) with a curing agent (A2) or initiator (C) include combinations of epoxy compounds and acid anhydrides, epoxy compounds and amine compounds, epoxy compounds and thiol compounds, epoxy compounds and phenol compounds, epoxy compounds and acrylic compounds with thiol compounds and initiator (C), and epoxy compounds and acrylic compounds with amine compounds and initiator (C). However, the combinations of reactive compound (A1) with curing agent (A2) or initiator (C) are not limited to those mentioned above.

[0048] As described above, it contains filler (B), which contains anti-reflective filler (B1).

[0049] As described above, the average particle size of the anti-reflective filler (B1) is 0.8 μm or more and 10 μm or less. If the average particle size of the anti-reflective filler (B1) is 0.8 μm or more, the composition (X) is less likely to thicken. If this average particle size is 10 μm or less, the fluidity of the composition (X) can be ensured when the composition (X) is permeated into a narrow gap or when it is dispensed by a dispensing method. This average particle size is preferably 1 μm or more, and more preferably 1.5 μm or more. Furthermore, this average particle size is preferably 5 μm or less, and more preferably 4 μm or less. Note that this average particle size is the median diameter calculated from the volume-based particle size distribution measured by laser diffraction scattering.

[0050] Furthermore, because the average diameter of the protrusions is between 100 nm and 500 nm, visible light is effectively scattered by the anti-reflective filler (B1), which can impart good anti-reflective properties to the cured product.

[0051] The diameter of the protrusions is determined by photographing the anti-reflective filler (B1) particles with a differential scanning electron microscope, measuring the major axis (vertical diameter) and the diameter perpendicular to this vertical axis (horizontal diameter) of the protrusions appearing in the resulting image, and then calculating the average value of the vertical and horizontal diameters. The average diameter of the protrusions is the average value of the diameters of all protrusions appearing in the image of 10 particles.

[0052] To more effectively scatter visible light, the average diameter of the protrusions of the anti-reflective filler (B1) is preferably 200 nm or more. It is even more preferable if the average diameter is 400 nm or more. It is also preferable that the average diameter of the protrusions of the anti-reflective filler (B1) is 500 nm or less. It is also preferable that the frequency of protrusions between 200 nm and 500 nm is high in the distribution of protrusion diameters of the anti-reflective filler (B1). For example, it is preferable that the total number of protrusions with a diameter between 200 nm and 500 nm accounts for 50% or more of the total number of protrusions. Furthermore, it is preferable that the frequency distribution curve of the protrusion diameter, with the number of protrusions on the vertical axis and the protrusion diameter on the horizontal axis, has a broad peak with a consistently high frequency in the range of protrusion diameters between 200 nm and 400 nm. In this case, the protrusions of the anti-reflective filler (B1) can effectively scatter light across a wide wavelength range in the visible light region.

[0053] It is preferable that the anti-reflective filler (B1) has protrusions on 10% or more of the surface area of ​​its particles. In this case, the anti-reflective filler (B1) can impart better anti-reflective performance to the cured product. In this case, the particle surface refers to the surface of the particles (hereinafter also referred to as base particles) when the protrusions are removed from the anti-reflective filler (B1) particles. Having protrusions on 10% or more of the surface area of ​​the particles means that the anti-reflective filler (B1) particles have a shape such that multiple protrusions are attached to the surface of the base particles, and the total area ratio of the parts of the base particle surface to which the protrusions are attached (hereinafter also referred to as the attachment area ratio) is 10% or more of the total surface area of ​​the base particle. The attachment area ratio is more preferably 20% or more, and even more preferably 30% or more. The attachment area ratio is also, for example, 100% or less, 95% or less, or 90% or less.

[0054] The proportion of the attached area can be determined by taking images with a differential scanning electron microscope and calculating the particle area and protrusion area from the obtained images.

[0055] The particles of the anti-reflective filler (B1) are preferably core-shell type particles having a core and a shell covering the core, and preferably having protrusions on the surface of the shell. That is, it is preferable that the base particles in the anti-reflective filler (B1) particles have a core and a shell. In this case, light scattering can occur at the interface between the core and the shell due to the difference in refractive index between the core and the shell. Therefore, the anti-reflective filler (B1) can scatter light more effectively.

[0056] It is preferable that the particles of the anti-reflective filler (B1) are organic resin particles. It is also preferable that both the core and the shell of the anti-reflective filler (B1) particles contain organic resin. In these cases, the cured product of composition (X) can have a lower modulus of elasticity, which can increase the impact resistance of the cured product.

[0057] The particles of the anti-reflective filler (B1) include at least one selected from the group consisting of acrylic resins such as PMMA (polymethyl methacrylate), silicone resins, styrene resins, melamine resins, and urethane resins. Furthermore, if the particles of the anti-reflective filler (B1) are core-shell type particles, each of the core and shell includes at least one selected from the group consisting of acrylic resins such as PMMA (polymethyl methacrylate), silicone resins, styrene resins, melamine resins, and urethane resins.

[0058] If the anti-reflective filler (B1) particles are of the core-shell type, for example, the core contains an acrylic resin such as PMMA (polymethyl methacrylate), and each of the shell and protrusions contains a silicone resin. In this case, the anti-reflective filler (B1) scatters light more effectively, and the anti-reflective filler (B1) can make the cured product have a lower modulus of elasticity.

[0059] If the anti-reflective filler (B1) particles are core-shell type particles, the core may be hollow. That is, the anti-reflective filler (B1) particles may be hollow particles having a cavity and a shell covering the cavity.

[0060] Furthermore, the particles of the anti-reflective filler (B1) do not necessarily have to be core-shell type particles. In other words, the particles of the anti-reflective filler (B1) may be homogeneous overall.

[0061] It is preferable that the refractive index of the anti-reflective filler (B1) particles is 1.7 or less, and that it is less than or equal to the refractive index of the cured product of the reactive component (A). In this case, the total light reflectance (i.e., the sum of diffuse reflectance and specular reflectance) of the cured product of composition (X) can be maintained or reduced. It is more preferable that the refractive index of the anti-reflective filler (B1) particles is 1.6 or less. It is also preferable that the refractive index of the anti-reflective filler (B1) particles is 1.3 or more.

[0062] The refractive index of the anti-reflective filler (B1) particles is the refractive index of the material of the particles if the anti-reflective filler (B1) particles are homogeneous overall, and the refractive index of the shell if the anti-reflective filler (B1) particles are core-shell type particles. It is preferable that the refractive index of the core, like that of the shell, satisfies at least one of the following conditions: 1.7 or less, and less than or equal to the refractive index of the cured reactive component (A).

[0063] A commercially available product can be used as the anti-reflective filler (B1). For example, the anti-reflective filler (B1) contains product name Silcrusta MKN03.

[0064] The filler (B) in composition (X) may further contain filler (B2) other than the anti-reflective filler (B1). If the average particle size of filler (B2) other than the anti-reflective filler (B1) is 100 nm or more and less than the average particle size of anti-reflective filler (B1), the specular reflectance of the cured product of composition (X) may be reduced. Even if the particle size of filler (B2) other than the anti-reflective filler (B1) is larger than the above range, if this filler (B2) partially dissolves during the curing of composition (X), thereby reducing the particle size of filler (B2) in the cured product, the specular reflectance of the cured product of composition (X) may be reduced by filler (B2). An example of filler (B2) that can partially dissolve during the curing of composition (X) is powdered polyamine (for example, ADEKA Corporation, product name EH-4357S). In other words, even if the average particle size of the filler (B2) in composition (X) is larger than the average particle size of the anti-reflective filler (B1), it is preferable that the average particle size of the filler (B2) in composition (X) is 100 nm or more and less than the average particle size of the anti-reflective filler (B1). The average particle size of the filler (B2) in the cured product is more preferably 0.1 μm or more, and even more preferably 0.2 μm or more. Furthermore, the average particle size of the filler (B2) is more preferably 3 μm or less, and even more preferably 2 μm or less. This average particle size is the median diameter calculated from the volume-based particle size distribution measured by laser diffraction scattering. The filler (B2) may completely dissolve during the curing of composition (X). In this case, if the filler (B2) completely dissolves, the particles of the anti-reflective filler (B1) are more likely to be exposed on the surface of the cured product, so the specular reflectance of the cured product can be further reduced, and the particles of the filler (B1) are less likely to hinder the reduction of the total light reflectance of the cured product.

[0065] The particles of filler (B2) preferably have an angular shape, such as a crushed shape. In this case, the specular reflectance of the cured product of composition (X) can be further reduced by the filler (B2).

[0066] The filler (B2) may contain, for example, at least one of a resin filler and an inorganic filler.

[0067] The inorganic filler contains at least one selected from the group consisting of, for example, silica, alumina, barium sulfate, talc, clay, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium dioxide, barium zirconate, and calcium zirconate.

[0068] Resin fillers can enhance the flexibility of the cured product. Resin fillers contain, for example, at least one selected from the group consisting of silicone powder, polystyrene powder, acrylic resin powder, benzoguanamine resin powder, and polybutadiene powder, as well as powders containing two or more of the above resins. The resins that can be contained in resin fillers are not limited to those mentioned above. Silicone powder contains, for example, at least one selected from the group consisting of powder made of silicone rubber (silicone rubber powder), powder made of silicone resin (silicone resin powder), and powder having a core made of silicone rubber and a shell made of silicone resin (silicone composite powder). Silicone resin is a silicone having a three-dimensional skeleton mainly composed of siloxane bonds, and silicone rubber is a silicone having a two-dimensional skeleton mainly composed of siloxane bonds.

[0069] The inorganic filler reduces curing shrinkage during the curing process of composition (X) to produce a cured product. Therefore, composition (X) becomes even more suitable for bonding parts in precision equipment such as camera modules. The inorganic filler contains at least one selected from the group consisting of silica, alumina, barium sulfate, talc, clay, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium dioxide, barium zirconate, and calcium zirconate.

[0070] If filler (B) contains filler (B2) other than anti-reflective filler (B1), it is preferable that filler (B2) does not contain silica and alumina, or has a low silica and alumina content, in order to reduce the elastic modulus of the cured product of composition (X). Specifically, it is preferable that the ratio of silica and alumina to composition (X) is 10% by volume or less.

[0071] The ratio of filler (B), including anti-reflective filler (B1), to composition (X) is preferably 10% by volume or more. In this case, when composition (X) is cured, the particles 3 of anti-reflective filler (B1) may be exposed on the surface of the cured product 1 due to curing shrinkage caused by the reaction of reactive component (A) (see Figure 1). As a result, the light scattering effect by anti-reflective filler (B1) is significantly reduced, and the specular reflectance of the cured product can be further reduced. The ratio of filler (B) is more preferably 20% by volume or more, and even more preferably 25% by volume or more. Furthermore, the ratio of filler (B) is preferably 45% by volume or less. In this case, the thickening of composition (X) by filler (B) can be suppressed. This ratio is more preferably 40% by volume or less, and even more preferably 35% by volume or less.

[0072] The amount of anti-reflective filler (B1) is preferably 5 parts by mass or more and 82 parts by mass or less per 100 parts by mass of reactive component (A). When the amount of anti-reflective filler (B1) is 5 parts by mass or more, the specular reflectance of light on the surface of the cured product can be particularly reduced by the anti-reflective filler (B1). When the amount of anti-reflective filler (B1) is 82 parts by mass or less, the thickening of composition (X) by the anti-reflective filler (B1) can be suppressed. The amount of anti-reflective filler (B1) is more preferably 5% by volume or more, and even more preferably 25% by volume or more. Furthermore, this amount is more preferably 66% by volume or less, and even more preferably 43% by volume or less.

[0073] The composition (X) preferably further contains a coloring agent (D). In this case, the specular reflectance and total reflectance of the cured product can be further reduced as light is absorbed by the coloring agent (D) inside the cured product of the composition (X).

[0074] It is preferable that the coloring agent (D) contains at least one selected from the group consisting of carbon black, titanium black, zirconium nitride, and dyes. In this case, the specular reflectance and total light reflectance of the cured product are more easily reduced. That is, by lowering the transmittance of the cured product with the coloring agent (D), it is possible to suppress the reflection of light that has entered the interior of the cured product from the interface with the member (adhesion object, etc.) in contact with the cured product and coming out to the outside.

[0075] The average transmittance of light in the wavelength range of 400 nm to 800 nm of the cured product of composition (X) is preferably 10% or less, and more preferably 1% or less. If the transmittance is 1% or less, the light that penetrates into the interior of the cured product and is reflected by the adherend or the like and emitted to the outside will have almost no effect on the specular reflectance of the cured product.

[0076] When composition (X) contains a coloring agent (D), the amount of coloring agent (D) is preferably more than 0 parts by mass and 10 parts by mass or less per 100 parts by mass of reactive component (A). The amount of coloring agent (D) is more preferably 0.1 parts by mass or more, and even more preferably 0.3 parts by mass or more. Furthermore, the amount of coloring agent (D) is more preferably 8 parts by mass or less, and even more preferably 5 parts by mass or less.

[0077] Composition (X) may further contain additives other than those mentioned above, to the extent that the effects of this embodiment are not excessively impaired. The additives include, for example, at least one selected from the group consisting of polymerization inhibitors, radical scavengers, diluents, flexibility imparters, coupling agents, antioxidants, thixotropy imparters (thixotropic agents), and dispersants.

[0078] It is preferable that composition (X) does not contain a solvent or contains only a solvent that is inevitably mixed in as a solvent. If composition (X) contains a solvent, it is preferable that the proportion of the solvent to composition (X) is 0.1% by mass or less. In this case, composition (X) can be suitably used as an adhesive or suitably used to produce an underfill material. Furthermore, in this embodiment, the anti-reflective performance of the cured product of composition (X) can be enhanced while suppressing the thickening of composition (X) by the filler (B). Therefore, composition (X) can have good fluidity even if it does not contain a solvent or has a low solvent content, and thus the coatability and moldability of composition (X) can be good.

[0079] It is preferable that the viscosity of composition (X) at 25°C, measured with a Type B rotational viscometer at a rotational speed of 20 rpm, is 200 Pa·s or less. In this case, composition (X) may have particularly good coatability and moldability. Furthermore, as described above, in this embodiment, the anti-reflective performance of the cured product of composition (X) can be enhanced while suppressing the thickening of composition (X) by the filler (B), thereby achieving the low viscosity of composition (X) as described above. This viscosity is more preferably 100 Pa·s or less, and even more preferably 50 Pa·s or less. Also, this viscosity is, for example, 2 Pa·s or more.

[0080] Furthermore, it is preferable that the thixotropy index (10rpm viscosity / 100rpm viscosity), which is the ratio of the viscosity of composition (X) at 25°C measured at a rotation speed of 2 rpm on a B-type rotational viscometer to the viscosity measured at 25°C on a B-type rotational viscometer at a rotation speed of 2 rpm, is between 1 and 7. In this case, composition (X) can have particularly good fluidity and can be more preferably used as an adhesive or for producing underfill material. In particular, in this case, composition (X) can be preferably used for producing underfill material for image sensors. In this embodiment, the anti-reflective performance of the cured product of composition (X) can be improved while suppressing the thickening of composition (X) by the filler (B), thereby achieving the aforementioned thixotropy index. This thixotropy index is more preferably 1.5 or higher, and even more preferably 1.8 or higher. It is also more preferably 5.0 or lower, and even more preferably 4.0 or lower.

[0081] A cured product is obtained by curing composition (X). In this case, composition (X) can be cured by reacting the reactive component (A) in a manner appropriate to the composition of the reactive component (A) contained in composition (X), and the composition of the initiator (C) and catalyst, etc., which composition (X) may contain as needed. For example, composition (X) can be cured by heating. Furthermore, if composition (X) contains an initiator (C), composition (X) can be cured by irradiating it with light such as ultraviolet light, or by further heating it after irradiating it with light.

[0082] Figure 1 shows a schematic example of a cured product 1 of composition (X). Before curing, anti-reflective filler (B2) particles 3 are embedded in composition (X), but when composition (X) hardens, curing shrinkage occurs due to the reaction of reactive component (A), so the anti-reflective filler (B2) particles 3 are exposed on the surface 2 of cured product 1. In the example shown in Figure 1, particles 3 are core-shell type particles having a core 32 and a shell 31, and particles 3 have a plurality of protrusions 33 on their surface. As described above, these protrusions 33 give the surface 2 of cured product 1 fine irregularities, so diffuse reflection of light is likely to occur on the surface 2 of cured product 1, and it is also possible to reduce the total light reflectance of this surface 2 itself. As a result, the specular reflectance of light of cured product 1 is reduced. Furthermore, as described above, if particles 3 are core-shell type particles, diffuse reflection of light is likely to occur at the interface between the core 32 and the shell 31 due to the refractive index difference between the core 32 and the shell 31, so the specular reflectance of light is likely to be further reduced. Furthermore, as mentioned above, if the average particle size of the anti-reflective filler (B1) is 0.8 μm or larger, composition (X) is less likely to thicken, and if it is 10 μm or smaller, the fluidity of composition (X) can be ensured for applications such as underfill material production.

[0083] The average specular reflectance of the cured product of composition (X), measured using an integrating sphere at an incident angle of 8° for light in the wavelength range of 400 nm to 800 nm, is preferably 0.5% or less, and more preferably 0.2% or less. The average specular reflectance of light in the wavelength range of 800 nm to 1000 nm, measured by the above method, is also preferably 0.5% or less, and more preferably 0.2% or less. The average specular reflectance of light in the wavelength range of 400 nm to 1000 nm, measured by the above method, is also preferably 0.5% or less, and more preferably 0.2% or less. In these cases, specular reflection of light in the cured product can be particularly reduced. Therefore, when the cured product of composition (X) is applied to optical equipment, noise caused by light reflection in the cured product can be reduced. In this embodiment, such a low average specular reflectance is achievable. In addition, a low diffuse reflectance in the cured product of composition (X) is also preferable for noise reduction.

[0084] It is preferable that the elastic modulus (storage modulus) of the cured product of composition (X) at -40°C is 10 GPa or less. In this case, the cured product of composition (X) tends to have good impact resistance, and therefore composition (X) can be used particularly suitably as an adhesive for camera modules. Note that an elastic modulus of 10 GPa or less at -40°C means that the elastic modulus of the cured product is low below the glass transition temperature. In this embodiment, such a low elastic modulus of the cured product can be achieved. This elastic modulus is more preferably 6 GPa or less, and even more preferably 5 GPa or less. Also, this elastic modulus is, for example, 1 GPa or more. The method for measuring the elastic modulus will be explained in the examples below.

[0085] As described above, composition (X) is suitable as an adhesive, for example, and more specifically as an adhesive for bonding components of optical equipment such as camera modules. In this case, even if the surface of the cured composition (X) bonding the components is exposed to the outside, specular reflection of light on this surface is suppressed. Therefore, in optical equipment such as camera modules, the noise caused by light reflected from the surface of the adhesive is suppressed. The material of the components to be bonded with composition (X) is not limited to, but is also not limited to, resin materials such as liquid crystal polymer, polycarbonate, polyester, and polyimide, metals such as nickel and copper, ceramics, glass, or various other substrate materials. When composition (X) is used as an adhesive, for example, the components can be bonded together by interposing composition (X) between two components and curing the composition (X) in an appropriate manner as described above.

[0086] As described above, composition (X) is also suitably used to produce underfill material. Underfill material is a sealing material that seals the gap between a substrate, such as a printed circuit board, and mounted components mounted on the substrate. Composition (X) is particularly suitable when the mounted components are optical elements such as image sensors. In this case, even if the surface of the underfill material, such as the edges, is exposed to the outside, specular reflection of light on this surface is suppressed, thereby preventing specular reflection of light from the surface of the underfill material from causing noise in the optical element. When producing underfill material from composition (X), for example, composition (X) is injected into the gap between the substrate and the mounted components mounted on the substrate, and then composition (X) is cured by an appropriate method as described above.

[0087] (summary) A reaction-curable composition according to a first aspect of this disclosure contains a reactive component (A) and a filler (B). The filler (B) contains an anti-reflective filler (B1). The average particle diameter of the anti-reflective filler (B1) is 0.8 μm or more and 10 μm or less, and the anti-reflective filler (B1) has a plurality of protrusions on its particle surface. The average diameter of the protrusions is 100 nm or more and 500 nm or less.

[0088] In this embodiment, by curing a reaction-curable composition to produce a cured product, the reflection of light on the surface of the cured product can be suppressed.

[0089] In a second embodiment, in the first embodiment, the anti-reflective filler (B1) has protrusions on a portion of the surface area of ​​its particles that covers 10% or more of the surface area.

[0090] In a third embodiment, in the first or second embodiment, the reactive component (A) contains a reactive compound (A1), and the reactive compound (A1) contains at least one of an epoxy compound and an acrylic compound.

[0091] In a fourth embodiment, in the third embodiment, the reactive component (A) further contains a curing agent (A2) that reacts with the reactive compound (A1).

[0092] In the fifth embodiment, the invention further contains an initiator (C) as in the third or fourth embodiment.

[0093] In the sixth embodiment, in any one of the first to fifth embodiments, the refractive index of the anti-reflective filler (B1) is 1.7 or less, and at least one of the refractive index of the cured product of the reactive component (A) is less than or equal to that of the anti-reflective filler (B1).

[0094] In the seventh embodiment, in any one of the first to sixth embodiments, the anti-reflective filler (B1) particles are core-shell type particles having a core and a shell covering the core, and having protrusions on the surface of the shell.

[0095] In the eighth aspect, as in the seventh aspect, the core contains acrylic resin, and each of the shell and protrusions contains silicone.

[0096] In the ninth embodiment, in any one of the first to eighth embodiments, the percentage of filler (B) to the reaction-curable composition is 10% by volume or more.

[0097] In the tenth embodiment, in any one of the first to ninth embodiments, the amount of anti-reflective filler (B1) per 100 parts by mass of reactive component (A) is 5 parts by mass or more and 82 parts by mass or less.

[0098] In the eleventh embodiment, in any one of the first to ten embodiments, the reaction-curable composition further contains a coloring agent (D).

[0099] In the twelfth embodiment, the coloring agent contains at least one selected from the group consisting of carbon black, titanium black, zirconium nitride, and dyes.

[0100] In the 13th embodiment, in the 11th or 12th embodiment, the amount of coloring agent (D) is greater than 0 parts by mass and 10 parts by mass or less per 100 parts by mass of reactive component (A).

[0101] In the 14th embodiment, in any one of the first to 13 embodiments, the average specular reflectance of the cured product of the reaction-curable composition is 0.5% or less, measured using an integrating sphere at an incident angle of 8° for light in the range of 400 nm to 800 nm.

[0102] In the 15th embodiment, in any one of the first to 14 embodiments, the viscosity of the reaction-curable composition at 25°C, as measured by a B-type rotational viscometer at 20 rpm, is 200 Pa·s or less.

[0103] In the sixteenth embodiment, in any one embodiment from the first to the fifteenth, the thixotropy index of the reaction-curable composition, which is the ratio of the viscosity at 25°C measured on a B-type rotational viscometer at 2 rpm to the viscosity at 25°C measured on a B-type rotational viscometer at 20 rpm, is 1 or more and 7 or less.

[0104] In the 17th embodiment, in any one of the first to 16 embodiments, the modulus of elasticity of the cured product of the reaction-curable composition is 10 GPa or less at -40°C.

[0105] In the 18th embodiment, in any one embodiment from the 1st to the 17th, the reaction-curable composition does not contain a solvent, or contains only a solvent that is inevitably mixed in as a solvent.

[0106] In the 19th embodiment, in any one embodiment from the 1st to the 18th, the reaction-curing composition is an adhesive.

[0107] In the 20th embodiment, in any one of the first to 18 embodiments, the reaction-curable composition is a composition for producing an underfill material. [Examples]

[0108] More specific embodiments of this model are presented below. However, this model is not limited to the embodiments described below.

[0109] 1. Preparation of the composition The composition was prepared by mixing the raw materials shown in Tables 1 to 4. Details of the raw materials shown in Tables 1 to 4 are as follows. - YD8125: Liquid bisphenol A type epoxy resin. Manufactured by Nippon Steel Chemical & Material Co., Ltd. Product name: YD8125. Specific gravity: 1.2. - YDF8170: Liquid bisphenol F type epoxy resin. Manufactured by Nippon Steel Chemical & Material Co., Ltd. Product name: YDF8170. Specific gravity: 1.2. - #230: 1,6-Hexanediol diacrylate. Manufactured by Osaka Organic Chemical Industry Co., Ltd. Product name: Viscoat #230. Specific gravity: 1.02. - MH-700: Liquid acid anhydride. Manufactured by Shin-Nippon Rika Co., Ltd., product name: Ricacid MH-700. Specific gravity 1.2. - EH-4357S: Powdered polyamine. Manufactured by ADEKA Corporation, product name EH-4357S. Specific gravity 1.2. - QX40: Liquid thiol compound. Manufactured by Mitsubishi Chemical Corporation. Pentaerythritol tetra(3-mercaptopropionate). Product name: Epomate QX40. Specific gravity: 1.26. - MEH8000H: Liquid allylated phenol novolac resin. Manufactured by Meiwa Chemicals Co., Ltd., product name MEH8000H. Specific gravity 1.2. - Omnirad 184: 1-Hydroxycyclohexyl-phenyl ketone. Manufactured by IGM Resins BV, product name Omnirad 184. Specific gravity 1.2. - 2P4MZ: 2-phenyl-4-methylimidazole. Manufactured by Shikoku Chemicals, Inc. Specific gravity 1.1. - HXA9322HP: Microencapsulated imidazole. Manufactured by Asahi Kasei E-Materials Corporation, product name Novacure HXA9322HP. - Filler #1: Core-shell type particle having protrusions on the particle surface, and comprising a core made of polymethyl methacrylate and a shell made of silicone resin. Average particle diameter 3 μm. Protrusion diameter 0.2~0.4 μm. Average protrusion diameter 0.3 μm. Protrusion adhesion area ratio 60%. Manufactured by Nikko Rica Co., Ltd., product name Silcrusta MKN03. Specific gravity 1.2. - Filler #2: Spherical silica. Average particle size 0.3 μm. Manufactured by Admatex, product name SC1053SQ. Specific gravity 2.2. - Filler #3: Spherical silicone powder. Manufactured by Nikko Rica Co., Ltd., product name MSP-SN08. Average particle size 0.8 μm. Specific gravity 1.2. - Filler #4: Silicone powder with protrusions on its surface. Average particle size 4 μm. Protrusion diameter 0.1 μm or less. Manufactured by Nikko Rica Co., Ltd., product name MSPTKN04. Specific gravity 1.2. - Filler #5: Silicone powder with protrusions on its surface. Average particle size 6 μm. Protrusion diameter 0.4 μm or larger, average protrusion diameter 0.6 μm. Manufactured by Nikko Rica Co., Ltd., product name NHRASN06. Specific gravity 1.2. - Filler #6: Spherical silica. Average particle size 1.0 μm. Manufactured by Admatex, product name SC4053SQ. Specific gravity 2.2. - MA600MJ2: Carbon black. Average particle size 20nm. Manufactured by Mitsubishi Chemical Corporation, product name MA600MJ2. Specific gravity 1.8. - UF-8: Titanium black. Average particle size 20nm. Manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd. Product name UF-8. Specific gravity 3.9.

[0110] 2. Evaluation Test The above compositions were subjected to the following evaluation tests. The results are shown in Tables 1 to 4.

[0111] (1) Preparation of hardened material The composition was applied to a glass slide to create a film with dimensions of 20 mm × 50 mm × 0.2 mm.

[0112] In Examples 1-10 and Comparative Examples 15-20, the above films were cured by heating to obtain cured products. The heating temperature and time were 120°C and 3 hours for Examples 1 and 2 and Comparative Examples 15-20, 80°C and 1 hour for Examples 3-8, and 120°C and 3 hours for Examples 9 and 10.

[0113] In Examples 11 and 12, the above-mentioned films were cured by irradiating them with ultraviolet light and then heating them to obtain cured products. The ultraviolet irradiation conditions were a wavelength of 365 nm and an irradiance of 500 mW / cm². 2 , cumulative light intensity 2000 mJ / cm 2 The heating temperature and time were 80°C and 1 hour.

[0114] In Examples 13 and 14, the above-mentioned films were cured by irradiation with ultraviolet light to obtain cured products. The ultraviolet irradiation conditions were a wavelength of 365 nm and an irradiance of 500 mW / cm². 2 , cumulative light intensity 2000 mJ / cm 2 That was the case.

[0115] (2) Viscosity at 25°C A Type B rotational viscometer (manufactured by Toki Sangyo Co., Ltd., model number TVB-10) was used to measure the viscosity of the composition at 25°C under conditions of a rotational speed of 20 rpm.

[0116] (3) Thixotrope at 25℃ A Type B rotational viscometer (manufactured by Toki Sangyo Co., Ltd., model number TVB-10) was used to measure the viscosity of the composition at 25°C under a rotational speed of 2 rpm. From this result and the viscosity obtained in "(1) Viscosity at 25°C" above, the thixotropic index (2rpm viscosity / 20rpm viscosity), which is the ratio of the viscosity at 25°C measured under a rotational speed of 20 rpm to the viscosity at 25°C measured under a rotational speed of 2 rpm, was calculated.

[0117] (4)400-800nm ​​average specular reflectance The cured material prepared in "(1) Preparation of Cured Material" above was used as an evaluation sample. The total reflectance at an incident angle of 8° and the diffuse reflectance at an incident angle of 0° were measured for this evaluation sample using a Shimadzu UV-3600i Plus spectrophotometer. The difference between the total reflectance and the diffuse reflectance was calculated as the specular reflectance. From these results, the average value of the specular reflectance in the wavelength range of 400-800 nm was determined and used as the average specular reflectance.

[0118] (5)800-1000nm average specular reflectance The cured material prepared in "(1) Preparation of Cured Material" above was used as an evaluation sample. The total reflectance at an incident angle of 8° and the diffuse reflectance at an incident angle of 0° were measured for this evaluation sample using a Shimadzu UV-3600i Plus spectrophotometer. The difference between the total reflectance and the diffuse reflectance was calculated as the specular reflectance. From these results, the average value of the specular reflectance in the wavelength range of 800-1000 nm was determined and used as the average specular reflectance.

[0119] (6) Average diffuse reflectance of 400-800 nm The cured material prepared in "(1) Preparation of Cured Material" above was used as an evaluation sample. The diffuse reflectance of this evaluation sample at an incident angle of 0° was measured using a Shimadzu UV-3600i Plus spectrophotometer. From the results, the average value of the diffuse reflectance in the wavelength range of 400-800 nm was calculated and defined as the average diffuse reflectance.

[0120] (7) Average diffuse reflectance of 800-1000 nm The cured material prepared in "(1) Preparation of Cured Material" above was used as an evaluation sample. The diffuse reflectance of this evaluation sample at an incident angle of 0° was measured using a Shimadzu UV-3600i Plus spectrophotometer. From the results, the average value of the diffuse reflectance in the wavelength range of 800-1000 nm was calculated and defined as the average diffuse reflectance.

[0121] (8)400-1000nm average transmittance The cured material prepared in "(1) Preparation of Cured Material" above was used as an evaluation sample. The light transmittance at an incident angle of 0° was measured for this evaluation sample using a Shimadzu UV-3600i Plus spectrophotometer. From these results, the average transmittance in the wavelength range of 400-1000 nm was calculated and used as the average transmittance.

[0122] (9) Adhesive strength The adhesive strength of the composition when used as an adhesive was measured by the following method. The composition was applied to a glass substrate to create a coating film with a diameter of 3 mm and a thickness of 0.5 mm. This coating film was cured under the same conditions as in "(1) Preparation of Cured Product" above to obtain a cured product. The shear adhesive strength of the cured product to the substrate was measured using a shear tester.

[0123] Based on these results, the adhesive strength was evaluated according to the following criteria. A: 15MPa or more. B: 5 MPa or more and less than 15 MPa. C: Less than 5 MPa.

[0124] (10) Elastic modulus A polyethylene terephthalate release film was placed on a glass plate, and a silicone spacer with a plan view of 3 mm x 50 mm and a thickness of 0.5 mm was placed on the release film. After pouring the composition into the spacer's internal space, a polyethylene terephthalate release film was placed on the top surface of the spacer, and the glass plate was placed on the release film. Subsequently, the composition was cured under the same conditions as in "(1) Preparation of Cured Product" above, and an evaluation sample was prepared.

[0125] The storage modulus of this evaluation sample was measured at -40°C using a viscoelasticity measuring instrument DMA7100 manufactured by Hitachi High-Tech Science Corporation, under the conditions of measurement frequency: 1 Hz, measurement mode: tensile, and evaluated according to the following criteria. A: Between 1 GPa and less than 4 GPa. B: 4 GPa or more and less than 7 GPa. C: 7GPa or more.

[0126] [Table 1]

[0127] [Table 2]

[0128] [Table 3]

[0129] 3. Additional evaluation (1) Evaluation of the protrusions of filler #1 Images were obtained by photographing particles of the above-mentioned filler #1 (manufactured by Nikko Rica Co., Ltd., product name Silcrusta MKN03) using a differential scanning electron microscope. The images are shown in Figure 7. As shown in Figure 7, the particles of filler #1 have protrusions across their entire surface. From the images, the vertical diameter (dimension of the major axis) and horizontal diameter (dimension in the direction perpendicular to the major axis) of the protrusions were measured for 10 particles (total number of protrusions of 100 or more), and the average value of the vertical and horizontal diameters was calculated as the diameter of the protrusion.

[0130] These results are shown in the graph in Figure 2. In this graph, the horizontal axis represents the diameter of the protrusions, and the vertical axis represents the frequency (number of protrusions). As shown in these results, the frequency of the diameter of the protrusions of filler #1 was consistently high in the range from 200 nm to 500 nm.

[0131] (2) Comparative evaluation of fillers A composition was prepared by mixing a mixture having the composition of Example 1 except that it does not contain filler, with the above-mentioned filler #1, so that the proportion of filler #1 was 40% by mass. In addition, compositions were prepared in the same manner using filler #3 (manufactured by Nikko Rica Co., Ltd., product name MSP-SN08), filler #4 (manufactured by Nikko Rica Co., Ltd., product name MSPTKN04), and filler #5 (manufactured by Nikko Rica Co., Ltd., product name NHRASN06), respectively, instead of filler #1.

[0132] Each composition was applied to a glass slide using a squeegee, and then cured by heating at 120°C for 3 hours to produce a 0.2 μm thick cured film. When the cured film using filler #1 was visually inspected, it had lower surface gloss compared to the other cured films.

[0133] Furthermore, the average specular reflectance of the surface of each cured product was measured using the same method as "(4) Average specular reflectance of 400-800nm" in "2. Evaluation Test" above. As a result, the average specular reflectance when using filler #3 was 2.53%, when using filler #4 was 2.18%, and when using filler #5 was 1.70%, while the average specular reflectance when using filler #1 was a remarkably low 0.14%.

[0134] (3) Evaluation of filler content The same compositions as in the case of "(2) Filler Comparison Evaluation" described above were prepared, except that the proportion of filler #1 in the composition was changed to 0 vol%, 10 vol%, 20 vol%, 30 vol%, 32 vol%, and 35 vol%, respectively.

[0135] Using each composition, a film-like cured product was prepared in the same manner as in the case of "(2) Filler Comparison Evaluation" described above.

[0136] The specular reflectance spectrum and diffuse reflectance spectrum of the surface of each cured material were measured using the same method as in "(4) Average specular reflectance at 400-800 nm" and "(6) Average diffuse reflectance at 400-800 nm" in "2. Evaluation Test" above. In addition, the total light reflectance spectrum was determined from the specular reflectance spectrum and diffuse reflectance spectrum for each cured material. The specular reflectance spectrum is shown in Figure 3, the diffuse reflectance spectrum in Figure 4, and the total light reflectance spectrum in Figure 5.

[0137] As these results show, the specular reflectance decreases as the proportion of filler #1 increases, and the specular reflectance becomes extremely low when the proportion of filler #1 changes from 20% by volume to 30% by volume. Also, the diffuse reflectance tends to increase as the proportion of filler #1 increases, and the diffuse reflectance becomes extremely high when the proportion of filler #1 changes from 20% by volume to 30% by volume, indicating that the proportion of filler #1 should be increased even further. This is presumed to be because when the proportion of filler #1 reaches 30% by volume, the particles of filler #1 are exposed to the outside on the surface of the cured material, dramatically increasing the diffusion of light by filler #1. In addition, the total light reflectance decreases as the proportion of filler #1 increases.

[0138] (4) Surface image of the cured product Figure 6 shows an image obtained by photographing the surface of the cured product using a differential scanning electron microscope when the proportion of filler #1 in the composition is 30% by volume, as described in "(3) Evaluation of filler content" above. From this, it can be confirmed that when the proportion of filler #1 is 30% by volume, the particles of filler #1 are exposed on the surface of the cured product.

Claims

1. It contains a reactive component (A) and a filler (B), The reactive component (A) contains a reactive compound (A1), and the reactive compound (A1) contains at least one of an epoxy compound and an acrylic compound. The reactive component (A) further contains a curing agent (A2) that reacts with the reactive compound (A1), The filler (B) contains an anti-reflective filler (B1), The average particle diameter of the anti-reflective filler (B1) is 0.8 μm or more and 10 μm or less, and the anti-reflective filler (B1) has a plurality of protrusions on its particle surface. The average diameter of the aforementioned protrusions is between 100 nm and 500 nm. Reaction-curable composition.

2. The anti-reflective filler (B1) has the protrusions on 10% or more of the surface area of ​​its particles. The reaction-curable composition according to claim 1.

3. Further comprising an initiator (C), The reaction-curable composition according to claim 1 or 2.

4. The refractive index of the anti-reflective filler (B1) is 1.7 or less, and the refractive index of the cured product of the reactive component (A) is less than or equal to one of the above, The reaction-curable composition according to claim 1 or 2.

5. The particles of the anti-reflective filler (B1) are core-shell type particles having a core and a shell covering the core, and having the protrusions on the surface of the shell. The reaction-curable composition according to claim 1 or 2.

6. The core contains acrylic resin, and each of the shell and the protrusions contains silicone. The reaction-curable composition according to claim 5.

7. The percentage ratio of the filler (B) to the reaction-curable composition is 10% by volume or more. The reaction-curable composition according to claim 1 or 2.

8. The amount of the anti-reflective filler (B1) per 100 parts by mass of the reactive component (A) is 5 parts by mass or more and 82 parts by mass or less. The reaction-curable composition according to claim 1 or 2.

9. A reactive component (A) and a filler (B), The filler (B) contains an anti-reflective filler (B1), The average particle diameter of the anti-reflective filler (B1) is 0.8 μm or more and 10 μm or less, and the anti-reflective filler (B1) has a plurality of protrusions on its particle surface. The average diameter of the aforementioned protrusions is between 100 nm and 500 nm. Further containing coloring agent (D), Reaction-curable composition.

10. The coloring agent (D) contains at least one selected from the group consisting of carbon black, titanium black, zirconium nitride, and dyes. The reaction-curable composition according to claim 9.

11. The amount of the coloring agent (D) is greater than 0 parts by mass and 10 parts by mass or less, relative to 100 parts by mass of the reactive component (A). The reaction-curable composition according to claim 9.

12. A reactive component (A) and a filler (B) are included. The filler (B) contains an anti-reflective filler (B1), The average particle diameter of the anti-reflective filler (B1) is 0.8 μm or more and 10 μm or less, and the anti-reflective filler (B1) has a plurality of protrusions on its particle surface. The average diameter of the aforementioned protrusions is between 100 nm and 500 nm. The average specular reflectance of the cured product of the reaction-curable composition, measured using an integrating sphere at an incident angle of 8°, for light in the wavelength range of 400 nm to 800 nm, is 0.5% or less. Reaction-curable composition.

13. A reactive component (A) and a filler (B) are contained, The filler (B) contains an anti-reflective filler (B1), The average particle diameter of the anti-reflective filler (B1) is 0.8 μm or more and 10 μm or less, and the anti-reflective filler (B1) has a plurality of protrusions on its particle surface. The average diameter of the aforementioned protrusions is between 100 nm and 500 nm. The viscosity at 25°C, measured using a Type B rotational viscometer at 20 rpm, is 200 Pa·s or less. Reaction-curable composition.

14. A reactive component (A) and a filler (B) are contained, The filler (B) contains an anti-reflective filler (B1), The average particle diameter of the anti-reflective filler (B1) is 0.8 μm or more and 10 μm or less, and the anti-reflective filler (B1) has a plurality of protrusions on its particle surface. The average diameter of the aforementioned protrusions is between 100 nm and 500 nm. The thixotropy, which is the ratio of the viscosity at 25°C measured at 2 rpm using a Type B rotational viscometer to the viscosity measured at 20 rpm using a Type B rotational viscometer, is between 1 and 7. Reaction-curable composition.

15. A reactive component (A) and a filler (B) are contained, The filler (B) contains an anti-reflective filler (B1), The average particle diameter of the anti-reflective filler (B1) is 0.8 μm or more and 10 μm or less, and the anti-reflective filler (B1) has a plurality of protrusions on its particle surface. The average diameter of the aforementioned protrusions is between 100 nm and 500 nm. The cured product of the reaction-curable composition has an elastic modulus of 10 GPa or less at -40°C. Reaction-curable composition.

16. A reactive component (A) and a filler (B) are contained, The filler (B) contains an anti-reflective filler (B1), The average particle diameter of the anti-reflective filler (B1) is 0.8 μm or more and 10 μm or less, and the anti-reflective filler (B1) has a plurality of protrusions on its particle surface. The average diameter of the aforementioned protrusions is between 100 nm and 500 nm. It does not contain solvents, or it contains only solvents that are inevitably mixed in as solvents. Reaction-curable composition.

17. A reactive component (A) and a filler (B), The filler (B) contains an anti-reflective filler (B1), The average particle diameter of the anti-reflective filler (B1) is 0.8 μm or more and 10 μm or less, and the anti-reflective filler (B1) has a plurality of protrusions on its particle surface. The average diameter of the aforementioned protrusions is between 100 nm and 500 nm. It is an adhesive, Reaction-curable composition.

18. A reactive component (A) and a filler (B), The filler (B) contains an anti-reflective filler (B1), The average particle diameter of the anti-reflective filler (B1) is 0.8 μm or more and 10 μm or less, and the anti-reflective filler (B1) has a plurality of protrusions on its particle surface. The average diameter of the aforementioned protrusions is between 100 nm and 500 nm. This is a composition for producing underfill material. Reaction-curable composition.

Images