Composition, magnetic particles containing hardened material, magnetic particles introduced into substrate, electronic materials

Abstract

To provide a composition having excellent fluidity and capable of forming a cured product having excellent magnetic properties and excellent filling suitability, to provide a magnetic particle-containing cured product formed using the composition, and to provide a magnetic particle-introduced substrate and an electronic material containing the magnetic particle-containing cured product.SOLUTION: A composition comprising magnetic particles, one or more components selected from the group consisting of a resin and a resin precursor, and a solvent, wherein the components comprise a resin having a repeating unit including a graft chain, a content of magnetic particles having a primary particle diameter of 4 μm or more is 25 mass% or more with respect to a total mass of the magnetic particles, a content of the magnetic particles is 91 mass% or more with respect to a total solid content of the composition, and a content of the solvent is 3 mass% to 24 mass% with respect to a total mass of the composition.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to compositions, magnetic particle-containing cured products, magnetic particle-introduced substrates, and electronic materials. [Background technology]

[0002] As electronic devices become more high-performance and smaller, the integration density of electronic circuits is increasing. One material that can improve this integration density is a coated composition containing magnetic particles. Using such a composition makes it possible to mount magnetic materials in any shape, thus making it easier to achieve miniaturization and high performance of electronic devices compared to conventional methods of placing individual pieces of magnetic material on a chip.

[0003] For example, Patent Document 1 discloses "a resin composition containing (A) a thermosetting resin, (B) a curing agent, (C) a thermoplastic resin, and (D) a magnetic filler, wherein the cured product obtained by thermosetting the resin composition has an elastic modulus of 7 GPa or more and 18 GPa or less at 23°C." [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] International Publication No. 2018 / 194099 [Overview of the project] [Problems that the invention aims to solve]

[0005] Incidentally, in recent years, attempts have been made to fabricate magnetic particle-introduced substrates by filling the holes in the substrate with magnetic material using a coating-type composition containing magnetic particles.

[0006] The present inventors, referring to the resin composition described in Patent Document 1, prepared a coating-type composition containing magnetic particles and investigated its performance as a hole-filling composition. They found that the resulting cured product may have low magnetic properties (permeability), and that voids and cracks may occur during the hole-filling process. In other words, they found that there is room for further improvement in the cured product formed from the above composition in terms of improving magnetic properties and suppressing void ratio (hereinafter also referred to as "excellent filling suitability").

[0007] Furthermore, the composition is also required to have excellent fluidity as a basic performance characteristic, from the viewpoint of ease of application and filling. For example, Japanese Patent Publication No. 6024927 discloses a solvent-free composition that does not contain a solvent and exhibits fluidity through a resin component. However, in solvent-free compositions, there is a limit to the amount of magnetic particles that can be introduced into the solid content of the composition in order to ensure the desired fluidity, and this leads to the problem that it is difficult to improve the magnetic properties (permeability) of the cured product.

[0008] Therefore, the object of the present invention is to provide a composition that can form a cured product with excellent fluidity, magnetic properties, and filling suitability. Furthermore, the present invention aims to provide a magnetic particle-containing cured product formed using the above composition. Furthermore, the present invention aims to provide a magnetic particle introduction substrate and an electronic material containing the above-mentioned magnetic particle-containing cured product. [Means for solving the problem]

[0009] As a result of diligent research to solve the above problems, the inventors of this invention have found that the above problems can be solved by the following configuration.

[0010] [1] Magnetic particles and, One or more components selected from the group consisting of resins and resin precursors, A composition comprising a solvent, The content of magnetic particles with a primary particle diameter of 4 μm or more is 25% by mass or more of the total mass of magnetic particles. The content of the above magnetic particles is 91% by mass or more relative to the total solid content of the composition. A composition in which the content of the above solvent is 3 to 24% by mass of the total mass of the composition. [2] The composition according to [1], wherein the magnetic particles are soft magnetic particles. [3] The composition according to [1] or [2], wherein the solvent includes a solvent having a boiling point of 80°C or higher. [4] The composition according to any one of [1] to [3], wherein the solvent includes a solvent having a boiling point of 160°C or higher. [5] The composition according to any one of [1] to [4], wherein the solvent contains a solvent having a boiling point of 160°C or higher, and its content is 3% by mass or more of the total mass of the composition. [6] The composition according to any one of [1] to [5], wherein the above components include at least one epoxy compound and an oxetane compound. [7] A cured product containing magnetic particles, formed using any of the compositions described in [1] to [6]. [8] A magnetic particle introduction substrate comprising a substrate having holes formed therein and a magnetic particle-containing cured material described in [7] disposed within the holes. [9] An electronic material including a magnetic particle introduction substrate as described in [8]. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a composition that can form a cured product with excellent fluidity, magnetic properties, and filling suitability. Furthermore, according to the present invention, a cured product containing magnetic particles formed using the above composition can be provided. Furthermore, according to the present invention, a magnetic particle introduction substrate and an electronic material containing the above-mentioned magnetic particle-containing cured product can be provided. [Modes for carrying out the invention]

[0012] The present invention will be described in detail below. The following description of the constituent elements may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, regarding the notation of groups (atomic groups), unless contrary to the spirit of the present invention, notations that do not specify substituted or unsubstituted include both substituted and unsubstituted groups. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups. Furthermore, in this specification, "organic group" means a group containing at least one carbon atom.

[0013] In this specification, "active light" or "radiation" means, for example, the emission line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, and electron beams (EB). In this specification, "light" means active light or radiation. In this specification, "exposure" includes not only exposure using emission line spectra from mercury lamps, far ultraviolet light such as those from excimer lasers, extreme ultraviolet light, X-rays, and EUV light, but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.

[0014] In this specification, "~" is used to mean that the numbers before and after it are included as the lower and upper limits, respectively.

[0015] In this specification, (meth)acrylate refers to acrylate and methacrylate, (meth)acrylic refers to acrylic and methacrylic, and (meth)acryloyl refers to acryloyl and methacryloyl.

[0016] In this specification, "solid content" of a composition means the components that form the magnetic particle-containing cured product (which may also be abbreviated as "cured product"). If the composition contains a solvent (organic solvent, water, etc.), it means all components excluding the solvent. Furthermore, any liquid components that form the cured product are also considered to be solid content.

[0017] In this specification, "boiling point" means the standard boiling point unless otherwise specified.

[0018] Furthermore, in this specification, the weight-average molecular weight (Mw) is the polystyrene equivalent value obtained by GPC (Gel Permeation Chromatography). In this specification, the GPC method is based on a method using HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, or TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) as the column, and THF (tetrahydrofuran) as the eluent.

[0019] Furthermore, in this specification, unless otherwise specified, each component may be represented by a single substance or by a combination of two or more substances. Here, when two or more substances are used in combination for each component, the content of that component refers to the total content of the combined substances, unless otherwise specified.

[0020] [Composition] The composition of the present invention, Magnetic particles and, One or more components selected from the group consisting of resins and resin precursors (hereinafter, resins and resin precursors are collectively referred to as "binder components"), A composition comprising a solvent, The content of magnetic particles with a primary particle diameter of 4 μm or more is 25% by mass or more of the total mass of magnetic particles. The content of the above magnetic particles is 91% by mass or more relative to the total solid content of the composition. The solvent content is 3 to 24% by mass relative to the total mass of the composition.

[0021] Compositions containing magnetic particles used as hole-filling compositions must not only exhibit excellent magnetic properties (permeability), but also, in their liquid state, have sufficient fluidity from the viewpoint of applicability and ease of filling work, and in their cured state, from the viewpoint of strength, voids and cracks must be suppressed (excellent filling suitability) as basic performance requirements. The present inventors have now discovered, through diligent research, that a composition with the above configuration exhibits excellent fluidity in a liquid state and can form a cured product with excellent magnetic properties (permeability) and filling suitability. Furthermore, as described later, it has been confirmed that when the solvent contains 3% or more by mass of a solvent with a boiling point of 160°C or higher relative to the total mass of the composition, the filling properties of the cured product formed by the composition are superior.

[0022] In the following, if the composition has superior fluidity, the cured product formed by the composition has superior magnetic properties (permeability), and / or the cured product formed by the composition has superior filling properties, then "the effects of the present invention are superior."

[0023] The following provides a detailed description of each component that may be included in the composition.

[0024] [Magnetic particles] The composition contains magnetic particles. Magnetic particles contain metal atoms. In this specification, the above-mentioned metal atoms also include metalloid atoms such as boron, silicon, germanium, arsenic, antimony, and tellurium. The above-mentioned metal atoms may be included in magnetic particles as an alloy containing a metal element (preferably a magnetic alloy), a metal oxide (preferably a magnetic oxide), a metal nitride (preferably a magnetic oxide), or a metal carbide (preferably a magnetic carbide). The content of the above metal atoms relative to the total mass of the magnetic particles is preferably 50 to 100% by mass, more preferably 75 to 100% by mass, and even more preferably 95 to 100% by mass.

[0025] The above metal atoms are not particularly limited, but it is preferable that they include at least one metal atom selected from the group consisting of Fe, Ni, and Co. The content of at least one metal atom selected from the group consisting of Fe, Ni, and Co (or the total content if multiple types are included) is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, relative to the total mass of metal atoms in the magnetic particles. The upper limit of the above content is not particularly limited, for example, it is 100% by mass or less, preferably 98% by mass or less, and more preferably 95% by mass or less.

[0026] Magnetic particles may contain materials other than Fe, Ni, and Co. Specific examples include Al, Si, S, Sc, Ti, V, Cu, Y, Mo, Rh, Pd, Ag, Sn, Sb, Te, Ba, Ta, W, Re, Au, Bi, La, Ce, Pr, Nd, P, Zn, Sr, Zr, Mn, Cr, Nb, Pb, Ca, B, C, N, and O. If the magnetic particles contain metal atoms other than Fe, Ni, and Co, it is preferable that they contain one or more selected from the group consisting of Si, Cr, B, and Mo.

[0027] Specific examples of magnetic particles include Fe-Co alloys (preferably Permendur), Fe-Ni alloys (e.g., Permalloy), Fe-Zr alloys, Fe-Mn alloys, Fe-Si alloys, Fe-Al alloys, Ni-Mo alloys (preferably Supermalloy), Fe-Ni-Co alloys, Fe-Si-Cr alloys, Fe-Si-B alloys, Fe-Si-Al alloys (preferably Sendust), Fe-Si-BC alloys, Fe-Si-B-Cr alloys, Examples of alloys include Fe-Si-B-Cr-C alloys, Fe-Co-Si-B alloys, Fe-Si-B-Nb alloys, Fe nanocrystalline alloys, Fe-based amorphous alloys, and Co-based amorphous alloys, as well as ferrites such as Ni ferrite, Mn ferrite, spinel ferrite (preferably Ni-Zn ferrite, Mn-Zn ferrite), and hexagonal ferrite (preferably barium ferrite, magnetoprumbite-type hexagonal ferrite). The above alloys may also be amorphous. Among the magnetic particles, soft magnetic particles are preferred because they have lower losses. Examples of soft magnetic particles include Fe-based amorphous alloys, Fe-Si-Cr alloys, Fe nanocrystalline alloys, Fe-Ni-Co alloys, Co-based amorphous alloys, Ni-Mo alloys, Ni ferrite, and Mn ferrite. Magnetic particles may be used individually or in combination of two or more types.

[0028] A surface layer may be provided on the surface of the magnetic particles. By having a surface layer on the magnetic particles, functions corresponding to the material of the surface layer can be imparted to the magnetic particles. Examples of surface layers include inorganic layers or organic layers.

[0029] As compounds for forming inorganic layers, metal oxides, metal nitrides, metal carbides, metal phosphate compounds, metal borate compounds, or silicate compounds (for example, silicate esters such as tetraethyl orthosilicate, and silicates such as sodium silicate) are preferred because they can form a surface layer that is excellent in at least one of the following: insulating properties, gas barrier properties, and chemical stability. Specific examples of elements contained in these compounds include Fe, Al, Ca, Mn, Zn, Mg, V, Cr, Y, Ba, Sr, Ge, Zr, Ti, Si, and rare earth elements. Materials that constitute the inorganic layer obtained using the inorganic layer-forming compound include silicon dioxide, germanium oxide, titanium dioxide, aluminum oxide, zirconium oxide, and magnesium oxide, and the inorganic layer may contain two or more of these materials.

[0030] Examples of compounds for forming organic layers include acrylic monomers. Specific examples of acrylic monomers include the compounds described in paragraphs 0022 to 0023 of Japanese Patent Publication No. 2019-067960. Acrylic resin is an example of a material that constitutes an organic layer obtained using an organic layer-forming compound.

[0031] The thickness of the surface layer is not particularly limited, but 3 to 1000 nm is preferred because it allows the surface layer to perform its function more effectively.

[0032] The lower limit of the average primary particle diameter of the magnetic particles is, for example, 0.1 μm or more, preferably 1 μm or more, more preferably 4 μm or more, and even more preferably 5 μm or more. The upper limit of the average primary particle diameter of the magnetic particles is preferably 100 μm or less, more preferably 50 μm or less, even more preferably 30 μm or less, particularly preferably 20 μm or less, and most preferably 7 μm or less. The particle diameter of primary magnetic particles can be measured, for example, by photographing magnetic particles with a transmission electron microscope at a magnification of 100,000x, printing the resulting image onto photographic paper to a total magnification of 500,000x, tracing the contours of the particles (primary particles) with a digitizer, and calculating the diameter of a circle with the same area as the traced region (circular area phase diameter). Here, primary particles refer to independent particles that are not aggregated. The imaging using the transmission electron microscope shall be performed using the direct method with an accelerating voltage of 300kV. Transmission electron microscope observation and measurement can be performed, for example, using a Hitachi H-9000 transmission electron microscope and Carl Zeiss KS-400 image analysis software. To determine the average primary particle diameter, 1000 particles are arbitrarily selected from the above particle photograph, and the volume of each particle is calculated based on the diameter of the circle described above. This is then used to determine the arithmetic mean primary particle diameter based on volume.

[0033] The shape of the magnetic particles is not particularly limited and may be plate-shaped, elliptical, spherical, or amorphous.

[0034] The content of magnetic particles with a primary particle diameter of 4 μm or more in the magnetic particles is 25% by mass or more of the total mass of the magnetic particles. When the content of magnetic particles with a primary particle diameter of 4 μm or more is 25% by mass or more of the total mass of the magnetic particles, the cured product formed by the composition is likely to have both excellent magnetic properties and excellent filling suitability. Preferably, the content of magnetic particles with a primary particle diameter of 4 μm or more in the magnetic particles is 30% by mass or more, more preferably 45% by mass or more, even more preferably 50% by mass or more, and particularly preferably 60% by mass or more, based on the total mass of the magnetic particles. The upper limit is preferably 100% by mass or less. In particular, among the magnetic particles, the content of magnetic particles with a primary particle diameter of 4 to 7 μm is preferably 55% by mass or more, more preferably 65% ​​by mass or more, and even more preferably 70% by mass or more, relative to the total mass of the magnetic particles, in order to achieve the effects of the present invention more favorably. There is no particular upper limit, but for example, it is 100% by mass or less.

[0035] Furthermore, the content of magnetic particles with a primary particle diameter of 4 μm or more in the magnetic particles can be determined, for example, by referring to the average primary particle diameter value obtained from a transmission electron microscope of the magnetic particles, as well as the volume ratio and specific gravity of the magnetic particles, based on a particle size distribution curve representing the volume-based frequency distribution of magnetic particles obtained by a laser diffraction scattering particle size distribution analyzer (for example, the "LA960N" product manufactured by Horiba, Ltd.).

[0036] Magnetic particles may be used individually or in combination of two or more types. The content of magnetic particles in the composition (total content if multiple types are included) is 91% by mass or more of the total solid content of the composition. When the content of magnetic particles is 91% by mass or more of the total solid content of the composition, the cured product formed by the composition has excellent magnetic properties. In particular, for the effects of the present invention to be more pronounced, the content of magnetic particles is preferably 92% by mass or more, and more preferably 95% by mass or more, of the total solid content of the composition. There is no particular upper limit to the above content, but it is preferably 99% by mass or less.

[0037] [Binder components] The composition contains one or more components (binder components) selected from the group consisting of resins and resin precursors. In other words, the binder component may be the resin itself or a resin precursor.

[0038] Examples of compositions that use the resin itself include compositions containing magnetic particles, a solvent, and a resin dissolved in the solvent. When the solvent in this composition evaporates, the resin precipitates, and a composition is obtained in which the resin functions as a binder.

[0039] The resin precursor is a component that can undergo polymerization and / or crosslinking to form a resin through a predetermined curing treatment using heat or light (such as ultraviolet light). The resin thus formed functions as a binder in the cured product. Examples of resin precursors include thermosetting compounds and photocurable compounds. These compounds may be monomers, oligomers, or polymers.

[0040] The following sections will explain specific examples of binder components.

[0041] Examples of binder components include (meth)acrylic resin, epoxy resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene etherphosphine oxide resin, polyimide resin, polyamide-imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, and phenoxy resin. One of these resins may be used alone, or two or more may be used in combination. As a cyclic olefin resin, norbornene resin is preferred from the viewpoint of improving heat resistance. Examples of commercially available norbornene resins include the ARTON series (e.g., ARTON F4520) manufactured by JSR Corporation. Examples of commercially available polyvinyl acetal resins include "KS-1" manufactured by Sekisui Chemical Co., Ltd. Another example of a commercially available phenoxy resin is "YX7553BH30" (manufactured by Mitsubishi Chemical Corporation). Examples of epoxy resins include epoxy resins which are glycidyl ethers of phenol compounds, epoxy resins which are glycidyl ethers of various novolac resins, alicyclic epoxy resins, aliphatic epoxy resins, heterocyclic epoxy resins, glycidyl ester epoxy resins, glycidylamine epoxy resins, epoxy resins which are glycidylated halogenated phenols, condensates of silicon compounds having epoxy groups and other silicon compounds, and copolymers of polymerizable unsaturated compounds having epoxy groups and other polymerizable unsaturated compounds. Additionally, epoxy resins such as Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, and G-01758 (manufactured by NOF Corporation, epoxy group-containing polymers) may be used.

[0042] Furthermore, as the binder component, the resin described in the examples of International Publication No. 2016 / 088645 may be used. Furthermore, it is also preferable that the binder component is a resin having ethylenically unsaturated groups (for example, (meth)acryloyl groups) in the side chains, and that the main chain and the ethylenically unsaturated groups are linked via divalent linking groups having an alicyclic structure.

[0043] Furthermore, the binder component is preferably a resin or resin precursor having cyclic polymerizable groups such as epoxy groups and oxetanyl groups. Examples of resins or resin precursors having cyclic polymerizable groups such as epoxy groups and oxetanyl groups include polymers having epoxy groups in their side chains, and polymerizable monomers or oligomers having two or more epoxy groups in their molecules. Specific examples include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, and aliphatic epoxy resins. These resins may be commercially available, or they can be obtained by introducing epoxy groups into the side chains of polymers. For commercially available products, for example, the description in paragraph 0191 of Japanese Patent Publication No. 2012-155288 can be considered, and the contents of these are incorporated into the present specification. Other examples include the ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (all manufactured by ADEKA), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (all manufactured by ADEKA), and JER1031S. Furthermore, specific examples of bisphenol A type epoxy resin and bisphenol F type epoxy resin include, for example, ZX1059 (manufactured by Nippon Steel Chemical & Material Co., Ltd.) and 828US (manufactured by Mitsubishi Chemical Corporation). Furthermore, commercially available phenol novolac type epoxy resins include JER-157S65, JER-152, JER-154, and JER-157S70 (all manufactured by Mitsubishi Chemical Corporation). In addition, polymerizable monomers or oligomers having two or more epoxy groups in the molecule can also be used, such as ZX1658GS (liquid 1,4-glycidylcyclohexane type epoxy resin, manufactured by Nippon Steel Chemical & Material Co., Ltd.), HP-4700 (naphthalene type tetrafunctional epoxy resin, manufactured by DIC Corporation), and NC3000L (biphenyl type epoxy resin, manufactured by Nippon Kayaku Co., Ltd.). Specific examples of polymers having oxetanyl groups in their side chains, and polymerizable monomers or oligomers having two or more oxetanyl groups in the molecule mentioned above, include Aronoxetane OXT-121, OXT-221, OX-SQ, and PNOX (all manufactured by Toagosei Co., Ltd.). When synthesizing resins containing epoxy groups by introducing epoxy groups into polymer side chains, the introduction reaction can be carried out by reacting in an organic solvent at a reaction temperature of 50 to 150°C for a predetermined time, using, for example, tertiary amines such as triethylamine and benzylmethylamine, quaternary ammonium salts such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, and tetraethylammonium chloride, pyridine, and triphenylphosphine as catalysts. The amount of alicyclic epoxy unsaturated compound introduced can be controlled so that the acid value of the resulting resin satisfies a range of 5 to 200 KOH mg / g. Furthermore, the weight-average molecular weight of the resin can be in the range of 500 to 5,000,000 (preferably 1,000 to 500,000). Instead of alicyclic epoxy unsaturated compounds, those having a glycidyl group as the epoxy group, such as glycidyl (meth)acrylates and allyl glycidyl ethers, can also be used. For example, one can refer to the description in paragraph 0045 of Japanese Patent Application Publication No. 2009-265518, and these contents are incorporated into the present specification.

[0044] Furthermore, resins having acidic groups, basic groups, or amide groups can also be used as binder components. Resins having acidic groups, basic groups, or amide groups are preferable because they readily function as dispersants for dispersing magnetic particles, thus providing superior effects for the present invention. Examples of acidic groups include carboxyl groups, phosphate groups, sulfo groups, and phenolic hydroxyl groups, and carboxyl groups are preferred because they exhibit superior effects compared to the present invention. Basic groups include amino groups (ammonia, primary amines, or secondary amines with one hydrogen atom removed) and imino groups. In particular, the resin is preferably one having a carboxyl group or an amide group, as this provides superior effects for the present invention.

[0045] When the resin has acidic groups, the acid value of the resin is preferably 10 to 500 mg KOH / g, and more preferably 30 to 400 mg KOH / g, from the viewpoint of achieving superior effects of the present invention.

[0046] As for the binder component, it is preferable to use a binder component with a solubility of 10 g / L or more in the solvent, and more preferable to use a binder component with a solubility of 20 g / L or more in the solvent, since this improves the dispersibility of the binder component in the composition and enhances the effects of the present invention. The upper limit of the solubility of the binder component in the solvent is preferably 2000 g / L or less, and more preferably 1000 g / L or less. The solubility of a binder component in a solvent refers to the amount (g) of the binder component that dissolves in 1 L of solvent at 25°C.

[0047] The binder component content is preferably 1 to 24% by mass, more preferably 1 to 15% by mass, even more preferably 1 to 12% by mass, particularly preferably 1 to 10% by mass, and most preferably 1 to 7% by mass, based on the total mass of the composition. The binder component content is preferably 0.8 to 24% by mass, more preferably 0.8 to 15% by mass, even more preferably 0.8 to 12% by mass, even more preferably 0.8 to 10% by mass, particularly preferably 0.8 to 8% by mass, and most preferably 0.8 to 7% by mass, based on the total solid content of the composition.

[0048] <Resin containing repeating units including graft chains (Resin A)> Examples of binder components include resins having repeating units including graft chains (hereinafter also referred to as "resin A"). Resin A can function as a dispersant for magnetic particles.

[0049] If the composition contains resin A, the content of resin A is preferably 1 to 24% by mass, more preferably 1 to 15% by mass, even more preferably 1 to 12% by mass, particularly preferably 1 to 10% by mass, and most preferably 1 to 7% by mass, based on the total mass of the composition. The content of resin A is preferably 0.8 to 24% by mass, more preferably 0.8 to 15% by mass, even more preferably 0.8 to 12% by mass, even more preferably 0.8 to 10% by mass, particularly preferably 0.8 to 8% by mass, and most preferably 0.8 to 7% by mass, relative to the total solid content of the composition.

[0050] (Repeating units including graft chains) In repeating units containing graft chains, the steric repulsion effect increases as the graft chain length increases, improving the dispersibility of magnetic particles. On the other hand, if the graft chain is too long, the adsorption force to the magnetic particles decreases, and the dispersibility of magnetic particles tends to decrease. For this reason, the number of atoms excluding hydrogen atoms in the graft chain is preferably 40 to 10,000, more preferably 50 to 2,000, and even more preferably 60 to 500. Here, a graft chain refers to the chain from the base of the main chain (the atom bonded to the main chain in a group branching off from the main chain) to the end of the group branching off from the main chain.

[0051] Furthermore, the graft chains preferably contain a polymer structure, and examples of such polymer structures include poly(meth)acrylate structures (e.g., poly(meth)acrylic structures), polyester structures, polyurethane structures, polyurea structures, polyamide structures, and polyether structures. To improve the interaction between the graft chain and the solvent, thereby enhancing the dispersibility of the magnetic particles, the graft chain is preferably a graft chain comprising at least one selected from the group consisting of polyester structure, polyether structure, and poly(meth)acrylate structure, and more preferably a graft chain comprising at least one of polyester structure and polyether structure.

[0052] Resin A may be a resin obtained using macromonomers containing graft chains (monomers that have a polymer structure and are bonded to the main chain to constitute graft chains). The macromonomers containing graft chains (monomers having a polymer structure that are bonded to the main chain to constitute graft chains) are not particularly limited, but macromonomers containing reactive double bond groups can be preferably used.

[0053] Commercially available macromonomers suitable for the synthesis of resin A, corresponding to the repeating units including the graft chains described above, include AA-6, AA-10, AB-6, AS-6, AN-6, AW-6, AA-714, AY-707, AY-714, AK-5, AK-30, and AK-32 (all trade names, manufactured by Toagosei Co., Ltd.), as well as Brembo PP-100, Brembo PP-500, Brembo PP-800, Brembo PP-1000, Brembo 55-PET-800, Brembo PME-4000, Brembo PSE-400, Brembo PSE-1300, and Brembo 43PAPE-600B (all trade names, manufactured by NOF Corporation). Among these, AA-6, AA-10, AB-6, AS-6, AN-6, or Brembo PME-4000 are preferred.

[0054] Resin A preferably contains at least one structure selected from the group consisting of methyl polyacrylate, polymethyl methacrylate, and cyclic or chain-like polyesters, more preferably contains at least one structure selected from the group consisting of methyl polyacrylate, polymethyl methacrylate, and chain-like polyesters, and even more preferably contains at least one structure selected from the group consisting of methyl polyacrylate structures, polymethyl methacrylate structures, polycaprolactone structures, and polyvalerolactone structures. Resin A may contain one of the above structures alone, or it may contain a plurality of these structures. Here, a polycaprolactone structure refers to a structure that contains a ring-opened ε-caprolactone as a repeating unit. A polyvalerolactone structure refers to a structure that contains a ring-opened δ-valerolactone as a repeating unit.

[0055] Furthermore, if resin A contains repeating units in formula (1) and formula (2) described later, where j and k are 5, the polycaprolactone structure described above can be introduced into resin A. Furthermore, if resin A contains repeating units in formula (1) and formula (2) described later, where j and k are 4, the polyvalerolactone structure described above can be introduced into the resin. Furthermore, resin A is X in equation (4) described later. 5 is a hydrogen atom, and R 4 If the resin A contains repeating units that are methyl groups, the above-described methyl polyacrylate structure can be introduced into resin A. Furthermore, resin A is X in equation (4) described later. 5 is a methyl group, R 4 If the resin A contains repeating units that are methyl groups, the polymethyl methacrylate structure described above can be introduced into resin A. Furthermore, if resin A contains formula (5) described later, and if it contains a repeating unit in formula (5) where j is 5, the polycaprolactone structure described above can be introduced into resin A. In addition, when the resin A contains the following formula (5), and when it contains a repeating unit in which j in the formula (5) is 4, the above-mentioned polyvalerolactone structure can be introduced into the resin.

[0056] As a repeating unit containing a graft chain, the resin A preferably contains a repeating unit represented by any one of the following formulas (1) to (4), and more preferably contains a repeating unit represented by any one of the following formula (1A), the following formula (2A), the following formula (3A), the following formula (3B), and the following (4).

[0057]

Chemical formula

[0058] In formulas (1) to (4), W 1 , W 2 , W 3 , and W 4 each independently represents an oxygen atom or NH. W 1 , W 2 , W 3 , and W 4 are preferably oxygen atoms. In formulas (1) to (4), X 1 , X 2 , X 3 , X 4 , and X 5 each independently represents a hydrogen atom or a monovalent organic group. X 1 , X 2 , X 3 , X 4 , and X 5 are preferably, from the viewpoint of synthetic constraints, each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (number of carbon atoms), more preferably each independently a hydrogen atom or a methyl group, and even more preferably a methyl group.

[0059] In formulas (1) to (4), Y 1 , Y 2 , Y 3 , and Y 4 each independently represents a divalent linking group, and the linking group is not particularly structurally restricted. Y1 , Y 2 , Y 3 , and Y 4 Examples of divalent linking groups represented by the formulas (Y-1) to (Y-21) below include the following linking groups. In the structures shown below, A and B represent the bonding sites to the left terminal group and the right terminal group in formulas (1) to (4), respectively. Of the structures shown below, (Y-2) or (Y-13) are more preferred due to the ease of synthesis.

[0060] [ka]

[0061] In equations (1) to (4), Z 1 , Z 2 , Z 3 , and Z 4 Each of these independently represents a hydrogen atom or a monovalent substituent. The structure of the above substituents is not particularly limited, but specifically, examples include alkyl groups, hydroxyl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, alkylthioether groups, arylthioether groups, heteroarylthioether groups, and amino groups. Among these, Z 1 , Z 2 , Z 3 , and Z 4 The groups represented by are preferably those that include a steric repulsion effect, particularly in terms of improving dispersibility, and more preferably each is an alkyl group or alkoxy group having 5 to 24 carbon atoms, and among these, more preferably each is a branched alkyl group, a cyclic alkyl group, or an alkoxy group having 5 to 24 carbon atoms. The alkyl group contained in the alkoxy group may be linear, branched, or cyclic. Also, Z 1 , Z 2 , Z 3 , and Z 4The substituent represented by is preferably a group containing a curable group such as a (meth)acryloyl group, an epoxy group, and / or an oxetanyl group. Examples of groups containing the above curable group include "-O-alkylene group-(-O-alkylene group-) AL An example is the "(meth)acryloyloxy group". AL represents an integer from 0 to 5, with 1 being preferred. Each of the above alkylene groups independently preferably has 1 to 10 carbon atoms. If the above alkylene group has a substituent, the substituent is preferably a hydroxyl group. The substituents described above may also be groups containing an onium structure. A group containing an onium structure is a group having an anionic part and a cationic part. An example of the anionic part is the oxygen anion (-O - Examples of substructures containing ) include oxygen anion (-O - ) is preferably directly bonded to the end of the repeating structure that is attached to n, m, p, or q in the repeating unit represented by formulas (1) to (4), and in the repeating unit represented by formula (1), the end of the repeating structure that is attached to n (i.e., -(-OC j H 2j -CO-) n It is more preferable that it is directly connected to the rightmost (of -). Examples of cations in the cation portion of a group containing an onium structure include ammonium cations. When the cation portion is an ammonium cation, the cation portion is a cationic nitrogen atom (>N). + This is a substructure containing a cationic nitrogen atom (>N). + The <) is preferably bonded to four substituents (preferably organic groups), of which 1 to 4 are preferably alkyl groups having 1 to 15 carbon atoms. It is also preferable that one or more of the four substituents (preferably one) are groups containing curable groups such as (meth)acryloyl groups, epoxy groups, and / or oxetanyl groups. Examples of groups containing the above curable groups that can be the substituents include the above-mentioned "-O-alkylene group-(-O-alkylene group-) AL In addition to the "-(meth)acryloyloxy group", there is also the "-alkylene group-(-O-alkylene group-)AL1 An example is the "(meth)acryloyloxy group". AL1 represents an integer from 1 to 5, with 1 being preferred. Each of the above alkylene groups independently preferably has 1 to 10 carbon atoms. If the above alkylene group has a substituent, the substituent is preferably a hydroxyl group.

[0062] In equations (1) to (4), n, m, p, and q are each independent integers between 1 and 500. Furthermore, in equations (1) and (2), j and k each independently represent integers from 2 to 8. In equations (1) and (2), j and k are preferably integers from 4 to 6, and more preferably 5. Furthermore, in formulas (1) and (2), n and m are, for example, integers of 2 or more, preferably integers of 6 or more, more preferably integers of 10 or more, and even more preferably integers of 20 or more. Also, when resin A contains a polycaprolactone structure and a polyvalerolactone structure, the sum of the number of repeats of the polycaprolactone structure and the number of repeats of the polyvalerolactone is preferably an integer of 10 or more, and more preferably an integer of 20 or more.

[0063] In formula (3), R 3 R represents a branched or linear alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, multiple R groups exist. 3 They may be the same or different from one another. In formula (4), R 4 R represents a hydrogen atom or a monovalent organic group, and the structure of this monovalent substituent is not particularly limited. 4 The preferred elements are hydrogen atoms, alkyl groups, aryl groups, or heteroaryl groups, with hydrogen atoms or alkyl groups being more preferred. 4 When is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms, more preferably a linear alkyl group having 1 to 20 carbon atoms, and even more preferably a linear alkyl group having 1 to 6 carbon atoms. In formula (4), when q is 2 to 500, there are multiple X present in the graft chain. 5and R 4 They may be the same or different from one another.

[0064] Furthermore, resin A may contain repeating units including graft chains with two or more different structures. That is, the molecule of resin A may contain repeating units represented by formulas (1) to (4) that have different structures from each other, and in formulas (1) to (4), n, m, p, and q each represent integers of 2 or more, in formulas (1) and (2), j and k in the side chains may have different structures from each other, and in formulas (3) and (4), there may be multiple R in the molecule. 3 , R 4 , and, X 5 They may be the same or different from one another.

[0065] The repeating unit represented by formula (1) is more preferably the repeating unit represented by formula (1A) below. Furthermore, the repeating unit represented by formula (2) is more preferably the repeating unit represented by formula (2A) below.

[0066] [ka]

[0067] In formula (1A), X 1 , Y 1 , Z 1 , and n is X in equation (1). 1 , Y 1 , Z 1 , and are synonymous with n, and the preferred range is the same. In equation (2A), X 2 , Y 2 , Z 2 , and m is X in equation (2). 2 , Y 2 , Z 2 , and are synonymous with m, and the preferred range is also the same.

[0068] Furthermore, the repeating unit represented by formula (3) is more preferably the repeating unit represented by formula (3A) or formula (3B) below.

[0069] [ka]

[0070] In equation (3A) or (3B), X 3 , Y 3 , Z 3 , and p is X in equation (3). 3 , Y 3 , Z 3 , and are synonymous with p, and the preferred range is also similar.

[0071] Resin A more preferably contains repeating units represented by formula (1A) as repeating units including graft chains.

[0072] Furthermore, if resin A contains repeating units represented by formulas (1) to (4) described above, it is also preferable that it contains other repeating units including graft chains, such as the repeating unit represented by formula (5) below.

[0073] [ka]

[0074] In equation (5), n represents an integer between 1 and 50, preferably between 2 and 30, more preferably between 2 and 10, and even more preferably between 2 and 5. Furthermore, j represents an integer between 2 and 8, preferably between 4 and 6, and more preferably 5. Also, in equation (5), X 5 and Z 5 These are, respectively, X in equation (1). 1 and Z 1 This is synonymous with the same thing, and the preferred embodiment is also the same.

[0075] Further, as the resin A, it is also preferable to contain a repeating unit containing a polyalkyleneimine structure and a polyester structure. The repeating unit containing a polyalkyleneimine structure and a polyester structure preferably contains a polyalkyleneimine structure in the main chain and a polyester structure as a graft chain.

[0076] The above polyalkyleneimine structure is a polymerized structure containing two or more identical or different alkyleneimine chains. Specific examples of the alkyleneimine chain include alkyleneimine chains represented by the following formula (4A) and the following formula (4B).

[0077]

Chemical formula

[0078] In formula (4A), R X1 and R X2 each independently represent a hydrogen atom or an alkyl group. a 1 represents an integer of 2 or more. * 1 represents the bonding position with a polyester chain, an adjacent alkyleneimine chain, or a hydrogen atom or a substituent.

[0079]

Chemical formula

[0080] In formula (4B), R X3 and R X4 each independently represent a hydrogen atom or an alkyl group. a 2 represents an integer of 2 or more. The alkyleneimine chain represented by formula (4B) binds through the formation of a salt crosslinking group by an anionic group-containing polyester chain and an anionic group contained in the polyester chain and N + explicitly shown in formula (4B).

[0081] *, in formula (4A) and formula (4B), and * 2Each independently represents an adjacent alkyleneimine chain or a position bonded to a hydrogen atom or a substituent. Among others, as the * in Formula (4A) and Formula (4B), it is preferable that it represents a position bonded to an adjacent alkyleneimine chain.

[0082] R in Formula (4A) X1 and R X2 and R in Formula (4B) X3 and R X4 each independently represents a hydrogen atom or an alkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 6, more preferably 1 to 3. In Formula (4A), R X1 and R X2 are preferably both hydrogen atoms. In Formula (4B), R X3 and R X4 are preferably both hydrogen atoms.

[0083] a in Formula (4A) 1 and a in Formula (4B) 2 are not particularly limited as long as they are integers of 2 or more. The upper limit is preferably 10 or less, more preferably 6 or less, still more preferably 4 or less, still more preferably 2 or 3, and particularly preferably 2.

[0084] In Formula (4A) and Formula (4B), * represents an adjacent alkyleneimine chain or a bonding position with a hydrogen atom or a substituent. Examples of the above-mentioned substituent include substituents such as an alkyl group (for example, an alkyl group having 1 to 6 carbon atoms). Further, a polyester chain may be bonded as the substituent.

[0085] The alkyleneimine chain represented by Formula (4A) is preferably linked to the polyester chain at the position of the above-mentioned * 1 . Specifically, it is preferable that the carbonyl carbon in the polyester chain is bonded at the position of the above-mentioned * 1 . Examples of the polyester chains mentioned above include those represented by the following formula (5A).

[0086] [ka]

[0087] If the alkyleneimine chain is an alkyleneimine chain represented by formula (4B), the polyester chain is anionic (preferably an oxygen anion O - ) includes this anionic property and N in formula (4B) + It is preferable that the two groups form a salt crosslinking group. Examples of such polyester chains include those represented by the following formula (5B).

[0088] [ka]

[0089] L in equation (5A) X1 , and L in equation (5B) X2 Each of these independently represents a divalent linking group. Preferably, the divalent linking group is an alkylene group having 3 to 30 carbon atoms.

[0090] b in equation (5A) 11 , and b in equation (5B) 21 Each of these independently represents an integer of 2 or more, preferably an integer of 6 or more, with an upper limit of, for example, 200 or less.

[0091] b in equation (5A) 12 , and b in equation (5B) 22 Each of these independently represents either 0 or 1.

[0092] X in equation (5A) A , and X in equation (5B) B Each of these independently represents a hydrogen atom or a substituent. Examples of substituents include alkyl groups, alkoxy groups, polyalkylene oxyalkyl groups, and aryl groups.

[0093] The alkyl group (which may be linear, branched, or cyclic) and the alkyl group contained in the alkoxy group (which may be linear, branched, or cyclic) may have 1 to 30 carbon atoms, with 1 to 10 being preferred. The alkyl group may also have further substituents, and examples of substituents include hydroxyl groups and halogen atoms (such as fluorine, chlorine, bromine, and iodine atoms).

[0094] Polyalkylene oxyalkyl groups are R X6 (OR X7 ) p (O) q - is a substituent represented by R X6 represents an alkyl group, R X7 The symbol represents an alkylene group, p represents an integer greater than or equal to 2, and q represents 0 or 1. R X6 The alkyl group represented by X A It is synonymous with the alkyl group represented by . Also, R X7 The alkylene group represented by X A Examples include groups obtained by removing one hydrogen atom from an alkyl group represented by . p is an integer greater than or equal to 2, and its upper limit is, for example, 10 or less, preferably 5 or less.

[0095] Examples of aryl groups include aryl groups having 6 to 24 carbon atoms (which may be monocyclic or polycyclic). The above aryl group may have further substituents, such as alkyl groups, halogen atoms, and cyano groups.

[0096] The polyester chains described above are preferably structures in which lactones such as ε-caprolactone, δ-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, enantractone, β-butyrolactone, γ-hexanolactone, γ-octanolactone, δ-hexalanolactone, δ-octanolactone, δ-dodecanolactone, α-methyl-γ-butyrolactone, and lactide (which may be the L or D form) are opened, and structures in which ε-caprolactone or δ-valerolactone are opened are more preferred.

[0097] The repeating units containing the polyalkylene imine structure and polyester structure described above can be synthesized according to the synthesis method described in Japanese Patent No. 5923557.

[0098] In resin A, the content of repeating units including graft chains is, for example, 2 to 100% by mass, preferably 2 to 95% by mass, more preferably 2 to 90% by mass, and even more preferably 5 to 30% by mass, based on the total mass of resin A. The effects of the present invention are better when the repeating units including graft chains are included within this range.

[0099] (Hydrophobic repeating unit) Furthermore, resin A may contain hydrophobic repeating units that are different from (i.e., do not correspond to) repeating units containing graft chains. However, in this specification, hydrophobic repeating units are repeating units that do not have acidic groups (e.g., carboxylic acid groups, sulfonic acid groups, phosphate groups, phenolic hydroxyl groups, etc.).

[0100] The hydrophobic repeating units are preferably repeating units derived from (corresponding to) compounds (monomers) with a ClogP value of 1.2 or higher, and more preferably repeating units derived from compounds with a ClogP value of 1.2 to 8. This allows the effects of the present invention to be more reliably expressed.

[0101] The ClogP value is calculated using the "CLOGP" program available from Daylight Chemical Information System, Inc. This program provides a "calculated logP" value derived from the fragment approach by Hansch, Leo (see reference below). The fragment approach is based on the chemical structure of a compound, dividing the chemical structure into substructures (fragments) and estimating the compound's logP value by summing the logP contributions assigned to each fragment. Details are described in the following reference. In this specification, we use ClogP values ​​calculated using the CLOGP v4.82 program. AJ Leo, Comprehensive Medicinal Chemistry, Vol.4, C. Hansch, PG Sammnens, JB Taylor and CA Ramsden, Eds., p.295, Pergamon Press, 1990 C. Hansch & AJ Leo. SUbstituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. AJ Leo. Calculating logPoct from structure. Chem. Rev., 93, 1281-1306, 1993.

[0102] logP represents the common logarithm of the partition coefficient P, and is a physical property that quantitatively expresses how an organic compound is distributed in equilibrium between oil (generally 1-octanol) and water, and is expressed by the following formula. logP = log(Coil / Cwater) In the formula, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the aqueous phase. As the value of logP increases in positive proportions around 0, oil solubility increases, and as the absolute value increases in negative proportions, water solubility increases. There is a negative correlation with the water solubility of organic compounds, and it is widely used as a parameter to estimate the hydrophilicity and hydrophobicity of organic compounds.

[0103] Resin A preferably contains one or more repeating units selected from repeating units derived from monomers represented by the following formulas (i) to (iii) as hydrophobic repeating units.

[0104] [ka]

[0105] In the above equations (i) to (iii), R 1 , R 2 , and R 3 Each of these independently represents a hydrogen atom, a halogen atom (e.g., fluorine atom, chlorine atom, and bromine atom), or an alkyl group having 1 to 6 carbon atoms (e.g., methyl group, ethyl group, and propyl group). R 1 , R 2 , and R 3 R is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. 2 and R 3 It is even more preferable that it be a hydrogen atom. X represents either an oxygen atom (-O-) or an imino group (-NH-), with the oxygen atom being preferred.

[0106] L is a single bond or a divalent linking group. Examples of divalent linking groups include divalent aliphatic groups (e.g., alkylene groups, substituted alkylene groups, alkenylene groups, substituted alkenylene groups, alkynylene groups, substituted alkynylene groups), divalent aromatic groups (e.g., arylene groups, substituted arylene groups), divalent heterocyclic groups, oxygen atoms (-O-), sulfur atoms (-S-), imino groups (-NH-), and substituted imino groups (-NR-). 31 -, here R 31Examples include aliphatic groups, aromatic groups, or heterocyclic groups, carbonyl groups (-CO-), and combinations thereof.

[0107] The divalent aliphatic group may have a cyclic or branched structure. The number of carbon atoms in the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. The aliphatic group may be unsaturated or saturated, but saturated aliphatic groups are preferred. The aliphatic group may also have substituents. Examples of substituents include halogen atoms, aromatic groups, and heterocyclic groups.

[0108] The number of carbon atoms in the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. The aromatic group may also have substituents. Examples of substituents include halogen atoms, aliphatic groups, aromatic groups, and heterocyclic groups.

[0109] The divalent heterocyclic group preferably contains a five-membered or six-membered ring as the heterocycle. Another heterocycle, aliphatic ring, or aromatic ring may be fused to the heterocycle. The heterocyclic group may also have substituents. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups (=O), thioxo groups (=S), imino groups (=NH), and substituted imino groups (=NR). 32 , here R 32 Examples include aliphatic groups, aromatic groups, or heterocyclic groups.

[0110] L is preferably a divalent linking group containing a single bond, an alkylene group, or an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L may also contain a polyoxyalkylene structure containing two or more repeating oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented as -(OCH2CH2)n-, where n is preferably an integer of 2 or more, and more preferably an integer from 2 to 10.

[0111] Examples of Z include aliphatic groups (e.g., alkyl groups, substituted alkyl groups, unsaturated alkyl groups, substituted unsaturated alkyl groups), aromatic groups (e.g., aryl groups, substituted aryl groups, arylene groups, substituted arylene groups), heterocyclic groups, and combinations thereof. These groups include oxygen atoms (-O-), sulfur atoms (-S-), imino groups (-NH-), substituted imino groups (-NR-). 31 -, here R 31 The group may contain an aliphatic group, an aromatic group, or a heterocyclic group, or a carbonyl group (-CO-).

[0112] Aliphatic groups may have a cyclic or branched structure. The number of carbon atoms in the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. Aliphatic groups further include ring-assembled hydrocarbon groups and crosslinked cyclic hydrocarbon groups. Examples of ring-assembled hydrocarbon groups include bicyclohexyl groups, perhydronaphthalenyl groups, biphenyl groups, and 4-cyclohexylphenyl groups. Examples of crosslinked cyclic hydrocarbon rings include bicyclic hydrocarbon rings such as pinane, bornane, norpinane, norbornane, bicyclooctane rings (bicyclo[2.2.2]octane rings and bicyclo[3.2.1]octane rings, etc.), homobredan, adamantane, and tricyclo[5.2.1.0 2,6 ] Decane and tricyclo[4.3.1.1 2,5 ]Tricyclic hydrocarbon rings such as undecane rings, and tetracyclo[4.4.0.1 2,5 .1 7,10 Examples include dodecane and tetracyclic hydrocarbon rings such as the perhydro-1,4-methano-5,8-methanonaphthalene ring. Bridged cyclic hydrocarbon rings also include condensed cyclic hydrocarbon rings, such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and perhydrophenalene rings, which are condensed rings formed by the fusion of multiple 5-8 membered cycloalkane rings. A saturated aliphatic group is preferred over an unsaturated aliphatic group. The aliphatic group may also have substituents. Examples of substituents include halogen atoms, aromatic groups, and heterocyclic groups. However, the aliphatic group does not have an acidic group as a substituent.

[0113] The aromatic group preferably has 6 to 20 carbon atoms, more preferably 6 to 15, and even more preferably 6 to 10 carbon atoms. The aromatic group may also have substituents. Examples of substituents include halogen atoms, aliphatic groups, aromatic groups, and heterocyclic groups. However, the aromatic group does not have an acid group as a substituent.

[0114] The heterocyclic group preferably includes a 5-membered or 6-membered ring as the heterocycle. Other heterocycles, aliphatic rings, or aromatic rings may be fused to the heterocycle. The heterocyclic group may also have substituents. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups (=O), thioxo groups (=S), imino groups (=NH), and substituted imino groups (=NR). 32 , here R 32 Examples include aliphatic groups, aromatic groups, or heterocyclic groups. However, heterocyclic groups do not have acidic groups as substituents.

[0115] In the above formula (iii), R 4 , R 5 , and R 6 Each of these independently represents a hydrogen atom, a halogen atom (e.g., fluorine, chlorine, and bromine), an alkyl group with 1 to 6 carbon atoms (e.g., methyl, ethyl, and propyl), Z, or LZ. Here, L and Z are synonymous with the groups described above. 4 , R 5 , and R 6 Preferably, the element is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

[0116] As the monomer represented by the above formula (i), R 1 , R 2 , and R 3A compound is preferred in which is a hydrogen atom or a methyl group, L is a divalent linking group containing a single bond or an alkylene group or oxyalkylene structure, X is an oxygen atom or an imino group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. Furthermore, as a monomer represented by the above formula (ii), R 1 A compound in which is a hydrogen atom or a methyl group, L is an alkylene group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group is preferred. Also, as the monomer represented by the above formula (iii), R 4 , R 5 , and R 6 A compound in which is a hydrogen atom or a methyl group and Z is an aliphatic group, a heterocyclic group, or an aromatic group is preferred.

[0117] Representative compounds represented by formulas (i) to (iii) include radical polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, and styrenes. For example, representative compounds represented by formulas (i) to (iii) can be found in paragraphs 0089 to 0093 of Japanese Patent Publication No. 2013-249417, and the contents of these publications are incorporated herein by reference.

[0118] In resin A, the content of hydrophobic repeating units is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass, relative to the total mass of resin A.

[0119] (Functional groups that can form interactions with magnetic particles) Resin A may have functional groups that can form interactions with magnetic particles. Resin A preferably further comprises repeating units containing functional groups that can form interactions with magnetic particles. Examples of functional groups that can form interactions with magnetic particles include acidic groups, basic groups, coordinating groups, and reactive functional groups. If resin A contains acidic groups, basic groups, coordinating groups, or reactive functional groups, it is preferable that it contains repeating units containing acidic groups, repeating units containing basic groups, repeating units containing coordinating groups, or repeating units having reactive functional groups, respectively.

[0120] The repeating unit containing the acid group may be the same as the repeating unit containing the graft chain described above, or it may be a different repeating unit, but the repeating unit containing the acid group is a different repeating unit from the hydrophobic repeating unit described above (i.e., it does not correspond to the hydrophobic repeating unit described above).

[0121] Examples of acidic groups that can form interactions with magnetic particles include carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, and phenolic hydroxyl groups. At least one of the carboxylic acid group, sulfonic acid group, and phosphoric acid group is preferred, with the carboxylic acid group being more preferred. Carboxylic acid groups have good adsorption to magnetic particles and high dispersibility. In other words, it is preferable that resin A further contains repeating units comprising at least one of a carboxylic acid group, a sulfonic acid group, and a phosphate group.

[0122] Resin A may have one or more repeating units containing acid groups. If resin A contains repeating units containing acid groups, the content of these units is preferably 5 to 80% by mass, and more preferably 10 to 60% by mass, relative to the total mass of resin A.

[0123] Examples of basic groups that can form interactions with magnetic particles include primary amino groups, secondary amino groups, tertiary amino groups, heterocycles containing N atoms, and amide groups. The preferred basic group is the tertiary amino group because it has good adsorption to magnetic particles and high dispersibility. Resin A may contain one or more of these basic groups. When the resin A contains a repeating unit containing a basic group, the content thereof is preferably 0.01 to 50% by mass, more preferably 0.01 to 30% by mass, based on the total mass of the resin A in terms of mass.

[0124] Examples of the coordinating group which is a functional group capable of forming an interaction with magnetic particles and the reactive functional group include an acetylacetoxy group, a trialkoxysilyl group, an isocyanate group, an acid anhydride, and an acid chloride. A preferable functional group is an acetylacetoxy group in terms of good adsorption force to magnetic particles and high dispersibility of magnetic particles. The resin A may have one or more of these groups. When the resin A contains a repeating unit containing a coordinating group or a repeating unit containing a reactive functional group, the content thereof is preferably 10 to 80% by mass, more preferably 20 to 60% by mass, based on the total mass of the resin A in terms of mass.

[0125] When the above resin A contains, in addition to the graft chain, a functional group capable of forming an interaction with magnetic particles, it only needs to contain a functional group capable of forming an interaction with the above various magnetic particles, and there is no particular limitation on how these functional groups are introduced. For example, the resin contained in the composition preferably contains one or more repeating units selected from the repeating units derived from the monomers represented by the following formulas (iv) to (vi).

[0126]

Chemical formula

[0127] In formulas (iv) to (vi), R 11 , R 12 , and R 13 each independently represents a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom, etc.), or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, and a propyl group, etc.). In formulas (iv) to (vi), R 11 , R 12 , and R 13As such, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferred, and a hydrogen atom or a methyl group is more preferred. In general formula (iv), R 12 and R 13 Hydrogen atoms are even more preferable.

[0128] In formula (iv), X1 represents an oxygen atom (-O-) or an imino group (-NH-), with the oxygen atom being preferred. Furthermore, Y in formula (v) represents either a methine group or a nitrogen atom.

[0129] Furthermore, L1 in formulas (iv) to (v) represents a single bond or a divalent linking group. The definition of a divalent linking group is the same as the definition of a divalent linking group represented by L in formula (i) above.

[0130] L1 is preferably a divalent linking group containing a single bond, an alkylene group, or an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L1 may also contain a polyoxyalkylene structure containing two or more repeating oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is -(OCH2CH2) n It is represented by -, where n is preferably an integer of 2 or more, and more preferably an integer between 2 and 10.

[0131] In formulas (iv) to (vi), Z1 represents a functional group that can interact with magnetic particles in addition to the graft chain, and is preferably a carboxylic acid group or a tertiary amino group, with a carboxylic acid group being more preferred.

[0132] In formula (vi), R 14 , R 15 , and R 16 Each of these independently represents a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, and a bromine atom), an alkyl group having 1 to 6 carbon atoms (e.g., a methyl group, an ethyl group, and a propyl group), -Z1, or L1-Z1. Here, L1 and Z1 are synonymous with L1 and Z1 above, and the preferred examples are similar.14 , R 15 , and R 16 Preferably, the element is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

[0133] As a monomer represented by formula (iv), R 11 , R 12 , and R 13 A compound is preferred in which each of the following is independently a hydrogen atom or a methyl group, L1 is a divalent linking group containing an alkylene group or an oxyalkylene structure, X1 is an oxygen atom or an imino group, and Z1 is a carboxylic acid group. Furthermore, as a monomer represented by equation (v), R 11 A compound in which is a hydrogen atom or a methyl group, L1 is an alkylene group, Z1 is a carboxylic acid group, and Y is a methine group is preferred. Furthermore, as a monomer represented by equation (vi), R 14 , R 15 , and R 16 A compound in which each of the elements is independently a hydrogen atom or a methyl group, and Z1 is a carboxylic acid group, is preferred.

[0134] The following are representative examples of monomers (compounds) represented by formulas (iv) to (vi). Examples of monomers include methacrylic acid, crotonic acid, isocrotonic acid, reaction products of compounds containing an addition-polymerizable double bond and a hydroxyl group in the molecule (e.g., 2-hydroxyethyl methacrylate) with succinic anhydride, reaction products of compounds containing an addition-polymerizable double bond and a hydroxyl group in the molecule with phthalic anhydride, reaction products of compounds containing an addition-polymerizable double bond and a hydroxyl group in the molecule with tetrahydroxyphthalic anhydride, reaction products of compounds containing an addition-polymerizable double bond and a hydroxyl group in the molecule with trimellitic anhydride, reaction products of compounds containing an addition-polymerizable double bond and a hydroxyl group in the molecule with pyromellitic anhydride, acrylic acid, acrylate dimer, acrylate oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, and 4-hydroxyphenylmethacrylamide.

[0135] The content of repeating units containing functional groups that can form interactions with magnetic particles is preferably 0.05 to 90% by mass, more preferably 1.0 to 80% by mass, and even more preferably 10 to 70% by mass, relative to the total mass of resin A, in terms of interaction with magnetic particles, stability over time, and permeability to the developing solution.

[0136] (ethylenically unsaturated group) Resin A may contain ethylenically unsaturated groups. The ethylenically unsaturated group is not particularly limited, but examples include (meth)acryloyl, vinyl, and styryl groups, with (meth)acryloyl being preferred. Among resins A, it is preferable that the resin A contains repeating units with ethylenically unsaturated groups in its side chains, and more preferably that the resin A contains repeating units with ethylenically unsaturated groups in its side chains and that are derived from (meth)acrylate (hereinafter also referred to as "(meth)acrylic repeating units with ethylenically unsaturated groups in their side chains"). (Meth)acrylic repeating units containing ethylenically unsaturated groups in their side chains can be obtained, for example, by adding an ethylenically unsaturated compound containing a glycidyl group or an alicyclic epoxy group to the carboxylic acid group in resin A, which contains a (meth)acrylic repeating unit containing a carboxylic acid group. By introducing it in this way, (meth)acrylic repeating units containing ethylenically unsaturated groups in their side chains can be obtained.

[0137] If resin A contains repeating units containing ethylenically unsaturated groups, the content of these units is preferably 30 to 70% by mass, and more preferably 40 to 60% by mass, relative to the total mass of resin A.

[0138] (Other curing groups) Resin A may contain other curable groups in addition to ethylenically unsaturated groups. Other curable groups include, for example, epoxy groups and oxetanyl groups. As the resin A, it is preferable that it contains a repeating unit containing other curable groups in the side chain, more preferably that it contains a repeating unit containing other curable groups in the side chain and a repeating unit derived from (meth)acrylate (hereinafter also referred to as "(meth)acrylic repeating unit containing other curable groups in the side chain"). Examples of the (meth)acrylic repeating unit containing other curable groups in the side chain include a repeating unit derived from glycidyl (meth)acrylate.

[0139] When the resin A contains a repeating unit containing other curable groups, its content is preferably 5 to 50% by mass, more preferably 10 to 30% by mass, based on the total mass of the resin A in terms of mass.

[0140] (Other repeating units) Furthermore, for the purpose of improving various properties such as film-forming ability, the resin A may further have other repeating units having various functions that are different from the above-mentioned repeating units as long as the effects of the present invention are not impaired. Examples of such other repeating units include repeating units derived from radical-polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like. One or more of these other repeating units can be used for the resin A, and its content is preferably 0 to 80% by mass, more preferably 10 to 60% by mass, based on the total mass of the resin A in terms of mass.

[0141] (Physical properties of resin A) The acid value of the resin A is not particularly limited, but for example, 0 to 400 mgKOH / g is preferable, 10 to 350 mgKOH / g is more preferable, 30 to 300 mgKOH / g is still more preferable, and the range of 50 to 200 mgKOH / g is particularly preferable. If the acid value of the resin A is 50 mgKOH / g or more, the sedimentation stability of the magnetic particles can be further improved.

[0142] In this specification, the acid value can be calculated, for example, from the average content of acid groups in the compound. Furthermore, a resin having a desired acid value can be obtained by changing the content of repeating units containing acid groups in the resin.

[0143] The weight-average molecular weight of resin A is not particularly limited, but for example, it is preferably 3,000 or more, more preferably 4,000 or more, even more preferably 5,000 or more, and particularly preferably 6,000 or more. As for the upper limit, for example, it is preferably 300,000 or less, more preferably 200,000 or less, even more preferably 100,000 or less, and particularly preferably 50,000 or less. Resin A can be synthesized based on known methods.

[0144] For specific examples of resin A, refer to the polymer compounds described in paragraphs 0127 to 0129 of Japanese Patent Publication No. 2013-249417, and the contents of these are incorporated herein.

[0145] Furthermore, as resin A, graft copolymers described in paragraphs 0037 to 0115 of Japanese Patent Application Publication No. 2010-106268 (corresponding to columns 0075 to 0133 of US2011 / 0124824) can also be used, and the contents of these can be incorporated herein by reference.

[0146] <Alkali-soluble resin> The binder component may include an alkali-soluble resin. In this specification, "alkali-soluble resin" means a resin containing a group that promotes alkali solubility (alkali-soluble group, such as an acidic group like a carboxylic acid group), and means a resin different from resin A described above.

[0147] Examples of alkali-soluble resins include resins containing at least one alkali-soluble group in their molecule, such as polyhydroxystyrene resins, polysiloxane resins, (meth)acrylic resins, (meth)acrylamide resins, (meth)acrylic / (meth)acrylamide copolymers, epoxy resins, and polyimide resins.

[0148] Specific examples of alkali-soluble resins include copolymers of unsaturated carboxylic acids and ethylenically unsaturated compounds. The unsaturated carboxylic acids are not particularly limited, but examples include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, and vinylacetic acid; dicarboxylic acids such as itaconic acid, maleic acid, and fumaric acid, or their acid anhydrides; and polycarboxylic acid monoesters such as phthalic acid mono(2-(meth)acryloyloxyethyl); and the like.

[0149] Examples of copolymerizable ethylenically unsaturated compounds include methyl (meth)acrylate. Furthermore, compounds described in paragraph 0027 of Japanese Patent Publication No. 2010-097210 and paragraphs 0036-0037 of Japanese Patent Publication No. 2015-068893 can also be used, and the above information is incorporated herein.

[0150] Furthermore, copolymerizable ethylenically unsaturated compounds containing ethylenically unsaturated groups in their side chains may be used in combination. In other words, alkali-soluble resins may contain repeating units with ethylenically unsaturated groups in their side chains. The preferred ethylenically unsaturated group in the side chain is the (meth)acrylic acid group. Repeating units containing ethylenically unsaturated groups in their side chains can be obtained, for example, by adding an ethylenically unsaturated compound containing a glycidyl group or an alicyclic epoxy group to a carboxylic acid group in a (meth)acrylic repeating unit containing a carboxylic acid group.

[0151] As the alkali-soluble resin, an alkali-soluble resin containing a curable group is also preferred. Examples of the curable groups mentioned above include, but are not limited to, ethylenically unsaturated groups (e.g., (meth)acryloyl groups, vinyl groups, and styryl groups) and cyclic ether groups (e.g., epoxy groups, oxetanyl groups). In particular, ethylenically unsaturated groups are preferred as curable groups, and (meth)acryloyl groups are more preferred, as they allow polymerization control via radical reactions. As alkali-soluble resins containing curable groups, alkali-soluble resins having curable groups in their side chains are preferred. Examples of alkali-soluble resins containing curable groups include the Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer, manufactured by Diamond Shamrock Co., Ltd.), Viscoat R-264, KS Resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (e.g., ACA230AA), Praxel CF200 series (both manufactured by Daicel Corporation), Ebecryl 3800 (manufactured by Daicel Ornex Co., Ltd.), and Acrycure RD-F8 (manufactured by Nippon Shokubai Co., Ltd.).

[0152] Examples of alkali-soluble resins include radical polymers containing carboxylic acid groups in the side chains described in Japanese Patent Publication No. 59-044615, Japanese Patent Publication No. 54-034327, Japanese Patent Publication No. 58-012577, Japanese Patent Publication No. 54-025957, Japanese Patent Publication No. 54-092723, Japanese Patent Publication No. 59-053836, and Japanese Patent Publication No. 59-071048; European Patent No. 993966, European Patent No. 1204000, and Acetal-modified polyvinyl alcohol-based binder resin containing alkali-soluble groups as described in Publication No. 2001-318463; polyvinylpyrrolidone; polyethylene oxide; alcohol-soluble nylon; and polyethers, which are reaction products of 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin; as well as polyimide resins as described in International Publication No. 2008 / 123097; can be used.

[0153] As alkali-soluble resins, for example, compounds described in paragraphs 0225 to 0245 of Japanese Patent Publication No. 2016-075845 can also be used, and the above content is incorporated herein.

[0154] Polyimide precursors can also be used as alkali-soluble resins. A polyimide precursor refers to a resin obtained by an addition polymerization reaction between a compound containing an acid anhydride group and a diamine compound at 40-100°C. Specific examples of the above polyimide precursors include, for example, the compounds described in paragraphs 0011 to 0031 of Japanese Patent Publication No. 2008-106250, the compounds described in paragraphs 0022 to 0039 of Japanese Patent Publication No. 2016-122101, the compounds described in paragraphs 0061 to 0092 of Japanese Patent Publication No. 2016-068401, the resin described in paragraph 0050 of Japanese Patent Publication No. 2014-137523, the resin described in paragraph 0058 of Japanese Patent Publication No. 2015-187676, and the resin described in paragraphs 0012 to 0013 of Japanese Patent Publication No. 2014-106326, and the above contents are incorporated herein by reference.

[0155] As alkali-soluble resins, copolymers of [benzyl (meth)acrylate / (meth)acrylic acid / other addition polymerizable vinyl monomers as needed] and [allyl (meth)acrylate / (meth)acrylic acid / other addition polymerizable vinyl monomers as needed] are preferred because they offer an excellent balance of film strength, sensitivity, and developability. The above-mentioned other addition polymerizable vinyl monomers may be one type or two or more types. The above copolymer preferably has a curable group, and more preferably contains an ethylenically unsaturated group such as a (meth)acryloyl group, as this provides superior moisture resistance to the cured film. For example, a monomer having a curable group may be used as the other addition polymerizable vinyl monomer mentioned above to introduce a curable group into the copolymer. Alternatively, a curable group (preferably an ethylenically unsaturated group such as a (meth)acryloyl group) may be introduced into some or all of one or more units derived from (meth)acrylic acid and / or the other addition polymerizable vinyl monomer in the copolymer. Examples of other addition polymerizable vinyl monomers include methyl (meth)acrylate, styrene monomers (such as hydroxystyrene), and ether dimers. Examples of the ether dimers mentioned above include compounds represented by the following general formula (ED1) and compounds represented by the following general formula (ED2).

[0156] [ka]

[0157] In general formula (ED1), R 1 and R 2 Each of these independently represents either a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms.

[0158] [ka]

[0159] In general formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. For specific examples of general formula (ED2), refer to the description in Japanese Patent Publication No. 2010-168539.

[0160] For specific examples of ether dimers, see, for example, paragraph 0317 of Japanese Patent Publication No. 2013-029760, which is incorporated herein by reference. The ether dimer may be one type or two or more types.

[0161] The acid value of the alkali-soluble resin is not particularly limited, but generally, 30 to 500 mg KOH / g is preferred, and 50 to 200 mg KOH / g or more is more preferred.

[0162] If the composition contains an alkali-soluble resin, the content of the alkali-soluble resin is preferably 1 to 24% by mass, more preferably 1 to 15% by mass, even more preferably 1 to 12% by mass, particularly preferably 1 to 10% by mass, and most preferably 1 to 7% by mass, based on the total mass of the composition. If the composition contains an alkali-soluble resin, the content of the alkali-soluble resin is preferably 0.8 to 24% by mass, more preferably 0.8 to 15% by mass, even more preferably 0.8 to 12% by mass, even more preferably 0.8 to 10% by mass, particularly preferably 0.8 to 8% by mass, and most preferably 0.8 to 7% by mass, based on the total solid content of the composition.

[0163] <Resin-type rheology control agent> The binder component may contain a resin-type rheology control agent. Rheology control agents are components that impart thixotropic properties to a composition, exhibiting high viscosity at low shear forces (shear rates) and low viscosity at high shear forces (shear rates). In this specification, the term "resin-type rheology control agent" means a resin having the above-described properties, and is a resin different from resin A described above.

[0164] Examples of resin-type rheology control agents include compounds having one or more (preferably two or more) adsorption groups and further having steric repulsion structural groups. The weight-average molecular weight of the resin-type rheology control agent is preferably 2000 or more, and preferably in the range of 2000 to 50000. One specific example of a resin-type rheology control agent is the organic rheology control agent, which is of resin type, as described later. When the binder component contains a resin-type rheology control agent, the content of the resin-type rheology control agent is preferably 1 to 24% by mass, more preferably 1 to 15% by mass, even more preferably 1 to 12% by mass, particularly preferably 1 to 10% by mass, and most preferably 1 to 7% by mass, based on the total mass of the composition. Furthermore, if the binder component contains a resin-type rheology control agent, the content of the resin-type rheology control agent is preferably 0.8 to 24% by mass, more preferably 0.8 to 15% by mass, even more preferably 0.8 to 12% by mass, even more preferably 0.8 to 10% by mass, particularly preferably 0.8 to 8% by mass, and most preferably 0.8 to 7% by mass, based on the total solid content of the composition.

[0165] Furthermore, as a binder component, commercially available wetting and dispersing agents such as "C-2093I" (manufactured by NOF Corporation) can also be used.

[0166] <Polymerizable compound> The binder component may contain polymerizable compounds. The molecular weight (or weight-average molecular weight) of the polymerizable compound is not particularly limited, but is preferably 2000 or less. If the binder component contains a polymerizable compound, its content is preferably 1 to 24% by mass, more preferably 1 to 15% by mass, even more preferably 1 to 12% by mass, particularly preferably 1 to 10% by mass, and most preferably 1 to 7% by mass, based on the total mass of the composition. If the binder component contains a polymerizable compound, its content is preferably 0.8 to 24% by mass, more preferably 0.8 to 15% by mass, even more preferably 0.8 to 12% by mass, even more preferably 0.8 to 10% by mass, particularly preferably 0.8 to 8% by mass, and most preferably 0.8 to 7% by mass, based on the total solid content of the composition.

[0167] (Compounds containing groups with ethylenically unsaturated bonds) Polymerizable compounds include, for example, compounds containing a group that includes an ethylenically unsaturated bond (hereinafter also simply referred to as an "ethylenically unsaturated group"). As polymerizable compounds, compounds containing one or more ethylenically unsaturated bonds are preferred, compounds containing two or more are more preferred, compounds containing three or more are even more preferred, and compounds containing five or more are particularly preferred. The upper limit is, for example, 15 or less. Examples of ethylenically unsaturated groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups.

[0168] As polymerizable compounds, for example, the compounds described in paragraph 0050 of Japanese Patent Publication No. 2008-260927 and paragraph 0040 of Japanese Patent Publication No. 2015-068893 can be used, and the above contents are incorporated herein.

[0169] The polymerizable compound may be in any chemical form, such as monomers, prepolymers, oligomers, mixtures thereof, or polymers thereof. The polymerizable compounds described above are preferably (meth)acrylate compounds with 3 to 15 functions, and more preferably (meth)acrylate compounds with 3 to 6 functions.

[0170] As polymerizable compounds, compounds containing one or more ethylenically unsaturated groups and having a boiling point of 100°C or higher are also preferred. For example, the compounds described in paragraph 0227 of Japanese Patent Publication No. 2013-029760 and paragraphs 0254-0257 of Japanese Patent Publication No. 2008-292970 can be considered, and this information is incorporated herein.

[0171] Preferred polymerizable compounds include dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin Nakamura Chemical Co., Ltd.), and structures in which the (meth)acryloyl group of these compounds is mediated by an ethylene glycol residue or a propylene glycol residue (for example, SR454 and SR499, commercially available from Sartomer). These oligomer types can also be used. In addition, NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040, KAYARAD DPEA-12LT, KAYARAD DPHA LT, KAYARAD RP-3060, and KAYARAD DPEA-12 (all trade names, manufactured by Nippon Kayaku Co., Ltd.) may also be used.

[0172] Polymerizable compounds may have acidic groups such as carboxylic acid groups, sulfonic acid groups, and phosphoric acid groups. Preferred polymerizable compounds containing acidic groups are esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, more preferably polymerizable compounds obtained by reacting the unreacted hydroxyl groups of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group, and even more preferably, compounds in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include Aronics TO-2349, M-305, M-510, and M-520 from Toagosei Co., Ltd.

[0173] The acid value of the polymerizable compound containing an acid group is preferably 0.1 to 40 mg KOH / g, and more preferably 5 to 30 mg KOH / g. If the acid value of the polymerizable compound is 0.1 mg KOH / g or higher, the development and dissolution characteristics are good, and if it is 40 mg KOH / g or lower, it is advantageous in terms of manufacturing and / or handling. Furthermore, it exhibits good photopolymerization performance and excellent curability.

[0174] As polymerizable compounds, compounds containing a caprolactone structure are also preferred embodiments. Compounds containing a caprolactone structure are not particularly limited as long as they contain a caprolactone structure within the molecule, but examples include ε-caprolactone-modified polyfunctional (meth)acrylates obtained by esterifying polyhydric alcohols such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, or trimethylolmelamine with (meth)acrylic acid and ε-caprolactone. Among these, compounds containing a caprolactone structure represented by the following formula (Z-1) are preferred.

[0175] [ka]

[0176] In equation (Z-1), all six Rs are groups represented by equation (Z-2) below, or 1 to 5 of the six Rs are groups represented by equation (Z-2) below, and the remainder are groups represented by equation (Z-3) below.

[0177] [ka]

[0178] In formula (Z-2), R 1 The symbol (*) indicates a hydrogen atom or a methyl group, m indicates a number (1 or 2), and "*" indicates a bond.

[0179] [ka]

[0180] In formula (Z-3), R 1 * indicates a hydrogen atom or a methyl group, and * indicates a bonding bond.

[0181] Polymerizable compounds containing a caprolactone structure include, for example, those commercially available from Nippon Kayaku as the KAYARAD DPCA series, such as DPCA-20 (where m=1 in formulas (Z-1) to (Z-3) above, the number of groups represented by formula (Z-2) = 2, R 1 (A compound in which all atoms are hydrogen atoms), DPCA-30 (same formula, m=1, number of groups represented by formula (Z-2) = 3, R 1 (A compound in which all atoms are hydrogen atoms), DPCA-60 (same formula, m=1, number of groups represented by formula (Z-2) = 6, R 1 Compounds in which all atoms are hydrogen atoms), and DPCA-120 (in the same formula, m=2, the number of groups represented by formula (Z-2) = 6, R 1 Examples include compounds in which all atoms are hydrogen atoms. Furthermore, a commercially available polymerizable compound containing a caprolactone structure is M-350 (trade name) (trimethylolpropane triacrylate) manufactured by Toagosei Co., Ltd.

[0182] As polymerizable compounds, compounds represented by the following formulas (Z-4) or (Z-5) can also be used.

[0183] [ka]

[0184] In equations (Z-4) and (Z-5), E is -((CH2) y CH2O)-, or ((CH2) y The symbol CH(CH3)O)- represents a group, y represents an integer from 0 to 10, and X represents a (meth)acryloyl group, a hydrogen atom, or a carboxylic acid group. In formula (Z-4), the total number of (meth)acryloyl groups is 3 or 4, m represents an integer from 0 to 10, and the sum of each m is an integer from 0 to 40. In formula (Z-5), the total number of (meth)acryloyl groups is 5 or 6, n represents an integer from 0 to 10, and the sum of each n is an integer from 0 to 60.

[0185] In equation (Z-4), m is preferably an integer between 0 and 6, and more preferably an integer between 0 and 4. Furthermore, the sum of each m is preferably an integer between 2 and 40, more preferably an integer between 2 and 16, and even more preferably an integer between 4 and 8. In equation (Z-5), n is preferably an integer between 0 and 6, and more preferably an integer between 0 and 4. Furthermore, the sum of each n is preferably an integer between 3 and 60, more preferably an integer between 3 and 24, and even more preferably an integer between 6 and 12. Also, -((CH2) in equation (Z-4) or equation (Z-5) y CH2O)- or ((CH2) y The CH(CH3)O)- group is preferably formed with the oxygen atom end bonded to X.

[0186] The compounds represented by formula (Z-4) or formula (Z-5) may be used individually or in combination of two or more. Particularly preferred are the form in which all six X in formula (Z-5) are acryloyl groups, and the form in which a mixture of a compound in which all six X in formula (Z-5) are acryloyl groups and a compound in which at least one of the six X is a hydrogen atom. Such a configuration can further improve developability.

[0187] Furthermore, the total content of the compound represented by formula (Z-4) or formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more. Among the compounds represented by formula (Z-4) or formula (Z-5), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferred.

[0188] Furthermore, the polymerizable compound may also contain a cardo skeleton. As polymerizable compounds containing a cardo skeleton, polymerizable compounds containing a 9,9-bisarylfluorene skeleton are preferred. Polymerizable compounds containing a cardo skeleton are not limited, but examples include the Oncoat EX series (manufactured by Nagase & Co., Ltd.) and Ogusol (manufactured by Osaka Gas Chemical Co., Ltd.). Polymerizable compounds that contain an isocyanuric acid skeleton as a central core are also preferred. An example of such a polymerizable compound is NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.). The ethylenically unsaturated group content of the polymerizable compound (meaning the number of ethylenically unsaturated groups in the polymerizable compound divided by the molecular weight (g / mol) of the polymerizable compound) is preferably 5.0 mmol / g or more. There is no particular upper limit, but it is generally 20.0 mmol / g or less.

[0189] (Compounds having epoxy groups and / or oxetanyl groups) The polymerizable compound is also preferably a compound having an epoxy group and / or an oxetanyl group. The polymerizable compound preferably has one or more epoxy groups and / or oxetanyl groups, and more preferably 2 to 10 such groups. In polymerizable compounds, epoxy groups and / or oxetanyl groups (preferably epoxy groups) may be fused with cyclic groups (such as alicyclic groups). The cyclic group fused with epoxy groups and / or oxetanyl groups preferably has 5 to 15 carbon atoms. In addition, the portion of the cyclic group other than the fused epoxy group and / or oxetanyl group may be monocyclic or polycyclic. A single cyclic group may have only one epoxy group or oxetanyl group fused with it, or it may have two or more epoxy groups and / or oxetanyl groups fused with it.

[0190] Examples of polymerizable compounds include monofunctional or polyfunctional glycidyl ether compounds. The polymerizable compound may be, for example, (poly)alkylene glycol diglycidyl ether.

[0191] The polymerizable compound may also be a compound containing the caprolactone structure represented by formula (Z-1) described above, in which the group represented by formula (Z-2) is changed to the group represented by formula (Z-2E) below, and the group represented by formula (Z-3) is changed to the group represented by formula (Z-3E).

[0192] [ka]

[0193] In formula (Z-2E), m represents a number of 1 or 2, X and Y each independently represent a hydrogen atom or a substituent (preferably an alkyl group, preferably having 1 to 3 carbon atoms), and "*" represents a bond. In formula (Z-3E), X and Y each independently represent a hydrogen atom or a substituent (preferably an alkyl group, preferably having 1 to 3 carbon atoms), and "*" indicates a bond.

[0194] The polymerizable compound may be a compound represented by the above formula (Z-4), in which X is a group represented by formula (Z-3E) or a hydrogen atom. In the modified equation (Z-4), the total number of bases represented by equation (Z-3E) is between 2 and 4.

[0195] The polymerizable compound may be a compound represented by the above formula (Z-5), in which X is a group represented by formula (Z-3E) or a hydrogen atom. In the modified formula (Z-5) in this way, the total number of groups represented by formula (Z-3E) is 2 to 6 (preferably 5 or 6).

[0196] The polymerizable compound may also be a compound in which N cyclic groups fused with epoxy groups and / or oxetanyl groups are linked via linking groups. N is an integer of 2 or more, preferably an integer between 2 and 6, and more preferably 2. The linking group preferably has a total number of atoms other than hydrogen atoms of 1 to 20, and more preferably 2 to 6. When N is 2, an example of the linking group is an alkyleneoxycarbonyl group.

[0197] Examples of commercially available polymerizable compounds include polyfunctional aliphatic glycidyl ether compounds such as Denacol EX-212L, EX-214L, EX-216L, EX-321L, and EX-850L (all manufactured by Nagase ChemteX Corporation). These are low-chlorine products, but non-low-chlorine products such as EX-212, EX-214, EX-216, EX-321, EX-614, and EX-850 can also be used in the same way. Additionally, commercially available products such as Celoxide 2021P (manufactured by Daicel Corporation, a polyfunctional epoxy monomer) can also be used. Additionally, commercially available EHPE 3150 (manufactured by Daicel Corporation, a polyfunctional epoxy / oxyranyl monomer) can also be used.

[0198] 〔solvent〕 The composition contains a solvent. Examples of solvents include water and organic solvents, with organic solvents being preferred. The lower limit of the boiling point of the solvent is preferably 55°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and particularly preferably 160°C or higher, in terms of achieving superior effects of the present invention. There is no particular limit to the upper limit of the boiling point of the solvent, but it is preferably 400°C or lower.

[0199] Examples of organic solvents include acetone (boiling point 56°C), methyl ethyl ketone (boiling point 79.6°C), cyclohexane (boiling point 80.8°C), ethyl acetate (boiling point 77.1°C), ethylene dichloride (boiling point 83.5°C), tetrahydrofuran (boiling point 66°C), cyclohexanone (boiling point 155.6°C), toluene (boiling point 110°C), ethylene glycol monomethyl ether (boiling point 124°C), ethylene glycol monoethyl ether (boiling point 135°C), ethylene glycol dimethyl ether (boiling point 84°C), and propylene glycol. Ethylene glycol monomethyl ether (boiling point 120°C), propylene glycol monoethyl ether (boiling point 132°C), acetylacetone (boiling point 140°C), cyclopentanone (boiling point 131°C), ethylene glycol monomethyl ether acetate (boiling point 144.5°C), ethylene glycol ethyl ether acetate (boiling point 145°C), ethylene glycol monoisopropyl ether (boiling point 141°C), diacetone alcohol (boiling point 166°C), ethylene glycol monobutyl ether acetate (boiling point 192°C), 1,4 -Butanediol diacetate ("1,4-BDDA", boiling point 232°C), 1,6-Hexanediol diacetate ("1,6-HDDA", boiling point 260°C), 1,3-Butylene glycol diacetate ("1,3-BGDA", boiling point 232°C), Propylene glycol diacetate ("PGDA", boiling point 190°C), Glycerol triacetic acid (boiling point 260°C), 3-Methoxy-1-propanol (boiling point 150°C), 3-Methoxy-1-butanol (boiling point 161°C), Diethylene glycol monomethyl ether (boiling point 19 (4°C), diethylene glycol monoethyl ether (boiling point 202°C), diethylene glycol dimethyl ether (boiling point 162°C), diethylene glycol diethyl ether (boiling point 188°C), propylene glycol monomethyl ether acetate ("PGMEA", boiling point 146°C), propylene glycol monoethyl ether acetate (boiling point 146°C), N,N-dimethylformamide (boiling point 153°C), dimethyl sulfoxide (boiling point 189°C), γ-butyrolactone (boiling point 204°C), ethyl acetate (boiling point 77°C).Examples include, but are not limited to, butyl acetate (boiling point 126°C), methyl lactate (boiling point 144°C), N-methyl-2-pyrrolidone (boiling point 202°C), and ethyl lactate (boiling point 154°C).

[0200] One preferred embodiment of the solvent is an acetate-based solvent, which is preferable in that the effects of the present invention are more pronounced. An acetate-based solvent refers to a solvent that contains one or more acetate groups in its molecule. The number of acetate groups in an acetate-based solvent is preferably two or more, as this enhances the effects of the present invention. There is no particular upper limit, but for example, it is six or less. The acetate-based solvent preferably has a boiling point of 160°C or higher.

[0201] Examples of acetate-based solvents containing two or more acetate groups in their molecules include the compound represented by formula (1A). Formula (1A) M-(OC(=O)-CH3) m In formula (1A), M represents an m-valent linking group. m represents 2 to 6.

[0202] Examples of linking groups M with m-valence (m=2~6) include the linking groups represented by the following formulas (M-1)~(M-5).

[0203] [ka]

[0204] In the above formulas (M-1) to (M-5), X 11 , X 21 , X 31 , X 41 , and X 51 Each of these independently represents an organic group. X 11 , X 21 , X 31 , X 41 , and X 51The organic group represented by this symbol specifically includes heteroatoms (for example, nitrogen, oxygen, and sulfur atoms. Also, heteroatoms include, for example, -O-, -S-, -SO2-, -NR 1 Examples include hydrocarbon groups formed from hydrocarbons that may contain -, -CO-, or linking groups formed by combining two or more of these. Specifically, linear or branched aliphatic hydrocarbon groups, aliphatic hydrocarbon ring groups, aromatic hydrocarbon ring groups, heterocyclic groups, or linking groups formed by combining several of these, which may contain heteroatoms, are preferred. Note that the above X 11 The hydrocarbon group that may contain heteroatoms as an organic group represented by means a divalent group formed by removing two hydrogen atoms from the above-mentioned hydrocarbon that may contain heteroatoms, and the above X 21 The hydrocarbon group that may contain heteroatoms as an organic group represented by means a trivalent group formed by removing three hydrogen atoms from the above-mentioned hydrocarbon that may contain heteroatoms, and the above X 31 The hydrocarbon group that may contain heteroatoms as an organic group represented by means a tetravalent group formed by removing four hydrogen atoms from the above-mentioned hydrocarbon that may contain heteroatoms, and the above X 41 The hydrocarbon group that may contain heteroatoms as an organic group represented by means a pentavalent group formed by removing five hydrogen atoms from the above-mentioned hydrocarbon that may contain heteroatoms, and the above X 51 The hydrocarbon group that may contain heteroatoms as an organic group, as represented by [the formula], refers to a hexavalent group formed by removing six hydrogen atoms from the hydrocarbon that may contain heteroatoms as described above.

[0205] The above R 1 represents a hydrogen atom or a substituent. The substituent is not particularly limited, but for example, alkyl groups (preferably having 1 to 6 carbon atoms; may be linear or branched) are preferred.

[0206] The linear or branched aliphatic hydrocarbon groups, aliphatic hydrocarbon ring groups, aromatic hydrocarbon ring groups, and heterocyclic groups described above, which may contain heteroatoms, may further have substituents.

[0207] The number of carbon atoms in the linear or branched aliphatic hydrocarbon group is not particularly limited, but is preferably 1 to 12, more preferably 1 to 10, and even more preferably 3 to 6. Examples of the above-mentioned aliphatic hydrocarbon group include alkylene groups.

[0208] The number of carbon atoms in the above-mentioned aliphatic hydrocarbon ring group (alicyclic group) is not particularly limited, but 3 to 30 is preferred, 6 to 20 is more preferred, 6 to 15 is even more preferred, and 6 to 12 is particularly preferred. The alicyclic group may be monocyclic or polycyclic, and may be a spiro ring. Examples of alicyclic groups constituting a monocyclic alicyclic group include monocyclic cycloalkanes such as cyclopentane, cyclohexane, and cyclooctane. Examples of alicyclic groups constituting a polycyclic alicyclic group include polycyclic cycloalkanes such as norbornane, tricyclodecane, tetracyclodecane, tetracyclododecane, and adamantane.

[0209] The number of carbon atoms in the aromatic hydrocarbon ring constituting the above aromatic hydrocarbon ring group is not particularly limited, but is preferably 6 to 30, more preferably 6 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. The aromatic hydrocarbon group may be monocyclic or polycyclic. Examples of the above aromatic hydrocarbon ring include benzene rings and naphthalene rings.

[0210] The number of carbon atoms in the heterocyclic group is not particularly limited, but is preferably 3 to 25, more preferably 3 to 20, even more preferably 6 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. The heterocyclic group may be monocyclic or polycyclic, and may be aromatic or aliphatic. Furthermore, the heterocyclic group may be a spiro ring. Examples of aromatic heterocyclic groups include furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, and pyridine rings. Examples of aliphatic heterocyclic groups include tetrahydropyran rings, lactone rings, sultone rings, and decahydroisoquinoline rings.

[0211] In the above formulas (M-1) to (M-5), L 11 , L 12 , L 21 ~L 23 , L 31 ~L 34 , L 41 ~L 45 , and L 51 ~L 56 Each of these independently represents a single bond or a divalent linking group. L 11 , L 12 , L 21 ~L 23 , L 31 ~L 34 , L 41 ~L 45 , and L 51 ~L 56 The divalent linking group represented by is not particularly limited, but includes alkylene groups, -CO-, and -CONR N It is preferable that the linking group is a divalent linking group consisting of -, -O-, and -S-, with one or more or a combination of two or more selected from the group. The alkylene group may be linear, branched, or cyclic. The number of carbon atoms in the alkylene group is preferably 1 to 10, and more preferably 1 to 4. The alkylene group may have further substituents. Note that the above R Nrepresents a hydrogen atom or a substituent. The substituent is not particularly limited, but for example, alkyl groups (preferably having 1 to 6 carbon atoms; may be linear or branched) are preferred.

[0212] In the above formulas (M-1) to (M-5), * indicates the bond position with the acetyl group ((OC(=O)-CH3)) explicitly shown in formula (1A).

[0213] One form of the divalent linking group M is a substituted or unsubstituted alkylene group. The alkylene group is preferably linear or branched. The number of carbon atoms is preferably 1 to 12, more preferably 1 to 10, and even more preferably 3 to 6.

[0214] Furthermore, one embodiment of the trivalent linking group M is the group represented by the following formula (1a). Formula (1a) R A -C-(L 1 -*)3 In formula (1a), R A L represents a hydrogen atom or substituent. 1 represents a single bond or an alkylene group having 1 to 6 carbon atoms that may have substituents. * represents the bond position with the acetyl group ((OC(=O)-CH3)) explicitly shown in formula (1A). Also, there are three L 1 They may be the same or different from one another. R A The substituent represented by is not particularly limited, and examples include a monovalent organic group, preferably an alkyl group having 1 to 6 carbon atoms which may have substituents, and more preferably an alkyl group having 1 to 3 carbon atoms which may have substituents. The substituent is not particularly limited, but examples include a hydroxyl group. R A Preferably, it is a hydrogen atom. L 1The alkylene group having 1 to 6 carbon atoms, which may have substituents, is preferably an alkyl group having 1 to 3 carbon atoms, which may have substituents. The substituent is not particularly limited, but for example, a hydroxyl group can be used.

[0215] Specific examples of compounds represented by formula (1A) include, for example, 1,4-BDDA, 1,6-HDDA, 1,3-BGDA, PGDA, and glycerol triacetic acid.

[0216] The solvent may be used alone or in combination of two or more types. The solvent content in the composition (total content if multiple types are included) is 3 to 24% by mass of the total mass of the composition. When the solvent content is 3% by mass or more of the total mass of the composition, the composition exhibits excellent fluidity. On the other hand, when the solvent content is 24% by mass or less of the total mass of the composition, the cured product formed by the composition exhibits excellent filling properties. In particular, for the best effect of the present invention, the upper limit of the above content is preferably 15% by mass or less, and more preferably 8% by mass or less.

[0217] Preferably, the composition contains 3% by mass or more of a solvent with a boiling point of 160°C or higher, relative to the total mass of the composition. When the composition contains 3% by mass or more of a solvent with a boiling point of 160°C or higher, curing shrinkage during film formation is less likely to occur, and the occurrence of voids and cracks can be suppressed. As a result, the cured product formed by the composition has superior filling properties. Furthermore, the upper limit for the content of solvents with a boiling point of 160°C or higher is 24% by mass or less, preferably 15% by mass or less, and more preferably 8% by mass or less, relative to the total mass of the composition.

[0218] [Rheology control agent] The composition may contain a rheology control agent. Rheology control agents are components that impart thixotropic properties to a composition, exhibiting high viscosity at low shear forces (shear rates) and low viscosity at high shear forces (shear rates). The content of the rheology control agent is preferably 1 to 24% by mass, more preferably 1 to 15% by mass, even more preferably 1 to 12% by mass, particularly preferably 1 to 10% by mass, and most preferably 1 to 7% by mass, based on the total mass of the composition. The content of the rheology control agent is preferably 0.8 to 24% by mass, more preferably 0.8 to 15% by mass, even more preferably 0.8 to 12% by mass, even more preferably 0.8 to 10% by mass, particularly preferably 0.8 to 8% by mass, and most preferably 0.8 to 7% by mass, based on the total solid content of the composition. Note that the above-mentioned rheology control agent content does not include resin-type rheology control agents. Resin-type rheology control agents correspond to the resin, which is the binder component mentioned above.

[0219] Examples of rheology control agents include organic rheology control agents and inorganic rheology control agents, with organic rheology control agents being preferred.

[0220] <Organic rheology control agent> The content of the organic rheology control agent is preferably 1 to 24% by mass, more preferably 1 to 15% by mass, even more preferably 1 to 12% by mass, particularly preferably 1 to 10% by mass, and most preferably 1 to 7% by mass, based on the total mass of the composition. The content of the organic rheology control agent is preferably 0.8 to 24% by mass, more preferably 0.8 to 15% by mass, even more preferably 0.8 to 12% by mass, even more preferably 0.8 to 10% by mass, particularly preferably 0.8 to 8% by mass, and most preferably 0.8 to 7% by mass, relative to the total solid content of the composition. Note that the above-mentioned content of organic rheology control agents does not include resin-type rheology control agents. Resin-type rheology control agents correspond to the resins that are binder components mentioned above. Organic rheology control agents may be used individually or in combination of two or more types.

[0221] Examples of organic rheology control agents include compounds having one or more (preferably two or more) adsorption groups, and further having steric repulsion structural groups. The adsorption groups interact with the surface of the magnetic particles, causing the organic rheology control agent to be adsorbed onto the surface of the magnetic particles. Examples of the adsorption groups mentioned above include acidic groups, basic groups, and amide groups. Examples of acidic groups include carboxyl groups, phosphoric acid groups, sulfol groups, phenolic hydroxyl groups, and their acid anhydride groups (such as the acid anhydride group of a carboxyl group). Carboxyl groups are preferred because they exhibit superior effects compared to the present invention. Examples of basic groups include amino groups (ammonia, primary amines, or secondary amines with one hydrogen atom removed) and imino groups. Among these, the adsorbent group is preferably a carboxyl group or an amide group, with the carboxyl group being more preferable. The steric repulsion structural group has a sterically bulky structure, which introduces steric hindrance to the magnetic particles to which the organic rheology control agent is adsorbed, thereby maintaining an appropriate space between the magnetic particles. As for the steric repulsion structural group, chain-like groups are preferred, long-chain fatty acid groups are more preferred, and long-chain alkyl groups are even more preferred. The organic rheology control agent may also preferably have hydrogen bonding units. The hydrogen-bonding unit is a substructure that functions to construct a hydrogen-bonding network between organic rheology control agents and between organic rheology control agents and other components. The organic rheology control agents that contribute to the formation of the above network may or may not be adsorbed on the surface of the magnetic particles. The hydrogen bonding unit may be the same as or different from the adsorption group described above. When the hydrogen bonding unit is the same as the adsorption group described above, a portion of the adsorption group is bonded to the surface of the magnetic particle, and the other portion functions as the hydrogen bonding unit. As hydrogen bonding units, carboxyl groups or amide groups are preferred. Carboxyl groups are preferred as hydrogen bonding units because they are easily incorporated into the curing reaction when producing cured products, while amide groups are preferred because they provide better long-term stability of the composition.

[0222] When the organic rheology control agent is a resin, the resin organic rheology control agent may or may not have repeating units containing the graft chains described above. When the resin organic rheology control agent does not substantially have repeating units containing the graft chains described above, the content of repeating units containing the graft chains described above, relative to the total mass of the resin organic rheology control agent, is preferably less than 2% by mass, more preferably 1% by mass or less, and even more preferably less than 0.1% by mass. The lower limit is 0% by mass or more.

[0223] The organic rheology control agent is preferably one or more selected from the group consisting of polycarboxylic acids (compounds having two or more carboxyl groups), polyanhydrides (compounds having two or more acid anhydride groups consisting of carboxyl groups), and amide waxes. These may be made of resin or other materials. Furthermore, these may also fall under the categories of flocculation control agents and / or flocculation dispersants, as described later.

[0224] Examples of organic rheology control agents include modified ureas, urea-modified polyamides, fatty acid amides, polyurethanes, polyamide amides, high molecular weight urea derivatives, and their salts (carboxylate salts, etc.). Modified ureas are reaction products of isocyanate monomers or their adducts with organic amines. Modified ureas are modified with polyoxyalkylene polyols (polyoxyethylene polyols, polyoxypropylene polyols, etc.) and / or alkyd chains. Urea-modified polyamides are, for example, compounds containing urea bonds and compounds to which a medium-polarity or low-polarity group has been introduced at the end. Examples of medium-polarity or low-polarity groups include polyoxyalkylene polyols (polyoxyethylene polyols, polyoxypropylene polyols, etc.) and alkyd chains. Fatty acid amides are compounds having a long-chain fatty acid group and an amide group in their molecule. These may be made of resin or other materials. Furthermore, these may also fall under the categories of flocculation control agents and / or flocculation dispersants, as described later.

[0225] The molecular weight (or weight-average molecular weight if it has a molecular weight distribution) of the organic rheology control agent is preferably in the range of 200 to 50,000. If the organic rheology control agent has an acid value, the acid value is preferably 5 to 400 mg KOH / g. If the organic rheology control agent has an amine acid value, the amine value is preferably 5 to 300 mg KOH / g.

[0226] (Agglutination control agent) Organic rheology control agents also include flocculation control agents. Flocculation control agents may be resins or other materials. The flocculation control agent has the function of binding to relatively dense aggregates such as magnetic particles, and further dispersing components such as resin precursors in the composition to create bulky aggregates. When the composition contains an aggregation control agent, the hard cake formation of magnetic particles in the composition is suppressed, and bulkier aggregates are formed, which can improve redispersibility.

[0227] Examples of flocculation control agents include cellulose derivatives. Examples of cellulose derivatives include carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxypropylethylcellulose, and salts thereof.

[0228] If the composition contains a flocculation control agent, the content of the flocculation control agent is preferably 1 to 24% by mass, more preferably 1 to 15% by mass, even more preferably 1 to 12% by mass, particularly preferably 1 to 10% by mass, and most preferably 1 to 7% by mass, based on the total mass of the composition. The content of the flocculation control agent is preferably 0.8 to 24% by mass, more preferably 0.8 to 15% by mass, even more preferably 0.8 to 12% by mass, even more preferably 0.8 to 10% by mass, particularly preferably 0.8 to 8% by mass, and most preferably 0.8 to 7% by mass, based on the total solid content of the composition. Note that the above-mentioned content of the flocculation control agent does not include the resin-type rheology control agent. The resin-type rheology control agent corresponds to the resin, which is the binder component mentioned above.

[0229] (Agglomerating agent) Organic rheological control agents also include flocculants and dispersants. The flocculant / dispersant may be a resin or something other than a resin. The flocculating dispersant adsorbs onto the surface of magnetic particles, separating them from one another. Through interactions between the dispersants, it maintains a certain distance between magnetic particles, preventing direct aggregation. As a result, aggregation of magnetic particles is suppressed, and even when aggregates form, they are relatively low-density aggregates. Furthermore, by dispersing components such as resin precursors within the composition, bulky aggregates can be created, potentially improving redispersibility.

[0230] As a flocculant / dispersant, an alkylol ammonium salt of a polybasic acid is preferred. Polybasic acids only need to have two or more acidic groups. Examples include acidic polymers containing repeating units with acidic groups (e.g., polyacrylic acid, polymethacrylic acid, polyvinyl sulfonic acid, and polyphosphate). Other examples of polybasic acids include polymers obtained by polymerizing unsaturated fatty acids such as crotonic acid. Alkyloll ammonium salts of polybasic acids are obtained by reacting these polybasic acids with alkylloll ammonium. Salts obtained by such reactions usually contain the following substructures. -C(=O)-N(-R 1 )(-R 2 -OH) Here, R 1 R is an alkyl group. 2 This is an alkylene group. The alkylol ammonium salt of the polybasic acid is preferably a polymer containing multiple of the above-mentioned substructures. When the alkylol ammonium salt of the polybasic acid is a polymer, the weight-average molecular weight is preferably 1,000 to 100,000, and more preferably 5,000 to 20,000. The polymer of the alkylol ammonium salt of the polybasic acid can bond to the surface of magnetic particles and form hydrogen bonds with other flocculant dispersant molecules, allowing the polymer's main chain structure to penetrate between magnetic particles and separate them.

[0231] One preferred embodiment of the flocculant and dispersant is an amide wax, which is a condensate obtained by dehydration condensation of (a) saturated aliphatic monocarboxylic acids and hydroxyl group-containing aliphatic monocarboxylic acids, and (b) at least one of the polybasic acids and (c) at least one of the diamines and tetraamines. It is preferable to use (a) to (c) above in a molar ratio of (a):(b):(c) = 1 to 3: 0 to 5: 1 to 6.

[0232] The saturated aliphatic monocarboxylic acids preferably have 12 to 22 carbon atoms. Specifically, examples include lauric acid, myristic acid, pentadecyl acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachidic acid, and behenic acid. The hydroxyl group-containing aliphatic monocarboxylic acids preferably have 12 to 22 carbon atoms. Specifically, examples include 12-hydroxystearic acid and dihydroxystearic acid. These saturated aliphatic monocarboxylic acids and hydroxyl group-containing aliphatic monocarboxylic acids may be used individually or in combination.

[0233] Polybasic acids are preferably dibasic acids or carboxylic acids having 2 to 12 carbon atoms, and dicarboxylic acids are more preferred. Examples of such dicarboxylic acids include aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,10-decanedicarboxylic acid, and 1,12-dodecanedicarboxylic acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid; and alicyclic dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and cyclohexylsuccinic acid. These polybasic acids may be used individually or in combination.

[0234] Diamines are preferably those having 2 to 14 carbon atoms. Specifically, examples include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, hexamethylenediamine, metaxylenediamine, tolylenediamine, paraxylenediamine, phenylenediamine, isophoronediamine, 1,10-decanediamine, 1,12-dodecanediamine, 4,4-diaminodicyclohexylmethane, and 4,4-diaminodiphenylmethane. Tetraamines are preferably those having 2 to 14 carbon atoms. Specifically, examples include butane-1,1,4,4-tetraamine and pyrimidine-2,4,5,6-tetraamine. These diamines and tetraamines may be used individually or in combination.

[0235] The amounts of diamines and tetraamines are adjusted according to the number of moles of saturated aliphatic monocarboxylic acid or hydroxyl group-containing aliphatic monocarboxylic acid and the number of moles of polybasic acids, so that the total number of carboxyl groups and the total number of amino groups are equivalent. For example, if there are 2 moles of aliphatic monocarboxylic acid and n moles (n=0~5) of aliphatic dicarboxylic acid, which is a polybasic acid, then if the amount of diamines is (n+1) moles, the acid and amine will be equivalent.

[0236] This amide wax may also be obtained as a mixture of multiple compounds having different molecular weights. The amide wax is preferably a compound represented by the following chemical formula (I). Note that the amide wax may be a single compound or a mixture. AC-(BC) m -A···(I) In formula (I), A is a dehydrated residue of a saturated aliphatic monocarboxylic acid and / or a hydroxyl group-containing saturated aliphatic monocarboxylic acid, B is a dehydrated residue of a polybasic acid, C is a dehydrogenated residue of a diamine and / or a tetraamine, and m is 0 ≤ m ≤ 5.

[0237] One preferred embodiment of the flocculant / dispersant is a compound represented by the following formula (II).

[0238] [ka]

[0239] In formula (II), R 1 R represents a monovalent linear aliphatic hydrocarbon group having 10 to 25 carbon atoms. 2 and R 3 Each of these independently represents a divalent aliphatic hydrocarbon group having 2, 4, 6, or 8 carbon atoms, a divalent alicyclic hydrocarbon group having 6 carbon atoms, or a divalent aromatic hydrocarbon group, R 4 R represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms. 5 and R 6 Each of these independently represents a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, or a hydroxyalkyl ether group. In formula (II), L1 ~L 3 Each of these independently represents an amide bond, L 1 and L 3 If it is -CONH-, then L 2 It is -NHCO-, and L 1 and L 3 If it is -NHCO-, then L 2 It is -CONH-.

[0240] R 1 A is a monovalent linear aliphatic hydrocarbon group having 10 to 25 carbon atoms, and examples include linear alkyl groups such as decyl, lauryl, myristyl, pentadecyl, stearyl, palmityl, nonadecyl, eicosyl, and behenyl groups; linear alkenyl groups such as decenyl, pentadecenyl, oleyl, and eicocenyl groups; and linear alkynyl groups such as pentadecinyl, octadecinyl, and nonadecinyl groups. Among them, R 1 The linear aliphatic hydrocarbon group is preferably a monovalent linear aliphatic hydrocarbon group having 14 to 25 carbon atoms, and more preferably a monovalent linear aliphatic hydrocarbon group having 18 to 21 carbon atoms. The linear aliphatic hydrocarbon group is preferably an alkyl group.

[0241] R 2 and R 3 Examples of divalent aliphatic hydrocarbon groups having 2, 4, 6, or 8 carbon atoms include ethylene, n-butylene, n-hexylene, and n-octylene groups. R 2 and R 3 Examples of divalent alicyclic hydrocarbon groups having 6 carbon atoms in this context include the 1,4-cyclohexylene group, the 1,3-cyclohexylene group, and the 1,2-cyclohexylene group. R 2 and R 3 Examples of divalent aromatic hydrocarbon groups in this context include arylene groups having 6 to 10 carbon atoms, such as 1,4-phenylene, 1,3-phenylene, and 1,2-phenylene.

[0242] Among them, R 2 and R3 In terms of excellent thickening effect, divalent aliphatic hydrocarbon groups having 2, 4, 6, or 8 carbon atoms are preferred, more preferably divalent aliphatic hydrocarbon groups having 2, 4, or 6 carbon atoms, even more preferably divalent aliphatic hydrocarbon groups having 2 or 4 carbon atoms, and most preferably divalent aliphatic hydrocarbon groups having 2 carbon atoms. Linear alkylene groups are preferred for the divalent aliphatic hydrocarbon groups.

[0243] R 4 This represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, and among these, linear or branched alkylene groups are preferred, with linear alkylene groups being more preferred, due to their excellent thickening effect. Also, R 4 The number of carbon atoms in the divalent aliphatic hydrocarbon group is 1 to 8, and in terms of excellent thickening effect, 1 to 7 is preferred, 3 to 7 is more preferred, 3 to 6 is even more preferred, and 3 to 5 is particularly preferred. Therefore, R 4 The linear or branched alkylene group having 1 to 8 carbon atoms is preferred, a linear alkylene group having 1 to 7 carbon atoms is more preferred, a linear alkylene group having 3 to 7 carbon atoms is even more preferred, a linear alkylene group having 3 to 6 carbon atoms is particularly preferred, and a linear alkylene group having 3 to 5 carbon atoms is most preferred.

[0244] R 5 and R 6 Examples of monovalent aliphatic hydrocarbon groups having 1 to 3 carbon atoms include linear or branched alkyl groups having 1 to 3 carbon atoms such as methyl, ethyl, propyl, and isopropyl groups; linear or branched alkenyl groups having 2 to 3 carbon atoms such as vinyl, 1-methylvinyl, and 2-propenyl groups; and linear or branched alkynyl groups having 2 to 3 carbon atoms such as ethynyl and propynyl groups.

[0245] R 5 and R 6 Examples of hydroxyalkyl ether groups in this context include mono- or di(hydroxy)C groups such as 2-hydroxyethoxy, 2-hydroxypropoxy, and 2,3-dihydroxypropoxy. 1-3Alkyl ether groups are one example.

[0246] Among them, R 5 and R 6 Each of these groups is preferably a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms, even more preferably a linear alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.

[0247] The compounds represented by formula (II) are preferably those represented by the following formulas (II-1) to (II-9).

[0248] [ka]

[0249] Examples of flocculants and dispersants include ANTI-TERRA-203, 204, 206, and 250 (all trade names, manufactured by BYK); ANTI-TERRA-U (trade name, manufactured by BYK); DISPER BYK-102, 180, and 191 (all trade names, manufactured by BYK); BYK-P105 (trade name, manufactured by BYK); TEGO Disper630 and 700 (both trade names, manufactured by Evonik Degussa Japan); TALEN VA-705B (trade name, manufactured by Kyoeisha Chemical Co., Ltd.); FLOWNON RCM-300TL and RCM-230AF (trade names, manufactured by Kyoeisha Chemical Co., Ltd., amide wax).

[0250] If the composition contains a flocculant, the content of the flocculant is preferably 1 to 24% by mass, more preferably 1 to 15% by mass, even more preferably 1 to 12% by mass, particularly preferably 1 to 10% by mass, and most preferably 1 to 7% by mass, based on the total mass of the composition. The content of the flocculant dispersant is preferably 0.8 to 24% by mass, more preferably 0.8 to 15% by mass, even more preferably 0.8 to 12% by mass, even more preferably 0.8 to 10% by mass, particularly preferably 0.8 to 8% by mass, and most preferably 0.8 to 7% by mass, based on the total solid content of the composition. Note that the above-mentioned content of the flocculating and dispersing agent does not include the resin-type rheology control agent. The resin-type rheology control agent corresponds to the resin, which is the binder component mentioned above.

[0251] <Inorganic rheology control agent> Examples of inorganic rheological control agents include bentonite, silica, calcium carbonate, and smectite.

[0252] [Hardening agent] The composition may contain a curing agent. In particular, if the composition contains a compound having an epoxy group and / or an oxetanyl group as a binder component, it is also preferable that the composition contains a curing agent. Examples of curing agents include phenol-based curing agents, naphthol-based curing agents, acid anhydride-based curing agents, active ester-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, carbodiimide-based curing agents, and amine adduct-based curing agents. The hardening agent may be used alone or in combination of two or more types.

[0253] Specific examples of phenol-based and naphthol-based curing agents include, for example, "MEH-7700," "MEH-7810," and "MEH-7851" from Meiwa Chemical Co., Ltd., "NHN," "CBN," and "GPH" from Nippon Kayaku Co., Ltd., "SN-170," "SN-180," "SN-190," "SN-475," "SN-485," "SN-495," "SN-375," and "SN-395" from Nippon Steel & Sumitomo Metal Chemical Co., Ltd., and "LA-7052," "LA-7054," "LA-3018," "LA-3018-50P," "LA-1356," "TD2090," and "TD-2090-60M" from DIC Corporation.

[0254] Examples of acid anhydride-based curing agents include curing agents having one or more acid anhydride groups in one molecule. Specific examples of acid anhydride-based curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexen-1,2-dicarboxylic acid anhydride, trimellitic anhydride, pyromellitic anhydride, and bensofenone tetracarboxylic acid di Examples include anhydrides, biphenyltetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and polymer-type acid anhydrides such as styrene-maleic acid resin obtained by copolymerizing styrene and maleic acid. Commercially available acid anhydride-based curing agents include "HNA-100," "MH-700," "MTA-15," "DDSA," "HF-08," and "OSA" from Shin Nippon Rika Co., Ltd., "YH306" and "YH307" from Mitsubishi Chemical Corporation, "H-TMAn" from Mitsubishi Gas Chemical Corporation, and "HN-2200," "HN-2000," "HN-5500," and "MHAC-P" from Hitachi Chemical Co., Ltd.

[0255] As the active ester-based curing agent, compounds having three or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are preferably used. Preferred active ester curing agents include active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated phenol novolac, and active ester compounds containing a benzoylated phenol novolac. Note that "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentalene-phenylene.

[0256] Commercially available active ester curing agents include active ester compounds containing a dicyclopentadiene-type diphenol structure such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L", and "EXB-8000L-65TM" (manufactured by DIC Corporation); active ester compounds containing a naphthalene structure such as "EXB9416-70BK" and "EXB-8150-65T" (manufactured by DIC Corporation); and phenol novolac. Examples of active ester compounds containing acetylated compounds include "DC808" (manufactured by Mitsubishi Chemical Corporation); examples of active ester compounds containing benzoylated phenol novolacs include "YLH1026" (manufactured by Mitsubishi Chemical Corporation); examples of active ester curing agents that are acetylated phenol novolacs include "DC808" (manufactured by Mitsubishi Chemical Corporation); and examples of active ester curing agents that are benzoylated phenol novolacs include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation).

[0257] Specific examples of benzoxazine-based curing agents include "JBZ-OP100D" and "ODA-BOZ" from JFE Chemical Corporation; "HFB2006M" from Showa Polymer Co., Ltd.; and "Pd" and "Fa" from Shikoku Chemicals Co., Ltd.

[0258] Specific examples of cyanate ester-based curing agents include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate ester resins) manufactured by Lonza Japan, "BA230", and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate is triazined and trimerized).

[0259] Specific examples of carbodiimide-based curing agents include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd.

[0260] Examples of commercially available amine adduct type curing agents include Amicure PN-23 and PN-50 (both manufactured by Ajinomoto Fine Techno Co., Ltd.).

[0261] When the composition contains a compound having an epoxy group (or a compound having an oxetanyl group) and a curing agent, the ratio of the content of the compound having an epoxy group (or a compound having an oxetanyl group) to the content of the curing agent is preferably such that the equivalent ratio of epoxy groups (or compounds having an oxetanyl group) in the compound having an epoxy group to the reactive groups (active hydrogen groups such as hydroxyl groups in the curing agent) ("number of epoxy groups (or oxetanyl groups)" / "number of reactive groups") is 30 / 70 to 70 / 30, more preferably 40 / 60 to 60 / 40, and even more preferably 45 / 55 to 55 / 45. Furthermore, if the composition includes a compound having an epoxy group, a compound having an oxetanyl group, and a curing agent, it is preferable that the equivalent ratio of the epoxy group and the compound having an oxetanyl group in the epoxy group-containing compound to the reactive group in the curing agent ("number of epoxy groups and number of oxetanyl groups" / "number of reactive groups") satisfies the above numerical range. The curing agent content is preferably 0.001 to 3.5% by mass, and more preferably 0.01 to 3.5% by mass, based on the total mass of the composition. The curing agent content is preferably 0.001 to 3.5% by mass, and more preferably 0.01 to 3.5% by mass, relative to the total solid content of the composition.

[0262] [Curing accelerator] The composition may also contain a curing accelerator. In particular, if the composition contains a compound having an epoxy group and / or an oxetanyl group as a binder component, it is also preferable that the composition contains a curing accelerator. Examples of curing accelerators include triphenylphosphine, methyltributylphosphonium dimethyl phosphate, tris-orthotolylphosphine, and boron trifluoride amine complexes. A commercially available phosphate-based curing accelerator is Hishikorin PX-4MP (manufactured by Nippon Chemical Industrial Co., Ltd.). Other curing accelerators include 2-methylimidazole (trade name; 2MZ), 2-undecylimidazole (trade name; C11-Z), 2-heptadecylimidazole (trade name; C17Z), 1,2-dimethylimidazole (trade name; 1,2DMZ), 2-ethyl-4-methylimidazole (trade name; 2E4MZ), 2-phenylimidazole (trade name; 2PZ), 2-phenyl-4-methylimidazole (trade name; 2P4MZ), and 1-benzyl-2-methylimidazole (trade name; 1B2M Z), 1-benzyl-2-phenylimidazole (trade name; 1B2PZ), 1-cyanoethyl-2-methylimidazole (trade name; 2MZ-CN), 1-cyanoethyl-2-undecylimidazole (trade name; C11Z-CN), 1-cyanoethyl-2-phenylimidazolium trimellitate (trade name; 2PZCNS-PW), 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine (trade name; 2MZ-A), 2,4-diamino-6-[2'-undecyl Midazolyl-(1')-ethyl-s-triazine (trade name: C11Z-A), 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine (trade name: 2E4MZ-A), 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate adduct (trade name: 2MA-OK), 2-phenyl-4,5-dihydroxymethylimidazole (trade name: 2PHZ-PW), 2-phenyl-4-methyl-5-hydroxy Examples of imidazole-based curing accelerators include methylimidazole (trade name: 2P4MHZ-PW), 1-cyanoethyl-2-phenylimidazole (trade name: 2PZ-CN), 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine (trade name: 2MZA-PW), and 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct (trade name: 2MAOK-PW) (all manufactured by Shikoku Chemicals, Inc.). Furthermore, as a triarylphosphine-based curing accelerator, the compound described in paragraph 0052 of Japanese Patent Publication No. 2004-043405 is also an example.As a phosphorus-based curing accelerator obtained by adding triphenylborane to triarylphosphine, the compound described in paragraph 0024 of Japanese Patent Application Publication No. 2014-005382 can also be cited. The curing accelerator content is preferably 0.0002 to 3% by mass, more preferably 0.002 to 2% by mass, and even more preferably 0.01 to 1% by mass, based on the total mass of the composition. The content of the curing accelerator is preferably 0.0002 to 3% by mass, more preferably 0.002 to 2% by mass, and even more preferably 0.02 to 1% by mass, based on the total solid content of the composition.

[0263] [Polymerization initiator] The composition may contain a polymerization initiator. In particular, if the composition contains a compound containing an ethylenically unsaturated group as a binder component, it is preferable that the composition also contains a polymerization initiator. The polymerization initiator is not particularly limited, and known polymerization initiators can be used. Examples of polymerization initiators include photopolymerization initiators and thermal polymerization initiators. If the composition contains a polymerization initiator, its content is preferably 0.5 to 10% by mass, more preferably 0.5 to 5% by mass, and even more preferably 0.5 to 3% by mass, based on the total mass of the composition. If the composition contains a polymerization initiator, its content is preferably 0.8 to 5% by mass, more preferably 0.8 to 4% by mass, and even more preferably 1.5 to 3% by mass, based on the total solid content of the composition.

[0264] <Thermal polymerization initiator> Examples of thermal polymerization initiators include azo compounds such as 2,2'-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismalenonitrile, and dimethyl-(2,2')-azobis(2-methylpropionate)[V-601], as well as organic peroxides such as benzoyl peroxide, lauroyl peroxide, and potassium persulfate. Specific examples of polymerization initiators include those described on pages 65-148 of "Ultraviolet Curing Systems" by Kiyoshi Kato (published by Sogo Gijutsu Center Co., Ltd., 1989).

[0265] <Photopolymerization initiator> The photopolymerization initiator is not particularly limited as long as it can initiate polymerization of the polymerizable compound, and known photopolymerization initiators can be used. Preferred photopolymerization initiators include, for example, those that are photosensitive to light in the ultraviolet to visible light range. Alternatively, an activator that interacts with a photoexcited sensitizer to generate active radicals may be used, or an initiator that initiates cationic polymerization depending on the type of polymerizable compound. Furthermore, the photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least 50 in the range of 300 to 800 nm (more preferably 330 to 500 nm).

[0266] Examples of photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds containing a triazine skeleton, compounds containing an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds, and hydroxyacetophenone. For specific examples of photopolymerization initiators, see, for example, paragraphs 0265 to 0268 of Japanese Patent Application Publication No. 2013-029760, the contents of which are incorporated herein by reference.

[0267] More specifically, as photopolymerization initiators, for example, the aminoacetophenone-based initiator described in Japanese Patent Publication No. 10-291969 and the acylphosphine-based initiator described in Japanese Patent Publication No. 4225898 can also be used. Examples of hydroxyacetophenone compounds that can be used include Omnirad-184, Omnirad-1173, Omnirad-500, Omnirad-2959, and Omnirad-127 (trade names, all manufactured by IGM Resins BV). As aminoacetophenone compounds, for example, commercially available products such as Omnirad-907, Omnirad-369, and Omnirad-379EG (trade names, all manufactured by IGM Resins BV) can be used. As aminoacetophenone compounds, compounds described in Japanese Patent Application Publication No. 2009-191179, whose absorption wavelengths are matched to long-wave light sources such as 365 nm or 405 nm, can also be used. As acylphosphine compounds, commercially available products such as Omnirad-819 and Omnirad-TPO (trade names, both manufactured by IGM Resins BV) can be used.

[0268] As a photopolymerization initiator, oxime ester-based polymerization initiators (oxime compounds) are more preferred. Oxime compounds are particularly preferred because they are highly sensitive, have high polymerization efficiency, and allow for easy design of high colorant content in the composition. Specific examples of oxime compounds include the compounds described in Japanese Patent Publication No. 2001-233842, the compounds described in Japanese Patent Publication No. 2000-080068, or the compounds described in Japanese Patent Publication No. 2006-342166. Examples of oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. Other examples include compounds described in JCSPerkin II (1979) pp.1653-1660, JCSPerkin II (1979) pp.156-162, Journal of Photopolymer Science and Technology (1995) pp.202-232, Japanese Patent Publication No. 2000-066385, Japanese Patent Publication No. 2000-080068, Japanese Patent Publication No. 2004-534797, and Japanese Patent Publication No. 2006-342166. Commercially available options include IRGACURE-OXE01 (BASF), IRGACURE-OXE02 (BASF), IRGACURE-OXE03 (BASF), or IRGACURE-OXE04 (BASF). Additionally, TR-PBG-304 (Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA Arclus NCI-831, ADEKA Arclus NCI-930 (ADEKA), or N-1919 (carbazole oxime ester skeleton-containing photoinitiator (ADEKA)) can also be used.

[0269] In addition, other oxime compounds not listed above may be used, such as the compound described in Japanese Patent Publication No. 2009-519904, in which an oxime is linked to the N position of carbazole; the compound described in U.S. Patent No. 7,626,957, in which a heterosubstituted group is introduced to the benzophenone moiety; the compound described in Japanese Patent Application Publication No. 2010-015025 and U.S. Patent Publication No. 2009-292039, in which a nitro group is introduced to the dye moiety; the ketoxime compound described in International Publication No. 2009-131189; and the compound described in U.S. Patent No. 7,556,910, which contains a triazine skeleton and an oxime skeleton in the same molecule; and the compound described in Japanese Patent Application Publication No. 2009-221114, which has an absorption maximum at 405 nm and good sensitivity to g-line light sources. For example, paragraphs 0274 to 0275 of Japanese Patent Publication No. 2013-029760 can be referenced, and this content is incorporated herein. Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). The NO bond of the oxime compound may be the (E) oxime compound, the (Z) oxime compound, or a mixture of the (E) and (Z) oxime compounds.

[0270] [ka]

[0271] In formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. In formula (OX-1), a monovalent nonmetallic group is preferred as the monovalent substituent represented by R. Examples of monovalent nonmetallic atomic groups include alkyl groups, aryl groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, heterocyclic groups, alkylthiocarbonyl groups, and arylthiocarbonyl groups. These groups may also have one or more substituents. Furthermore, the aforementioned substituents may be further substituted with other substituents. Examples of substituents include halogen atoms, aryloxy groups, alkoxycarbonyl groups or aryloxycarbonyl groups, acyloxy groups, acyl groups, alkyl groups, and aryl groups. In formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group, with the aryl group or heterocyclic group being preferred. These groups may have one or more substituents. Examples of substituents include those mentioned above. In formula (OX-1), the divalent organic group represented by A is preferably an alkylene group, a cycloalkylene group, or an alkylylene group having 1 to 12 carbon atoms. These groups may have one or more substituents. Examples of substituents include those mentioned above.

[0272] Oxime compounds containing a fluorine atom can also be used as photopolymerization initiators. Specific examples of oxime compounds containing a fluorine atom include the compound described in Japanese Patent Publication No. 2010-262028; compounds 24, 36-40 described in Japanese Patent Publication No. 2014-500852; and compound (C-3) described in Japanese Patent Publication No. 2013-164471; etc. This information is incorporated herein by reference.

[0273] Compounds represented by the following general formulas (1) to (4) can also be used as photopolymerization initiators.

[0274] [ka]

[0275] [ka]

[0276] In equation (1), R 1 and R 2 Each of these independently represents an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. 1 and R 2 If R is a phenyl group, the phenyl groups may bond together to form a fluorene group, 3 and R 4 Each of these independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or a carbonyl group.

[0277] In equation (2), R 1 , R 2 , R 3 , and R 4 R in equation (1) 1 , R 2 , R 3 , and R 4 It is synonymous with R 5 is, -R 6, -OR 6 , -SR 6 , -COR 6 ,-CONR 6 R 6 , -NR 6 COR 6 , -OCOR 6 ,-COOR 6 -SCOR 6 ,-OCSR 6 ,-COSR 6 -CSOR 6 -CN represents a halogen atom or a hydroxyl group, R 6 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms; X represents a direct bond or a carbonyl group; and a represents an integer from 0 to 4.

[0278] In equation (3), R 1 R represents an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. 3 and R 4 Each of these independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or a carbonyl group.

[0279] In equation (4), R 1 , R 3 , and R 4 R in equation (3) is 1 , R 3 , and R 4 It is synonymous with R 5 is, -R 6 , -OR 6 , -SR 6 , -COR 6 ,-CONR 6 R 6 , -NR 6 COR 6 , -OCOR 6 ,-COOR 6 -SCOR 6 ,-OCSR6 ,-COSR 6 -CSOR 6 -CN represents a halogen atom or a hydroxyl group, R 6 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms; X represents a direct bond or a carbonyl group; and a represents an integer from 0 to 4.

[0280] In the above equations (1) and (2), R 1 and R 2 The group is preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group, or a phenyl group. 3 The group is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a xylyl group. 4 A C1-C6 alkyl group or phenyl group is preferred. 5 The group is preferably a methyl group, ethyl group, phenyl group, tolyl group, or naphthyl group. X is preferably directly bonded. Furthermore, in the above equations (3) and (4), R 1 The group is preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group, or a phenyl group. 3 The group is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a xylyl group. 4 A C1-C6 alkyl group or a phenyl group is preferred. 5 The group is preferably a methyl group, ethyl group, phenyl group, tolyl group, or naphthyl group. X is preferably directly bonded. Specific examples of compounds represented by formulas (1) and (2) include, for example, the compounds described in paragraphs 0076 to 0079 of Japanese Patent Publication No. 2014-137466. This information is incorporated herein by reference.

[0281] Specific examples of oxime compounds preferably used in the above composition are shown below. Among the oxime compounds shown below, the oxime compound represented by the general formula (C-13) is more preferred. Furthermore, as oxime compounds, those listed in Table 1 of International Publication No. 2015-036910 can also be used, and the above information is incorporated herein.

[0282] [ka]

[0283] [ka]

[0284] The oxime compound preferably has a maximum absorption wavelength in the 350-500 nm wavelength range, more preferably in the 360-480 nm wavelength range, and even more preferably has high absorbance at wavelengths of 365 nm and 405 nm. From the viewpoint of sensitivity, the molar extinction coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and even more preferably 5,000 to 200,000. The molar extinction coefficient of a compound can be determined using known methods, but it is preferable to measure it using an ultraviolet-visible spectrophotometer (Cary-5 spctrophotometer, Varian) with ethyl acetate at a concentration of 0.01 g / L. Two or more photopolymerization initiators may be used in combination as needed.

[0285] Furthermore, as photopolymerization initiators, compounds described in paragraph 0052 of Japanese Patent Publication No. 2008-260927, paragraphs 0033-0037 of Japanese Patent Publication No. 2010-097210, and paragraph 0044 of Japanese Patent Publication No. 2015-068893 can also be used, and the above content is incorporated herein. Additionally, oxime initiators described in Korean Published Patent No. 10-2016-0109444 can also be used.

[0286] [Polymerization inhibitors] The composition may contain polymerization inhibitors. The polymerization inhibitor is not particularly limited, and known polymerization inhibitors can be used. Examples of polymerization inhibitors include phenolic polymerization inhibitors (e.g., p-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol, 4,4'-thiobis(3-methyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4-methoxynaphthol, etc.); hydroquinone polymerization inhibitors (e.g., hydroquinone, 2,6-di-tert-butylhydro) Examples include: loquinone, quinone-based polymerization inhibitors (e.g., benzoquinone, etc.); free radical polymerization inhibitors (e.g., 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, etc.); nitrobenzene-based polymerization inhibitors (e.g., nitrobenzene, 4-nitrotoluene, etc.); and phenothiazine-based polymerization inhibitors (e.g., phenothiazine, 2-methoxyphenothiazine, etc.). Among these, phenolic polymerization inhibitors or free radical polymerization inhibitors are preferred.

[0287] Polymerization inhibitors are particularly effective when used in conjunction with resins containing curable groups. The content of polymerization inhibitor in the composition is not particularly limited, but is preferably 0.0001 to 0.5% by mass, more preferably 0.0001 to 0.2% by mass, and even more preferably 0.0001 to 0.05% by mass, relative to the total mass of the composition. The polymerization inhibitor content is preferably 0.0001 to 0.5% by mass, more preferably 0.0001 to 0.2% by mass, and even more preferably 0.0001 to 0.05% by mass, relative to the total solid content of the composition.

[0288] [Surfactants] The composition may contain a surfactant. The surfactant contributes to improving the applicability of the composition. If the composition contains a surfactant, the surfactant content is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 0.5% by mass, and even more preferably 0.005 to 0.1% by mass, based on the total mass of the composition. The surfactant content is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 0.5% by mass, and even more preferably 0.01 to 0.1% by mass, relative to the total solid content of the composition.

[0289] Examples of surfactants include fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants.

[0290] For example, if the composition contains a fluorine-based surfactant, the liquid properties of the composition (especially its fluidity) are further improved. That is, when forming a film using a composition containing a fluorine-based surfactant, the interfacial tension between the surface to be coated and the coating liquid is reduced, improving the wettability to the surface and thus improving the coatability to the surface. Therefore, even when forming a thin film of several micrometers with a small amount of liquid, it is effective in more favorably forming a film of uniform thickness with less thickness variation.

[0291] The fluorine content in the fluorinated surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 7 to 25% by mass. Fluorinated surfactants with a fluorine content within this range are effective in terms of uniformity of coating film thickness and / or liquid saving, and also have good solubility in the composition.

[0292] Examples of fluorinated surfactants include those described in paragraphs 0060 to 0064 of Japanese Patent Publication No. 2014-041318 (corresponding to paragraphs 0060 to 0064 of International Publication No. 2014 / 017669), those described in paragraphs 0117 to 0132 of Japanese Patent Publication No. 2011-132503, and those described in Japanese Patent Publication No. 2020-008634, the contents of which are incorporated herein by reference. Examples of commercially available fluorine-based surfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, R-41, R- 41-LM, R-01, R-40, R-40-LM, R-43, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (all manufactured by DIC Corporation), Florard FC430, FC431, FC171 (all manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC Inc.), PolyFox Examples include PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA), and Futtergent 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F (all manufactured by NEOS Corporation). Block polymers can also be used as fluorine-based surfactants, and a specific example is the compound described in Japanese Patent Publication No. 2011-089090. Examples of silicone-based surfactants include KF6001 and KF6007 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0293] From an environmental perspective, the use of perfluoroalkyl sulfonic acids and their salts, as well as perfluoroalkyl carboxylic acids and their salts, may be restricted. When reducing the content of the above compounds in the composition, the content of perfluoroalkyl sulfonic acid (particularly perfluoroalkyl sulfonic acid with 6 to 8 carbon atoms in the perfluoroalkyl group) and its salts, and perfluoroalkyl carboxylic acid (particularly perfluoroalkyl carboxylic acid with 6 to 8 carbon atoms in the perfluoroalkyl group) and its salts is preferably 0.01 to 1,000 ppb, more preferably 0.05 to 500 ppb, and even more preferably 0.1 to 300 ppb, relative to the total solid content of the composition. Furthermore, the composition may not substantially contain perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts. For example, by using compounds that can substitute for perfluoroalkyl sulfonic acid and its salts, and compounds that can substitute for perfluoroalkyl carboxylic acid and its salts, a composition substantially free of perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts, may be made. Examples of compounds that can substitute for regulated compounds include compounds that have been excluded from regulation due to differences in the number of carbon atoms in the perfluoroalkyl group. However, the foregoing does not preclude the use of perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts. The composition may contain perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts, to the maximum permissible extent.

[0294] [Adhesion enhancer] The composition may also preferably contain a silane coupling agent as an adhesion enhancer. Examples of silane coupling agents include N-phenyl-3-aminopropyltrimethoxysilane, phenyltrimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N-(2-(vinylbenzylamino)ethyl)3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, and 3-chloropropyltrimethoxysilane. Examples of commercially available silane coupling agents include the KBM series and KBE series (e.g., KBM-573, KBM-103) manufactured by Shin-Etsu Chemical Co., Ltd. If the composition contains an adhesion aid, the content of the adhesion aid is preferably 0.05 to 2% by mass, more preferably 0.05 to 1% by mass, and even more preferably 0.05 to 0.8% by mass, based on the total mass of the composition. The content of the adhesion aid is preferably 0.05 to 2% by mass, more preferably 0.05 to 1% by mass, and even more preferably 0.05 to 0.8% by mass, relative to the total solid content of the composition.

[0295] [Other optional ingredients] The composition may further contain other optional components in addition to those described above. Examples include sensitizers, co-sensitizers, plasticizers, diluents, oil-sensing agents, fillers, and rubber components. Furthermore, known additives such as auxiliary agents (e.g., defoamers, flame retardants, leveling agents, peel accelerators, antioxidants, fragrances, surface tension modifiers, and chain transfer agents) may be added as needed.

[0296] [Physical properties of the composition] The viscosity of the composition at 23°C is preferably 1 to 1,000,000 Pa·s, more preferably 10 to 50,000 Pa·s, and even more preferably 50 to 10,000 Pa·s, from the viewpoint of superior settling stability of magnetic particles when the shear rate is 0.1 (1 / s). The viscosity of the composition at 23°C is preferably 100 Pa·s or less, more preferably 50 Pa·s or less, and even more preferably 10 Pa·s or less, when the shear rate is 1000 (1 / s), from the viewpoint of superior settling stability of the magnetic particles. The lower limit when the shear rate is 1000 (1 / s) is preferably 0.001 Pa·s or more. Here, the viscosity of the composition at 23°C is obtained by measuring it at 23°C using an MCR-102 (manufactured by Anton Paar) while increasing the speed from 0.1 / s to 1000 / s.

[0297] [Method for manufacturing the composition] The composition can be prepared by mixing the above components using a known mixing method (for example, a mixing method using a stirrer, homogenizer, high-pressure emulsifier, wet grinder, or wet disperser). When preparing the composition, each component may be blended together at once, or each component may be dissolved or dispersed in a solvent and then blended sequentially. Furthermore, there are no particular restrictions on the order of addition or working conditions during blending. For example, when using multiple types of other resins, they may be blended together at once, or each type may be blended in multiple separate steps.

[0298] [Application] The composition can be suitably used as a hole-filling composition for holes such as via holes and through holes provided in a substrate. When the composition is used as a hole-filling composition, it is preferable that the composition contains a resin precursor as a binder component, and it is even more preferable that it contains an epoxy compound and / or an oxetanyl compound in that the effects of the present invention are superior. When the composition contains an epoxy compound and / or an oxetanyl compound as a binder component, an example of a specific procedure for filling the holes is a method comprising the following steps 1 to 3. Step 1: A step of filling holes in a substrate having holes such as via holes or through holes by applying a composition using a known coating method such as slit coating, inkjet coating, rotary coating, casting coating, roll coating, and screen printing. Step 2: A step to cure the epoxy compound and / or oxetanyl compound in the composition by heating the composition on the substrate after Step 1 at, for example, approximately 120 to 180°C for approximately 30 to 90 minutes. Step 3: Remove any excess material protruding from the substrate surface of the cured material by physical polishing to create a flat surface.

[0299] Furthermore, if the composition contains a photocurable resin precursor as a binder component, it is preferable to change step 2 in steps 1 to 3 above to a step that includes an exposure treatment by irradiating with active light or radiation.

[0300] Furthermore, it is preferable that the composition be formed into a film. Furthermore, when curing the composition, it is preferable that the composition contains a resin precursor as a binder component, and it is even more preferable that it contains an epoxy compound and / or an oxetanyl compound in that the effects of the present invention are superior. The film formed by the composition is suitably used as an electronic component such as an antenna and inductor, which are installed in electronic communication equipment and the like. The thickness of the film formed by the composition is preferably 1 to 10,000 μm, more preferably 10 to 1,000 μm, and particularly preferably 15 to 800 μm, from the viewpoint of superior magnetic permeability.

[0301] [Cured product (cured product containing magnetic particles)] The cured product of the present invention (magnetic particle-containing cured product) is formed using the composition of the present invention described above. The shape of the cured product of the present invention is not particularly limited; for example, as described above, it may be a shape that conforms to the shape of the holes provided in the substrate, or it may be in the form of a film.

[0302] [Method for manufacturing hardened products] The cured product of the present invention can be obtained, for example, by curing the above composition. When curing the composition, it is preferable that the composition contains a resin precursor as a binder component, and it is even more preferable that it contains an epoxy compound and / or an oxetanyl compound in that the effects of the present invention are superior. The method for producing the cured product is not particularly limited, but it is preferable to include the following steps. ·Composition layer formation process ·Curing process

[0303] The following describes the method for manufacturing a cured product according to the present invention, using the case where the cured product is a film as an example. Hereinafter, the film-like cured product will be referred to as a magnetic particle-containing cured film.

[0304] <Composition layer formation process> In the composition layer formation process, the composition is applied to a substrate (support) or the like to form a layer of the composition (composition layer). The substrate may be, for example, a wiring board having an antenna portion or an inductor portion.

[0305] Various coating methods can be applied to the substrate, including slit coating, inkjet coating, rotary coating, casting coating, roll coating, and screen printing. The film thickness of the composition layer is preferably 1 to 10,000 μm, more preferably 10 to 1,000 μm, and even more preferably 15 to 800 μm. The composition layer coated on the substrate may be heated (pre-baked), which can be done, for example, by heating it at a temperature of 50 to 140°C for 10 to 1,800 seconds using a hot plate, oven, etc. Pre-baking is especially preferable when the composition contains a solvent.

[0306] <Curing process> The curing process is not particularly limited as long as it can cure the composition layer, but examples include a heat treatment to heat the composition layer and an exposure treatment to irradiate the composition layer with active light or radiation.

[0307] When heat treatment is performed, the heat treatment can be carried out continuously or in batches using heating means such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater. The heating temperature during the heat treatment is preferably 120 to 260°C, and more preferably 150 to 240°C. While there are no particular restrictions on the heating time, 10 to 1800 seconds is preferred. Furthermore, the pre-baking process in the composition layer formation step may also serve as the heat treatment in the curing step.

[0308] When performing exposure processing, there are no particular limitations on the method of irradiation with active light or radiation, but it is preferable to irradiate through a photomask having a patterned opening. Exposure is preferably carried out by irradiation with radiation. Preferred radiation for exposure is ultraviolet light such as g-rays, h-rays, or i-rays, and a high-pressure mercury lamp is preferred as the light source. The irradiation intensity is 5 to 1500 mJ / cm². 2 Preferably, 10 to 1000 mJ / cm² 2 This is preferable. If the composition contains a thermal polymerization initiator, the composition layer may be heated during the exposure treatment described above. The heating temperature is not particularly limited, but 80 to 250°C is preferred. The heating time is also not particularly limited, but 30 to 300 seconds is preferred. Furthermore, when the composition layer is heated during the exposure process, this process may also serve as a post-heating step, as described later. In other words, when the composition layer is heated during the exposure process, the method for manufacturing the magnetic particle-containing cured film does not need to include a post-heating step.

[0309] <Developing process> If exposure is performed during the curing process, a development process may be included in the process. The development step involves developing the above-mentioned composition layer after exposure to form a hardened film containing magnetic particles. In this step, the parts of the composition layer that were not irradiated with light during the exposure process are dissolved, leaving only the photo-cured parts, and a patterned hardened film containing magnetic particles is obtained. While there are no particular restrictions on the type of developer used in the development process, an alkaline developer is preferable as it will not damage the circuitry. The development temperature is, for example, 20-30°C. The development time is typically 20 to 90 seconds. In recent years, development has sometimes been extended to 120 to 180 seconds to better remove residue. Furthermore, to further improve residue removal, the developer solution may be shook out every 60 seconds, and the process of supplying fresh developer solution may be repeated several times.

[0310] As the alkaline developer, an alkaline aqueous solution prepared by dissolving an alkaline compound in water to a concentration of 0.001 to 10% by mass (preferably 0.01 to 5% by mass) is preferred. Examples of alkaline compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo[5.4.0]-7-undecene (of which organic alkalis are preferred). When used as an alkaline developer, the film is generally washed with water after development.

[0311] <Post-bake> When exposure treatment is performed in the curing process, it is preferable to perform a heat treatment (post-bake) after the curing process. Post-bake is a heat treatment to complete the curing. When a development process is performed, it is preferable to perform post-bake after the development process. The heating temperature is preferably 240°C or lower, and more preferably 220°C or lower. There is no particular lower limit, but considering efficient and effective processing, 50°C or higher is preferable, and 100°C or higher is preferable. There is no particular limit to the heating time, but 10 to 1800 seconds is preferable. Post-baking can be carried out continuously or in batches using heating means such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater.

[0312] The above post-bake is preferably carried out in a low-oxygen atmosphere. The oxygen concentration is preferably 19% by volume or less, more preferably 15% by volume or less, even more preferably 10% by volume or less, particularly preferably 7% by volume or less, and most preferably 3% by volume or less. There is no particular lower limit, but 10 ppm by volume or more is practical.

[0313] Alternatively, instead of post-baking by heating as described above, curing may be completed by UV (ultraviolet) irradiation. In this case, the composition preferably further contains a UV curing agent. The UV curing agent is preferably one that can cure at a wavelength shorter than 365 nm, which is the exposure wavelength of the polymerization initiator added for the lithography process using normal i-line exposure. An example of a UV curing agent is Ciba IrgaCure 2959 (trade name). When UV irradiation is performed, it is preferable that the composition layer is made of a material that cures at a wavelength of 340 nm or less. There is no particular lower limit for the wavelength, but 220 nm or more is common. The exposure amount for UV irradiation is preferably 100 to 5000 mJ, more preferably 300 to 4000 mJ, and even more preferably 800 to 3500 mJ. It is preferable to perform this UV curing process after the exposure treatment in order to perform low-temperature curing more effectively. It is preferable to use an ozone-free mercury lamp as the exposure light source.

[0314] [Magnetic particle introduced substrate, electronic materials] The magnetic particle introduction substrate of the present invention comprises a substrate having holes formed therein, and a cured product of the present invention (magnetic particle-containing cured product) disposed within the holes. The holes may be through holes or recesses. Examples of substrates on which holes are formed include wiring boards with via holes or through holes. The method for forming the cured product of the present invention is as described above. The above-mentioned magnetic particle-introduced substrate can be applied to electronic materials such as inductors. [Examples]

[0315] The present invention will be described in more detail based on the following examples. The materials, amounts used, ratios, treatment details, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below. In the following, unless otherwise specified, “%” means “mass %” and “part” means “part by mass”.

[0316] [Various components used in the preparation of the composition] In preparing the composition, each component described in Table 1 was prepared. The outlines of each component described in Table 1 are shown below.

[0317] [Magnetic particles] · P-1: 80% Ni - 4Mo PF-5F (manufactured by Epson Atmix Corporation, solid content concentration: 100 mass %, average primary particle diameter: 4 μm) · P-2: 80% Ni - 4Mo PF-15F (manufactured by Epson Atmix Corporation, solid content concentration: 100 mass %, average primary particle diameter: 8 μm) · P-3: 80% Ni - 4Mo WA13 (manufactured by Epson Atmix Corporation, solid content concentration: 100 mass %, average primary particle diameter: 12.5 μm) · P-4: KUAMET-CT5-25μm (manufactured by Epson Atmix Corporation, solid content concentration: 100 mass %, average primary particle diameter: 15 μm) · P-5: AW2-08 PF-3F (manufactured by Epson Atmix Corporation, solid content concentration: 100 mass %, average primary particle diameter: 3 μm) · P-6: AW2-08 PF-8F (manufactured by Epson Atmix Corporation, solid content concentration: 100 mass %, average primary particle diameter: 5 μm) · P-7: AW2-08 PF-20F (manufactured by Epson Atmix Corporation, solid content concentration: 100 mass %, average primary particle diameter: 10 μm) · P-8: KUAMET6B2 (manufactured by Epson Atmix Corporation, solid content concentration: 100 mass %, average primary particle diameter: 24 μm) · P-9: EA-SMP-10 PF-5F (manufactured by Epson Atmix Corporation, solid content concentration: 100 mass %, average primary particle diameter: 10 μm) • P-10: KUAMETNC (manufactured by Epson Atomics, solid content: 100% by mass, average primary particle size: 25 μm) • P-11: BSN-125 (Manufactured by Toda Kogyo, solid content concentration: 100% by mass, average primary particle size: 8 μm) • P-12: BSN-714 (Manufactured by Toda Kogyo, solid content concentration: 100% by mass, average primary particle size: 30 μm) • P-13: BSN-828 (Manufactured by Toda Kogyo, solid content concentration: 100% by mass, average primary particle size: 66 μm) • P-14: BSF-547 (Manufactured by Toda Kogyo, solid content concentration: 100% by mass, average primary particle size: 11 μm) • P-15: KNS-415 (Manufactured by Toda Kogyo, solid content concentration: 100% by mass, average primary particle size: 4 μm) P-16: Particles prepared by referring to [Production Example 1] in Japanese Patent Publication No. 2019-067960, solid content concentration: 100% by mass, average primary particle diameter: 10 μm) • P-17: M05S (Manufactured by Powdertech, Solids content: 100% by mass, Average primary particle size: 10 μm)

[0318] [Binder components] • B-1: Product name "BYK-P105" (Low molecular weight unsaturated carboxylic acid polymer, manufactured by BYK, solids content: 100% by mass) ·B-2: Product name "Tallen VA-705B" (High-grade fatty acid amide, manufactured by Kyoeisha Chemical Co., Ltd., solid content concentration: 100% by mass) • B-3: Product name "FLOWNON RCM-230AF" (High-grade fatty acid amide, manufactured by Kyoeisha Chemical Co., Ltd., solid content concentration: 10% by mass, diluent: butyl acetate (boiling point 126°C) / 3-methoxy-3-methyl-1-butanol (boiling point 174°C) (mixing ratio (mass ratio): 2 / 1))

[0319] ·B-4: A solution containing the following compound (weight-average molecular weight 10000) (solid content concentration: 30% by mass, diluent: PGMEA (boiling point 146°C)). The numerical values ​​attached to each repeating unit constituting the main chain represent the mass ratio, and the numerical values ​​attached to each repeating unit contained in the side chain represent the number of repeating units.

[0320] [ka]

[0321] • B-5: A solution containing the following compound (weight-average molecular weight 25000) (solid content concentration: 30% by mass, diluent: PGMEA (boiling point 146°C)). The numerical values ​​attached to each repeating unit constituting the main chain represent the mass ratio, and the numerical values ​​attached to each repeating unit contained in the side chain represent the number of repeating units.

[0322] [ka]

[0323] • B-6: A solution containing the following compound (weight-average molecular weight 10000) (solid content concentration: 30% by mass, diluent: PGMEA (boiling point 146°C)). The numerical values ​​attached to each repeating unit constituting the main chain represent the mass ratio, and the numerical values ​​attached to each repeating unit contained in the side chain represent the number of repeating units.

[0324] [ka]

[0325] • B-7: Product name "C-2093I" (Wetting and dispersing agent. Manufactured by NOF Corporation, solid content concentration: 100% by mass) • B-8: Product name "EHPE 3150" (1,2-epoxy-4-(2-oxyranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, manufactured by Daicel Chemical Industries, Ltd., solids content: 100% by mass) • B-9: Product name "Acrycure RD-F8" (Alkali-soluble resin containing a curable group, manufactured by Nippon Shokubai Co., Ltd., solid content concentration: 40% by mass, diluent: PGMEA (boiling point 146°C)) ·B-10: Product name "Celoxide 2021P" (3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, manufactured by Daicel Chemical Industries, Ltd., solids content: 100% by mass) B-11: Product name "Denacol EX-411" (Pentaerythritol polyglycidyl ether, manufactured by Nagase ChemteX, solid content concentration: 100% by mass) ·B-12: Product name "KAYARAD RP-1040" (The compound listed below, manufactured by Nippon Kayaku Co., Ltd., solid content concentration: 100% by mass)

[0326] [ka]

[0327] • B-13: Product name "A-TMMT" (Polyfunctional acrylic monomer, manufactured by Toagosei Co., Ltd., Solids content: 100% by mass) ·B-14: Product name "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin, manufactured by Nippon Steel Chemical & Material Co., Ltd., solid content concentration: 100% by mass) ·B-15: Product name "ZX1658GS" (Liquid 1,4-glycidylcyclohexane type epoxy resin, manufactured by Nippon Steel Chemical & Material Co., Ltd., solids content concentration: 100% by mass) ·B-16: Product name "HP-4700" (Naphthalene-type tetrafunctional epoxy resin, manufactured by DIC Corporation, solid content concentration: 100% by mass) • B-17: Product name "YX7553BH30" (Phenoxy resin, manufactured by Mitsubishi Chemical Corporation, solid content concentration: 30% by mass, diluent: MEK (boiling point 80°C) / cyclohexanone (boiling point 155.6°C)) • B-18: Product name "KS-1" (Polyvinyl acetal resin, manufactured by Sekisui Chemical Co., Ltd., solid content concentration: 100% by mass) • B-19: Product name "828US" (Bisphenol A epoxy resin, manufactured by Mitsubishi Chemical Corporation, solid content concentration: 100% by mass) • B-20: Product name "NC3000L" (Biphenyl-type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., solid content concentration: 100% by mass) · B-21: Product name "HPC-4032" (Naphthalene-type bifunctional epoxy resin, manufactured by DIC Corporation, solids content: 100% by mass)

[0328] [Additives] <Hardening agent / Hardening accelerator> · A-1: ​​Product name "Hishikorin PX-4MP" (phosphate-based epoxy curing accelerator, manufactured by Nippon Chemical Industrial Co., Ltd., solid content concentration: 100% by mass) ·A-2: Product name "2MZA-PW" (Imidazole-based curing accelerator, manufactured by Shikoku Chemicals Co., Ltd., solid content concentration: 100% by mass) • A-3: Product name "LA-7054" (Novolac-type phenolic resin curing agent, manufactured by DIC Corporation, solid content concentration: 60% by mass, diluent: MEK (boiling point 80°C)) · A-4: Product name "2E4MZ" (2-ethyl-4-methylimidazole (curing accelerator), manufactured by Shikoku Chemicals Co., Ltd., solid content concentration: 100% by mass) · A-5: Product name "2PHZ-PW" (Imidazole-based epoxy curing accelerator, manufactured by Shikoku Chemicals Co., Ltd., solid content concentration: 100% by mass) • A-6: Product name "LA-3018-50P" (Novolac-type phenolic resin curing agent, manufactured by DIC Corporation, solid content concentration: 50% by mass, diluent: 2-methoxypropanol (boiling point 120°C)) • A-7: Product name "HPC-8000-65T" (ester resin type epoxy curing agent, manufactured by DIC Corporation, solid content concentration: 65% by mass, diluent: toluene (boiling point 111°C)) • A-8: Product name "V-03" (Epoxy hardener, manufactured by Nisshinbo Chemical Co., Ltd., Solids content concentration: 50% by mass, Diluting solvent: Toluene (boiling point 111°C)) · A-9: Product name "DMAP" (4-dimethylaminopyridine, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., solid content concentration: 100% by mass) • A-10: Product name "PN-50" (Amine adduct-type curing agent, manufactured by Ajinomoto Fine Techno Co., Ltd., solid content concentration: 100% by mass) · A-16: Product name "HNA-100" (acid anhydride-based curing agent, manufactured by Shin Nippon Rika Co., Ltd., solid content concentration: 100% by mass)

[0329] <Filler> • A-11: Product name "SO-C2" (Silica particles, manufactured by Admatex, Solid content concentration: 100% by mass)

[0330] <Silane coupling agent> • A-12: Product name "KBM-573" (N-phenyl-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., solid content concentration: 100% by mass) A-13: Product name "KBM-103" (phenyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., solid content concentration: 100% by mass)

[0331] <Photopolymerization initiator> A-14: Product name "OXE-03" (Oxime ester-based photopolymerization initiator, manufactured by BASF, solid content concentration: 100% by mass) • A-15: Product name "Omnirad369" (alkylphenone-based photopolymerization initiator, manufactured by BASF, solids content: 100% by mass)

[0332] [Surfactants] • Sur-1: Product name "MEGAFAC F-781F" (Fluorine-based surfactant, manufactured by DIC Corporation, solid content concentration: 100% by mass) • Sur-2: Product name "KF-6001" (silicone-based surfactant, manufactured by Shin-Etsu Chemical Co., Ltd., solid content concentration: 100% by mass)

[0333] 〔solvent〕 • S-1: PGMEA (Propylene glycol monomethyl ether acetate (boiling point 146°C), manufactured by TCI) • S-2: 1,6-HDDA (1,6-Hexanediol diacetate (boiling point 260°C), manufactured by Daicel Chemical Industries, Ltd.) • S-3: Glycerol triacetic acid (boiling point 260°C, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) • S-4: 1,3-BGDA (1,3-butylene glycol diacetate (boiling point 232°C), manufactured by Daicel Chemical Industries, Ltd.) • S-5: 1,4-BDDA (1,4-butanediol diacetate (boiling point 232°C), manufactured by Daicel Chemical Industries, Ltd.) • S-6: PGDA (Propylene glycol diacetate (boiling point 190°C), manufactured by Daicel Chemical Industries, Ltd.) • S-7: Cyclohexanone (boiling point 155.6°C, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) • S-8: Toluene (boiling point 110°C, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) • S-9: 3-Methoxy-1-butanol (boiling point 161°C, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) • S-10: Isopropyl acetate (boiling point 89°C, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) • S-11: MEK (Methyl ethyl ketone (boiling point 80°C), manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) • S-12: Ethanol (boiling point 78°C, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0334] [Preparation of compositions for the examples and comparative examples] For components other than the solvent shown in Table 1, the components listed in Table 1 were mixed to achieve the composition ratio (by mass) shown in Table 1 and placed in a sealed container made of PTFE (polytetrafluoroethylene). Subsequently, the solvent was added to achieve the composition ratio (by mass) shown in Table 1, the container was sealed, and the mixture was dispersed at 50 G for 2 hours using a Resodyn RAM (low-frequency resonant acoustic mixer) to prepare the compositions for each example and comparative example.

[0335] [evaluation] [Magnetic properties] <Preparation of sample substrates for measurement> A substrate was fabricated by coating a 100 μm thick Si Wafer with CT4000 (manufactured by Fujifilm Electronic Materials Corporation). On the obtained substrate, each of the compositions from the examples and comparative examples was applied using an applicator with a gap of 100 μm to form a coating film. Next, if the applied composition did not contain a photopolymerization initiator, the obtained coating film was heat-dried at 100°C for 120 seconds, and then further heated at 230°C for 15 minutes to produce a substrate with a cured film. If the applied composition contained a photopolymerization initiator, it was heated in a proximity exposure machine at 1000 mJ / cm². 2 A substrate with a cured film was fabricated by performing an exposure treatment under the specified conditions and then heating it at 230°C for 10 minutes. Next, the resulting cured film-coated substrate was cut into 1 cm × 2.8 cm pieces to prepare sample substrates for measurement.

[0336] <Fabrication of a reference board for measurement> A measurement reference substrate was prepared in the same manner as the measurement sample substrate preparation method described above, except that the following composition (composition for preparing the measurement reference substrate) was used. In the composition for fabricating the reference substrate for measurement, the same type of magnetic particles used were those used in the compositions of the Examples and Comparative Examples. Furthermore, when multiple magnetic particles were used in combination, the same mixing ratio was maintained. In other words, taking Example 17 as an example, in the fabrication of a reference substrate for measurement using the composition of Example 17, the composition for fabricating the reference substrate for measurement contained P-3 and P-1 as magnetic particles in a 1:1 mass ratio, similar to Example 17. Furthermore, in the composition for fabricating the reference substrate for measurement, the binder component B-4 and the solvent S-1 are as previously described.

[0337] (Composition for fabricating reference substrates for measurement) Magnetic particles (same type and mixing ratio as in the compositions of the Examples and Comparative Examples): 85.8% by mass Binder component (using B-4): 5.2% by mass Solvent (using S-1): 9.0% by mass

[0338] Next, the magnetic properties (relative permeability μ' at 100 MHz) of the films on each of the obtained sample substrates and reference substrates were measured using the PER-01 (high-frequency magnetic permeability measuring device manufactured by Keycom). Based on the obtained relative permeability μ' value, the permeability ratio (Δμ') was derived using the following formula (1), and evaluation was performed based on the evaluation criteria described later. A larger value for the permeability ratio (Δμ') indicates that the formulation is able to maintain the intrinsic magnetic properties of the magnetic particles. In practice, an evaluation of "3" or higher is preferable, an evaluation of "4" or higher is more preferable, and "5" is most preferable. Equation (1) Δμ'=μ'A / μ'B Δμ': Magnetic permeability ratio μ'A: Relative permeability μ' of the measurement sample substrate at 100 MHz μ'B: Relative permeability μ' of the measurement reference substrate at 100 MHz

[0339] <Evaluation Criteria> "5": 0.9<Δμ', and μ'B>15 "4": 0.75<Δμ'≦0.9 and μ'B>15 "3": 0.6<Δμ'≦0.75, and μ'B>15 "2": 0.4<Δμ'≦0.6, and μ'B>15 "1": Δμ'≦0.4 or μ'B≦15

[0340] [Liquidity] Fluidity was evaluated based on whether or not application using an applicator was possible for magnetic property evaluation. Specifically, the evaluation was carried out based on the following evaluation criteria. <Evaluation Criteria> "A": Applicable "B": The composition slides off the substrate and cannot be applied.

[0341] [Suitability for filling] A 0.8mm thick FR-4 substrate was prepared, and through-holes with a diameter of 0.4mm were formed on it. Next, the DP-320 (Newlong Precision Industries) was used to fill the through-holes with each of the compositions from the examples and comparative examples. If the composition did not contain a photopolymerization initiator, the resulting substrate with the embedded composition was heated at 160°C for 1 hour to cure the composition. If the composition contained a photopolymerization initiator, it was cured using a proximity exposure machine at 1000 mJ / cm². 2 The composition was cured by exposure treatment under the specified conditions and then heating at 230°C for 10 minutes. The obtained substrate was polished to expose the cross-section of the embedded portion, and the internal state was observed using a Scanning Electron Microscope (SEM). Images were acquired for n=30 samples, and the void ratio calculated using ImageJ was averaged to serve as an index of filling suitability. Based on the averaged value (Va), evaluation was conducted according to the following evaluation criteria. A smaller Va value indicates fewer voids and cracks in the cured material, resulting in better quality. In practical terms, an evaluation of "3" or higher is preferable, an evaluation of "4" or higher is more preferable, and "5" is the most preferable.

[0342] <Evaluation Criteria> "5": 3% > Va "4": 5% > Va ≥ 3% "3": 8% > Va ≥ 5% "2": 15% > Va ≥ 8% "1": Va ≥ 15%

[0343] Table 1 below shows the formulations of each composition and the results of the evaluation tests conducted on each composition. Note that in Table 1, the units of the values ​​listed in the "Quantity" and "Total Quantity" columns are "parts by mass". Furthermore, in Table 1, under "Content of solvent with a boiling point of 160°C or higher relative to the total mass of the composition (mass%)", "N" represents the case where the content of solvent with a boiling point of 160°C or higher is less than 3% by mass relative to the total mass of the composition, and "P" represents the case where the content of solvent with a boiling point of 160°C or higher is 3% by mass or more relative to the total mass of the composition. Furthermore, in Table 1, "Content (mass%) of magnetic particles with a primary particle diameter of 4 μm or more" refers to the content (mass%) of magnetic particles with a primary particle diameter of 4 μm or more relative to the total mass of magnetic particles.

[0344] [Table 1]

[0345] [Table 2]

[0346] [Table 3]

[0347] [Table 4]

[0348] The results in Table 1 clearly show that the composition of the present invention can form a cured product with excellent fluidity and filling properties, as well as excellent magnetic properties. Furthermore, from the results of the examples (for example, a comparison of Examples 1 to 16), it was confirmed that when the average primary particle diameter of the magnetic particles is 20 μm or less (preferably 7 μm or less), the filling suitability of the formed cured product is superior. It is presumed that in Example 15, the filling suitability was further improved because the magnetic particles were surface-coated particles. Furthermore, from the results of the examples (for example, a comparison of Examples 3, 24-27, etc.), it was confirmed that when the magnetic particle content is 92% by mass or more (preferably 95% by mass or more) relative to the total solid content of the composition, the magnetic properties of the resulting cured product are superior. Furthermore, the results of the examples (for example, a comparison of Examples 3, 28-33, etc.) confirmed that when the solvent content is 15% by mass or less (preferably 8% by mass or less) relative to the total mass of the composition, the composition exhibits superior filling suitability. Furthermore, the results of the examples (for example, comparisons of Examples 58-62, 68-71, and 78-80) confirmed that when a composition contains an adhesion aid such as a silane coupling agent, the composition exhibits superior filling suitability. In the comparison of Examples 58-62, it is presumed that the inclusion of an adhesion aid such as a silane coupling agent and the solvent content being 8% by mass or less of the total mass of the composition contributed to the improvement in filling suitability (in particular, in Example 61, it is also presumed that the surface coating of the magnetic particles in the composition contributed to the improvement in filling suitability). Furthermore, the results of the examples (for example, a comparison of Examples 83 to 96) confirmed that when the composition contains a solvent with a boiling point of 160°C or higher, and its content is 3% by mass or more of the total mass of the composition, the composition exhibits superior filling suitability. Similar results can be obtained in Examples 24-33 by replacing the magnetic particles P-3 with P-2 or P-4.

[0349] On the other hand, the comparative example composition did not exhibit the desired effect. Furthermore, in Comparative Example 3, the solvent content in the composition was too low, resulting in poor fluidity and difficulty in application with an applicator.

Claims

1. Magnetic particles and, One or more components selected from the group consisting of resins and resin precursors, A composition comprising a solvent, The aforementioned component comprises a resin having repeating units including graft chains. The content of magnetic particles with a primary particle diameter of 4 μm or more is 25% by mass or more of the total mass of magnetic particles. The content of the magnetic particles is 91% by mass or more relative to the total solid content of the composition. The solvent content is 3 to 24% by mass relative to the total mass of the composition. The graft chain comprises at least one of a polyester structure and a polyether structure.

2. The composition according to claim 1, wherein the magnetic particles are soft magnetic particles.

3. The composition according to claim 1 or 2, wherein the solvent comprises a solvent having a boiling point of 80°C or higher.

4. The composition according to any one of claims 1 to 3, wherein the solvent comprises a solvent having a boiling point of 160°C or higher.

5. The composition according to any one of claims 1 to 4, wherein the solvent comprises a solvent having a boiling point of 160°C or higher, and its content is 3% by mass or more of the total mass of the composition.

6. The composition according to any one of claims 1 to 5, wherein the aforementioned component comprises at least one epoxy compound and an oxetane compound.

7. The composition according to any one of claims 1 to 6, wherein the magnetic particles include ferrite.

8. The composition according to any one of claims 1 to 7, wherein the content of the aforementioned component is 7% by mass or more with respect to the total solid content of the composition.

9. The composition according to any one of claims 1 to 8, wherein the component comprises a resin having an acid group, a basic group, or an amide group.

10. The composition according to any one of claims 1 to 9, wherein the content of the solvent is 6 to 24% by mass with respect to the total mass of the composition.

11. The composition according to any one of claims 1 to 10, wherein the solvent comprises a solvent having a boiling point of 160°C or higher and 260°C or lower.

12. The composition according to any one of claims 1 to 11, wherein the solvent comprises at least one selected from propylene glycol monomethyl ether acetate, 1,6-hexanediol diacetate, glycerol triacetic acid, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, propylene glycol diacetate, cyclohexanone, toluene, 3-methoxy-1-butanol, isopropyl acetate, methyl ethyl ketone, and ethanol.

13. The composition according to any one of claims 1 to 12, wherein the solvent comprises an acetate-based solvent containing two or more acetate groups in its molecule.

14. The composition according to any one of claims 1 to 13, further comprising an organic rheology control agent.

Images